JP2008239987A - Dendrimer and organic semiconductor using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic semiconductor material which is good in solubility in a solvent, keeps a stable and high carrier transportation property in a wide temperature range including room temperature, and has good film forming property by a coating method, and to provide an organic semiconductor using the same. <P>SOLUTION: The dendrimer is derived from a polyalkyleneimine dendrimer and in which the terminal group is a group selected from the group consisting of groups represented by formulas (B1) a polyalkyleneimine terminal-modified compound comprising cyclohexylene, phenylene, naphthalene, pyrimidine, pyridine, benzothiazole and oxadiazole, (B2) a polyalkyleneimine terminal-modified compound comprising thiophene, (B3) a polyalkyleneimine terminal-modified compound comprising thiophene, phenylene, and naphthalene, (B4) a polyalkyleneimine terminal-modified compound comprising condensed thiophene, and (B5) a polyalkyleneimine terminal-modified compound comprising condensed thiophene, thiazolothiazole, fluorene, or carbazole. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dendrimer having a group having carrier transportability at the terminal. The present invention further relates to an organic semiconductor thin film, an organic semiconductor element, and an organic thin film transistor using the dendrimer compound.

  Conventionally, silicon, which is an inorganic semiconductor material used for semiconductor devices, requires a high-temperature process and a high-vacuum process in forming a thin film. Since a high-temperature process is required, silicon cannot be formed into a thin film on a plastic substrate or the like, so that flexibility cannot be imparted to a product incorporating a semiconductor device or weight reduction cannot be achieved. Moreover, since a high vacuum process is required, it is difficult to increase the area and cost of a product incorporating a semiconductor device.

  In recent years, research on organic semiconductor devices using organic semiconductor materials has been actively conducted. Specific examples of the organic semiconductor device include an organic thin film transistor, an organic thin film photoelectric conversion device, and an organic electroluminescence (organic EL) device. Since these organic semiconductor materials can significantly reduce the manufacturing process temperature as compared with inorganic semiconductor materials, they can be formed on a plastic substrate or the like. Furthermore, a thin film can be formed using a coating method that does not require a vacuum process, such as an ink jet apparatus, for an organic semiconductor having high solubility in a solvent and good film formability. Area reduction and cost reduction are possible.

  As described above, organic semiconductor materials are advantageous in terms of large area, flexibility, weight reduction, cost reduction, and the like compared to inorganic semiconductor materials. Applications are actively being made. For example, it is applied to displays such as information tags, large area sensors such as electronic artificial skin sheets and sheet type scanners, liquid crystal displays, electrophoretic displays (electronic paper), and organic EL panels.

Main element characteristics required for an organic thin film transistor using an organic semiconductor material are as follows.
(1) The on / off ratio is large and the off current is small.

(2) Low drive voltage (low threshold voltage and high on-current)
(3) The cut-off frequency is high.
(4) The variation in characteristics of the organic thin film transistor is small.

(5) Operates stably in the atmosphere and has little deterioration over time.
In order to satisfy these device characteristics, the characteristics required for the organic semiconductor material are as follows.

(I) Field effect mobility (μ) is high.
(Ii) Excellent film formability and easy thin film formation process.
(Iii) Resistant to oxygen and moisture and stable in the atmosphere.

In particular, it is a major premise that the field effect mobility (μ) of (i) is large. From this viewpoint, in recent years, organic semiconductor materials having field effect mobility comparable to amorphous silicon have been reported one after another. Regarding (ii), it is important that the film formation process of the organic semiconductor film can be formed by coating rather than vacuum deposition. For this purpose, it is essential that the solubility in a solvent is good and the film formability is good.

  Organic semiconductor materials are roughly classified into low molecular weight systems (including oligomers) and high molecular weight systems. As a low molecular weight organic semiconductor material, for example, an organic FET (Field Effect Transistor) using pentacene has been manufactured, and high mobility has been reported (see Non-Patent Document 1).

  However, pentacene, which is an organic semiconductor layer, is disadvantageous in terms of large area, flexibility, weight reduction, and cost reduction because it is formed by a vacuum deposition method. In addition, a method of forming pentacene crystals in a dilute solution of trichlorobenzene without using a vacuum deposition method has been proposed (see Patent Document 1), but a manufacturing method is difficult and a stable element has not yet been obtained. These low molecular weight organic semiconductor materials are difficult to stably produce a uniform film in a highly crystallized state, and the crystal grain boundary of the crystal phase directly induces variations in FET elements. When the degree of crystallinity is high, it is difficult to obtain good film formability when using a coating method.

  Thus, a liquid crystal organic semiconductor utilizing liquid crystallinity has been proposed as a low-fraction organic semiconductor material that is not affected by the grain boundaries and is soluble in an organic solvent (see Non-Patent Document 2). The mobility of the liquid crystal organic semiconductor can be further increased by orientation control using a known method. However, in general, a liquid crystal organic semiconductor has a crystalline state at room temperature because the temperature range in which a liquid crystal phase is exhibited is higher than room temperature.

  Therefore, although it exhibits stable carrier transportability without being affected by crystal grain boundaries in the temperature range showing the liquid crystal phase, the film formability is poor at room temperature and does not exhibit stable carrier transportability (see Non-Patent Document 3). ). Also, the mobility value is insufficient. On the other hand, in order to obtain a liquid crystal organic semiconductor with high mobility, it is necessary to introduce a molecular structure having a large π-conjugated system. Therefore, the lower limit value of the temperature range indicating the liquid crystal phase tends to increase more and better. Film forming property and stable carrier transport property at room temperature cannot be provided.

Thus, it has been difficult to obtain an organic transistor that can be used for coating film formation and has stable characteristics without variations at room temperature.
An organic FET using polythiophene is disclosed as a polymer organic semiconductor material (see Patent Document 2). The organic FET is excellent in film formability in that it can be easily formed into a thin film by solution coating, but has not yet achieved sufficient FET characteristics.

  In recent years, hyperbranched polymer compounds having dendrimers and hyperbranched structures have been studied as polymer organic semiconductor materials having excellent film forming properties and good FET characteristics (see Patent Documents 3 to 7). . These are amorphous, soluble in an organic solvent, and have a feature that a functional group can be introduced at the terminal. However, the mobility value is insufficient, and furthermore, it is difficult to control the orientation, or because it has a structure showing isotropic conductivity that does not require the orientation control, the mobility is improved. I can't expect.

As described above, although many developments have been made on organic semiconductor materials including low molecular weight systems and polymer systems, organic semiconductor materials that have sufficiently satisfied various characteristics have not yet been developed.
Yen-Yi Lin. , IEEE Transaction on Electron Device, Vol. 44, No8 p. 1325 (1997) M.M. Funahashi and J.H. Hanna, Jpn. J. et al. Appl. Phys. , (1999) 38, L132-135 M.M. Funahashi, Appl. Phys. Lett. , Vol. 73, no. 25 (1998) 3733 JP 2005-281180 A JP-A-63-076378 JP 2000-336171 A JP 2003-243660 A JP 2003-92407 A JP 2003-324203 A JP 2004-107625 A

  As described above, the conventional liquid crystal organic semiconductor compound having liquid crystallinity generally has a lower limit of the temperature range showing a liquid crystal phase higher than room temperature, and shows a crystalline state at room temperature. Although it exhibits stable carrier transport characteristics in the liquid crystal temperature range, it does not exhibit stable carrier transport properties due to the influence of crystal grain boundaries in the crystalline state. Therefore, an organic transistor using such a liquid crystal organic semiconductor has a problem that it does not exhibit switching characteristics over a wide temperature range including room temperature.

  Therefore, in order to solve such problems, the present invention, for example, has good solubility in a solvent and maintains a stable and high carrier transportability in a liquid crystal temperature range, and in a wide temperature range including room temperature. It is an object of the present invention to provide an organic semiconductor material that has (1) a structure that exhibits a liquid crystal phase, or (2) a structure that lowers the degree of crystallinity, and has good film forming properties by a coating method.

  Another object of the present invention is to provide an organic transistor having good switching characteristics, for example, by reducing variation in elements by using the organic semiconductor material of the present invention.

  The present inventors have found that the above-mentioned problems can be solved by using a dendrimer in which a specific group is introduced at the terminal of a polyalkylene dendrimer having a flexible molecular structure core and a building block, and have completed the present invention.

  That is, the dendrimer of the present invention is derived from a polyalkyleneimine dendrimer, and is characterized in that at least a part of the end groups is a group selected from the group consisting of groups represented by formulas (B1) to (B5). Yes.

式（Ｂ１）〜（Ｂ５）中、Ｙ¹は水素、ハロゲン、シアノ、炭素数１から２０のアルキ
ルまたは炭素数１から２０のハロゲン化アルキルであり、Ｙ¹が炭素数１から２０のアル
キルまたは炭素数１から２０のハロゲン化アルキルである場合には、直鎖アルキルまたは分岐アルキルのいずれかであり、基中の少なくとも１つの−ＣＨ₂−は、−Ｏ−、−Ｓ−
、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられていてもよく、基中の炭素はＳｉで置き換えられてもよい。

In formulas (B1) to (B5), Y ¹ is hydrogen, halogen, cyano, alkyl having 1 to 20 carbons or halogenated alkyl having 1 to 20 carbons, and Y ¹ is alkyl having 1 to 20 carbons or When it is a halogenated alkyl having 1 to 20 carbon atoms, it is either a straight chain alkyl or a branched alkyl, and at least one —CH ₂ — in the group is —O—, —S—.
, —COO—, —OCO—, —CH═CH—, or —C≡C—, and carbon in the group may be replaced with Si.

Z ¹ is alkylene having 1 to 30 carbon atoms, and at least one —CH ₂ — in the group is —CO—, —O—, —COO—, —OCO—, —CH═CH—, or —C ≡C— may be substituted, Z ² , Z ³ and Z ⁴ are independently a single bond, —CH═CH—, —C≡C
—, —CH ₂ —O—, —O—CH ₂ —, —COO—, or —OCO—, wherein Z ⁵ and Z ⁶ are independently a single bond or —C≡C—, Z ⁷ and Z ⁸ is independently a single bond, —CO
—, —O—, —CH═CH—, —C≡C—, —CH ₂ —O—, —O—CH ₂ —, —COO—, or —OCO—.

A ¹ , A ² , A ³ and A ⁴ are each independently a single bond, 1,4-cyclohexylene, 1,4-phenylene, 2,6-naphthalene, 2,5-pyrimidine, 2,5-pyridine, 2,6-benzothiazole or 2,5-oxadiazole (provided that A ¹ , A ² , A ³ and A ⁴
Of which at least three are independently 1,4-phenylene, 2,6-naphthalene, 2,5-pyrimidine, 2,5-pyridine, or 2,5-oxadiazole).

A ⁵ and A ⁷ are independently a single bond, 1,4-phenylene or 2,5-thiophene, A ⁶ is 1,4-phenylene or 2,6-naphthalene, and A ⁸ and A ⁹ are independently Single bond, 1,4-phenylene or 2,5-thiophene, and A ¹⁰ , A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are independently a single bond, fused thiophene, 2,5-thiophene, 2 , 2′-dithiophene, thiazolothiazole, fluorene, carbazole, or 1,4-phenylene (wherein at least one of A ¹⁰ , A ¹¹ , A ¹² , A ¹³ and A ¹⁴ is independently Fused thiophene, thiazolothiazole, fluorene, or carbazole).

p is an integer of 1 to 5. In the formulas (B1) to (B5), at least one hydrogen in the side orientation of 1,4-phenylene, 2,6-naphthalene, 2,5-thiophene, condensed thiophene, fluorene, and carbazole is halogen, cyano, It may be substituted with alkyl having 1 to 20 carbon atoms, or alkyl halide having 1 to 20 carbon atoms, and when substituted with alkyl having 1 to 20 carbon atoms or alkyl halide having 1 to 20 carbon atoms, At least one —CH ₂ — represents —O—, —S—, —CH═CH— or —.
C≡C— may be substituted.

In the formulas (B1) to (B5), Y ¹ is a linear or branched alkyl having 1 to 20 carbon atoms (provided that at least one —CH ₂ — in the group is —O—, — COO-, -O
CO—, —CH═CH— or —C≡C— may be substituted), and Z ² to Z ⁸ may be a single bond.

  Furthermore, the dendrimer of the present invention is derived from a polyalkyleneimine dendrimer, and at least some of the end groups are represented by the formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3 A group selected from the group consisting of groups represented by -b), (B4-a), (B4-b), (B5-a), (B5-b) or (B5-c); preferable.

式（Ｂ１−ａ）、（Ｂ１−ｂ）、（Ｂ２−ａ）、（Ｂ３−ａ）、（Ｂ３−ｂ）、（Ｂ４−ａ）、（Ｂ４−ｂ）、（Ｂ５−ａ）、（Ｂ５−ｂ）および（Ｂ５−ｃ）中、Ｙ²はハロ
ゲン、または炭素数１から２０のアルキルであり、Ｙ²が炭素数１から２０のアルキルで
ある場合には、直鎖アルキルまたは分岐アルキルのいずれかであり、基中の少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ
−で置き換えられていてもよい。
Ｚ¹は炭素数１から３０のアルキレンであり、基中の少なくとも１つの−ＣＨ₂−は、−ＣＯ−、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられていてもよい。

Formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a), ( In B5-b) and (B5-c), Y ² is halogen or alkyl having 1 to 20 carbons, and when Y ² is alkyl having 1 to 20 carbons, linear alkyl or branched alkyl And at least one —CH ₂ — in the group is —O—, —COO—, —OCO—, —CH═CH—, or —C≡C.
It may be replaced with-.
Z ¹ is alkylene having 1 to 30 carbon atoms, and at least one —CH ₂ — in the group is —CO—, —O—, —COO—, —OCO—, —CH═CH—, or —C It may be replaced with ≡C-.

A ¹⁵ and A ¹⁶ are each independently a single bond, 1,4-phenylene, 4,4′-biphenyl, or 2,6-naphthalene (provided that both A ¹⁵ and A ¹⁶ are single bonds, And A ¹⁵ and A ¹⁶ are both 4,4′-biphenyl);
A ¹⁷ , A ¹⁸ , A ¹⁹ and A ²⁰ are independently a single bond or 1,4-phenylene, and A ²¹ and A ²² are independently 1,4-phenylene, 2,5-thiophene or 2,2 '-Bithiophene; A ²³ and A ²⁴ are independently a single bond, 2,5-thiophene, or 1,4-phenylene.

q is an integer of 3 to 7.
Also, the formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a) , (B5-b) and (B5-c), at least one hydrogen in the side orientation of 1,4-phenylene, 2,6-naphthalene, 4,4′-biphenyl and 2,5-thiophene is halogen, It may be replaced with methyl or ethyl.

Further, the formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a) ), (B5-b) and (B5-c), Y ² is linear or branched alkyl having 1 to 20 carbon atoms (provided that at least one —CH ₂ — in the group is —O— , -COO-, -OCO-, -CH = CH- or -C≡
C ¹⁵ may be substituted), A ¹⁵ is a single bond, A ¹⁶ is 1,4-phenylene, A ¹⁷ and A ¹⁸ are single bonds, and A ¹⁹ and A ²⁰ are single bonds. Yes, A ²¹ and A ²² may be 2,2′-bithiophene, and A ²³ and A ²⁴ may independently be a single bond or 2,5-thiophene.

  The polyalkyleneimine dendrimer is preferably a polypropyleneimine dendrimer and preferably has a generation number of 0 to 5 from the viewpoint of good film formability and ease of synthesis. Further, the preferred number of generations is 0 to 3, and the particularly preferred number of generations is 1 and 2.

  Moreover, it is preferable that the dendrimer of this invention has a liquid crystal phase (intermediate phase) from a viewpoint of the favorable film formability using the apply | coating method, and high mobility. More preferably, it exhibits a liquid crystal phase at room temperature (25 ° C.). It is particularly preferable that the liquid crystal phase is a smectic phase.

  The organic semiconductor of the present invention is characterized by using the above-mentioned dendrimer or having increased orientation by using a magnetic field, and the organic transistor of the present invention uses the organic semiconductor. It is characterized by being.

  The dendrimer of the present invention is stable in a wide temperature range including room temperature because a specific group having good carrier transportability is introduced at the terminal of the polyalkyleneimine dendrimer having a flexible molecular structure core and building block. Excellent carrier transportability and high mobility.

Moreover, if the dendrimer of this invention is used, the organic-semiconductor layer and organic transistor (liquid crystal organic semiconductor) which have the favorable film-forming property by the apply | coating method can be provided.
Furthermore, if the dendrimer of the present invention is used, the orientation can be easily controlled by using an external field (electric field, magnetic field) in the organic semiconductor layer deposition step, so that the mobility can be further improved. .

Next, the present invention will be specifically described.
The dendrimer of the present invention is derived from a polyalkyleneimine dendrimer and is characterized in that at least a part of the end groups is a group selected from the group consisting of groups represented by formulas (B1) to (B5).

  In the present specification, these specific groups introduced into the terminal group of the polyalkyleneimine dendrimer are also referred to as “mesogen groups”.

式（Ｂ１）〜（Ｂ５）中、Ｙ¹は水素、ハロゲン、シアノ、炭素数１から２０のアルキ
ルまたは炭素数１から２０のハロゲン化アルキルであり、Ｙ¹が炭素数１から２０のアル
キルまたは炭素数１から２０のハロゲン化アルキルである場合には、直鎖アルキルまたは分岐アルキルのいずれかであり、基中の少なくとも１つの−ＣＨ₂−は、−Ｏ−、−Ｓ−
、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられていてもよく、基中の炭素はＳｉで置き換えられてもよい。

In formulas (B1) to (B5), Y ¹ is hydrogen, halogen, cyano, alkyl having 1 to 20 carbons or halogenated alkyl having 1 to 20 carbons, and Y ¹ is alkyl having 1 to 20 carbons or When it is a halogenated alkyl having 1 to 20 carbon atoms, it is either a straight chain alkyl or a branched alkyl, and at least one —CH ₂ — in the group is —O—, —S—.
, —COO—, —OCO—, —CH═CH—, or —C≡C—, and carbon in the group may be replaced with Si.

Preferred Y ¹ is preferably an alkyl having 1 to 20 carbon atoms or an alkyl halide having 1 to 20 carbon atoms from the viewpoint of good orientation, a wide liquid crystal phase temperature range and reliability. Here, Y ¹ may be either linear alkyl or branched alkyl, and at least one —CH ₂ — in the group is —O—, —S—, —COO—, —OCO—, — CH═CH— or —C≡C— may be substituted, and carbon in the group may be substituted with Si. Further preferred Y ¹ is alkyl having 5 to 20 carbons or alkyl halide having 5 to 20 carbons. Here, Y ¹ is a linear alkyl, and at least one —CH ₂ — in the group is —O—, —COO—, —OCO—, —CH═CH—, or —C≡C. −
It may be replaced with.

Z ¹ is alkylene having 1 to 30 carbon atoms, and at least one —CH ₂ — in the group is —CO—, —O—, —COO—, —OCO—, —CH═CH—, or —C ≡C— may be substituted, Z ² , Z ³ and Z ⁴ are independently a single bond, —CH═CH—, —C≡C
—, —CH ₂ —O—, —O—CH ₂ —, —COO—, or —OCO—, wherein Z ⁵ and Z ⁶ are independently a single bond or —C≡C—, Z ⁷ and Z ⁸ is independently a single bond, —CO
—, —O—, —CH═CH—, —C≡C—, —CH ₂ —O—, —O—CH ₂ —, —COO—, or —OCO—. Z ¹ is preferably alkylene having 5 or more carbon atoms from the viewpoint of maintaining high mobility, that is, from the viewpoint of maintaining the interaction between mesogenic groups.

More preferred is alkylene having 10 or more carbon atoms. Among these, from the viewpoint of ease of synthesis, one —CH ₂ — in the group is preferably alkylene substituted with —CO—.
Desirable Z ² , Z ³ and Z ⁴ are independently a single bond, —C≡C—, from the viewpoint of high mobility.

Further preferred Z ² , Z ³ and Z ⁴ are single bonds. Preferred Z ⁵ and Z ⁶ are single bonds from the viewpoint of high mobility. Desirable Z ⁷ and Z ⁸ are independently a single bond or —C≡C— from the viewpoint of high mobility. Further preferred Z ⁷ and Z ⁸ are a single bond.

A ¹ , A ² , A ³ and A ⁴ are each independently a single bond, 1,4-cyclohexylene, 1,4-phenylene, 2,6-naphthalene, 2,5-pyrimidine, 2,5-pyridine, 2,6-benzothiazole or 2,5-oxadiazole (provided that A ¹ , A ² , A ³ and A ⁴
Of which at least three are independently 1,4-phenylene, 2,6-naphthalene, 2,5-pyrimidine, 2,5-pyridine, or 2,5-oxadiazole). Desirable A ¹ , A ² , A ³ and A ⁴ are independently a single bond, 1,4-phenylene or 2,6-naphthalene from the viewpoints of high mobility, a wide liquid crystal phase temperature range and reliability. .

A ⁵ and A ⁷ are independently a single bond, 1,4-phenylene or 2,5-thiophene, A ⁶ is 1,4-phenylene or 2,6-naphthalene, and A ⁸ and A ⁹ are independently Single bond, 1,4-phenylene or 2,5-thiophene, and A ¹⁰ , A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are independently a single bond, fused thiophene, 2,5-thiophene, 2 , 2'-dithiophene, thiazolothiazole, fluorene, carbazole, 1,4-phenylene (provided, however, that ^{a 10, a 11, a 12} , a 13 and a ^14, at least one independently, condensation Thiophene, thiazolothiazole, fluorene, or carbazole).

From the viewpoint of high mobility and a wide liquid crystal temperature range, at least one of A ¹⁰ , A ¹¹ , A ¹² , A ¹³ and A ¹⁴ is preferably condensed thiophene or thiazolothiazole. As the condensed thiophene, thienothiophene or dithienothiophene is preferable. A particularly preferred fused thiophene is thienothiophene.

p is an integer of 1 to 5.
In the formulas (B1) to (B5), at least one hydrogen in the side orientation of 1,4-phenylene, 2,6-naphthalene, 2,5-thiophene, condensed thiophene, fluorene, and carbazole is halogen, cyano, It may be substituted with alkyl having 1 to 20 carbon atoms, or alkyl halide having 1 to 20 carbon atoms, and when substituted with alkyl having 1 to 20 carbon atoms or alkyl halide having 1 to 20 carbon atoms, At least one of —CH ₂ — may be replaced by —O—, —S—, —CH═CH— or —C≡C—.

  In this case, from the viewpoints of high reliability, a wide liquid crystal phase temperature range and a lower limit of the liquid crystal phase temperature range, etc., preferred substituents are halogen, alkyl having 1 to 20 carbons, or alkyl having 1 to 20 carbons. Alkoxy is mentioned. Further preferred substituents are fluorine, alkyl having 1 to 5 carbons or alkoxy. Particularly preferred substituents are methyl or ethyl.

The dendrimers of the present invention are derived from polyalkyleneimine dendrimers, which are derived from polyamidoamine dendrimers and carbosilane dendrimers because they have a flexible molecular core and building blocks. Compared to dendrimers, the interaction between mesogenic groups is easily retained. Therefore, in combination with the specific group introduced at the terminal of the polyalkyleneimine dendrimer, the liquid crystallinity is remarkably easily expressed, and stable carrier transportability and high in a wide temperature range including room temperature. Mobility can be maintained.

The specific end group in the dendrimer of the present invention is a rod-shaped mesogen group having a large π conjugation and exhibits excellent liquid crystallinity.
Preferred examples of the formulas (B1) to (B5) include, for example, formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4- a), (B4-b), (B5-a), (B5-b) or (B5-c).

式（Ｂ１−ａ）、（Ｂ１−ｂ）、（Ｂ２−ａ）、（Ｂ３−ａ）、（Ｂ３−ｂ）、（Ｂ４−ａ）、（Ｂ４−ｂ）、（Ｂ５−ａ）、（Ｂ５−ｂ）および（Ｂ５−ｃ）中、Ｙ²はハロ
ゲン、または炭素数１から２０のアルキルであり、Ｙ²が炭素数１から２０のアルキルで
ある場合には、直鎖アルキルまたは分岐アルキルのいずれかであり、基中の少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ
−で置き換えられていてもよい。

Formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a), ( In B5-b) and (B5-c), Y ² is halogen or alkyl having 1 to 20 carbons, and when Y ² is alkyl having 1 to 20 carbons, linear alkyl or branched alkyl And at least one —CH ₂ — in the group is —O—, —COO—, —OCO—, —CH═CH—, or —C≡C.
It may be replaced with-.

Z ¹ has the same meaning as Z ¹ in the formula (B1) ~ (B5).
A ¹⁵ and A ¹⁶ are each independently a single bond, 1,4-phenylene, 4,4′-biphenyl, or 2,6-naphthalene (provided that both A ¹⁵ and A ¹⁶ are single bonds, and unless both of a ¹⁵ and a ¹⁶ is a 4,4'-biphenyl). A ¹⁷ , A ¹⁸ , A ¹⁹ and A ²⁰ are each independently a single bond or 1,4-phenylene, and A ²¹ and A ²² are independently 1,4-phenylene, 2,5-thiophene or 2, 2′-bithiophene; A ²³ and A ²⁴ are independently a single bond, 2,5-thiophene, or 1,4-phenylene.

  Also, the formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a) , (B5-b) and (B5-c), at least one hydrogen in the side orientation of 1,4-phenylene, 2,6-naphthalene, 4,4′-biphenyl and 2,5-thiophene is halogen, It may be replaced with methyl or ethyl.

Further, the formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a) ), (B5-b) and (B5-c), Y ² is linear or branched alkyl having 1 to 20 carbon atoms (provided that at least one —CH ₂ — in the group is —O— , -COO-, -OCO-, -CH = CH- or -C≡
C ¹⁵ may be substituted), A ¹⁵ is a single bond, A ¹⁶ is 1,4-phenylene, A ¹⁷ and A ¹⁸ are single bonds, and A ¹⁹ and A ²⁰ are 1,4. -Phenylene, A ²¹ and A ²² are preferably 2,2′-bithiophene, and A ²³ and A ²⁴ are independently a single bond or 2,5-thiophene.

  Formula (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a), In (B5-b) and (B5-c), the formula (B1-a), (B2-a), (B3-a), (B3-b), (B4-a) or (B4-b) is Formulas (B1-a), (B2-a), and (B4-b) are more preferable.

  Formulas (B1), (B2), (B3), (B4), (B5), (B1-a), (B1-b), (B2-a), (B3-a), (B3-b) ), (B4-a), (B4-b), (B5-a), (B5-b) and (B5-c), more specifically, for example, the formulas (B1-1) to (B5) -10). Among these, from the viewpoint of high mobility and good film formability, the formulas (B1-1) to (B1-6), the formulas (B2-1) to (B2-4), the formula (B3-1), Formula (B3-2) and formula (B4-1) to formula (B4-9) are preferable.

本発明のデンドリマーは、ポリアルキレンイミンデンドリマーの末端基のうち、少なくとも一部の末端基が前記特定の基（メソゲン基）で修飾されていればよい。高いキャリア輸送性の観点から、末端基の７５％以上が上記特定の基（メソゲン基）で修飾されているのが好ましく、末端基の９０％以上が上記特定の基（メソゲン基）で修飾されているのがより好ましい。

In the dendrimer of the present invention, at least a part of the end groups of the polyalkyleneimine dendrimer may be modified with the specific group (mesogenic group). From the viewpoint of high carrier transportability, 75% or more of the end groups are preferably modified with the specific group (mesogenic group), and 90% or more of the end groups are modified with the specific group (mesogenic group). More preferably.

Furthermore, it is particularly preferable that 100% of the end groups are modified with the specific group (mesogenic group). In addition, the organic semiconductor of the present invention may use a mixture of a dendrimer in which all terminal groups are modified with the specific group and a dendrimer in which some terminal groups are modified. The modification rate of the terminal group can be confirmed by H ¹ -NMR and elemental analysis.

Furthermore, since the dendrimer of the present invention is derived from a polyalkyleneimine dendrimer having a flexible molecular structure core and a building block, the number of generations of the resulting dendrimer can be easily controlled. Examples of 0th generation, 1st generation, 2nd generation and 3rd generation polypropylene imine dendrimers are shown below. The following example is NH ₂ — (CH ₂ ) _4.
—NH ₂ (1,4-diaminobutane) is the 0th generation central structure, and the central structure is NH ₂ — (CH ₂ ) _n —NH ₂ (where n is an integer of 1 to 20). Good.

デンドリマーの世代数とは、上述のように規則分岐の次数を示している。本発明のデンドリマー化合物の分岐構造に特に制限はなく、完全に制御されたデンドリマーでなくても差し支えない。本発明のデンドリマーの世代数は、高いキャリア輸送性、良好な成膜性および合成の容易性の観点から、通常０〜８であり、好ましくは０〜５であり、より好ましくは０〜３である。

The number of generations of dendrimers indicates the order of regular branching as described above. The branched structure of the dendrimer compound of the present invention is not particularly limited, and may not be a completely controlled dendrimer. The number of generations of the dendrimer of the present invention is usually from 0 to 8, preferably from 0 to 5, more preferably from 0 to 3, from the viewpoints of high carrier transportability, good film formability and ease of synthesis. is there.

In the present specification, the “dendrimer of the present invention” has a broad meaning including a 0th generation dendrimer.
The polyalkyleneimine dendrimer used in the present invention is not particularly limited, but a polypropyleneimine dendrimer is preferable from the viewpoint of easy synthesis and high carrier transportability. These imine dendrimers may be synthesized by a known method, for example, the method described in Patent Document 5, or commercially available ones may be used.

For example, DAB-Am-4 (polypropyleneiminetetramine dendrimer: [—CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ NH ₂ ) ₂ ] ₂ : generation number = 1), DAB manufactured by Aldrich -am-8 (polypropylene imine octa Min dendrimer: [- CH _{2
CH 2 N [(CH 2)} 3 N [(CH 2) 3 NH 2] 2] 2] 2: Generation Number = 2), DAB-Am- 1
6 (polypropylenimine hexadecamine dendrimer: [—CH ₂ CH ₂ N [(CH ₂ ) ₃ N [(CH ₂ ) ₃ N [(CH ₂ ) ₃ NH ₂ ] ₂ ] ₂ ] ₂ ] ₂ : number of generations = 3) or DAB-Am-
64 (polypropyleneimine tetra hexa contaminant emissions _{Dendrimer: [- CH 2 CH 2 N} [(CH 2) 3 N [(CH 2) 3 N [(CH 2) 3 N [(CH 2) 3 N [(CH 2) 3 NH ₂ ] ₂ ] ₂ ] ₂ ] ₂ ] ₂ ] ₂ : number of generations = 5) and the like can be used.

The dendrimer of the present invention can be obtained by substituting H of the NH ₂ group at the terminal of these polyalkyleneimine dendrimers with the specific group.
An acrylic ester derivative is used for modification of the end of the polypropyleneimine dendrimer, which is a polyfunctional amine compound. That is, the dendrimer of the present invention can be obtained by reacting the polyfunctional amine compound with an acrylate derivative in an organic solvent.

The reaction ratio between the polyfunctional amine compound and the acrylate is preferably an amine compound 1
It is 1.0-3.0 mol of acrylic acid ester with respect to mol, More preferably, it is 1.1-1.5 mol. As the reaction solvent, conventionally known solvents can be used as these solvents.

  Specifically, halogenated hydrocarbons such as tetrachloroethylene, 1,2-dichloroethane or chloroform, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, cyclic ether solvents such as tetrahydrofuran or dioxane, toluene or xylene, etc. Examples include an aprotic polar solvent such as an aromatic hydrocarbon solvent, N-methyl-2-pyrrolidone, N, N-dimethylformamide or N, N-dimethylacetamide. These may be used alone or in combination of two or more.

The reaction temperature is preferably −50 ° C. to 150 ° C., more preferably 25 ° C. to 80 ° C. Within this temperature range, there is no fear that the reaction rate will decrease, and the stability of the polyfunctional amine compound or the liquid crystalline acrylate derivative can be maintained. Confirmation of the substitution of the terminal group can be performed by measuring ¹ H-NMR of the unreacted amine. As described above, in the dendrimer of the present invention, all of the end groups may not be completely replaced.

  Since the dendrimer of the present invention is derived from a polyalkyleneimine dendrimer having a flexible molecular structure core and building block, it is excellent in the coating method in combination with the specific group introduced at the terminal of the polyalkyleneimine dendrimer. Film forming property and high mobility. In order to have good film formability, it is necessary to lower the crystallinity at room temperature and to maintain good solubility in a solvent. In particular, it preferably has a liquid crystal phase at room temperature.

In this specification, “room temperature” means 25 ° C.
The temperature range in which the dendrimer of the present invention can maintain liquid crystallinity is usually 0 to 100 ° C, preferably -20 to 150 ° C, more preferably -40 to 200 ° C. As described above, since the dendrimer of the present invention can maintain excellent liquid crystallinity over a wide temperature range including room temperature, it can have sufficiently stable carrier transportability and high mobility even at room temperature. By using a coating film forming method that does not require a high temperature process, it is possible to easily form a thin film. However, since the dendrimer of the present invention does not crystallize at room temperature and has good film forming properties, it does not necessarily show a liquid crystal phase at room temperature.

The mobility is determined by the mobility (μ ^TOF ) according to the TOF (Time of Flight) method.
: Unit cm ² / V · s), and mobility obtained by organic FET element (mu ^FET unit: cm ² / V · s) may, as mu ^TOF is high, it is possible to increase the mu ^FET.

The mobility (μ ^TOF ) is expressed by the following formula (i) where the voltage between electrodes of the TOF measurement cell is (V), the distance between the electrodes is d, and the time traversing the film thickness calculated from the photocurrent waveform is Tr. Is required.

μ ^TOF = d ² / (V · Tr) (i)
The mobility (μ ^FET ) is obtained by the following equation (ii) using a transfer characteristic curve obtained by fixing the drain voltage (V _D ) and changing the gate voltage (V _G ).

式（ii）中、Ｃ_inは、ゲート絶縁膜の単位面積当たりの電気容量、Ｉ_Dはドレイン電流
、Ｌはチャネル長、Ｗはチャネル幅、Ｖ_THは閾値電圧である。

In formula (ii), C _in is the electric capacity per unit area of the gate insulating film, I _D is the drain current, L is the channel length, W is the channel width, and V _TH is the threshold voltage.

The mobility (μ ^TOF ) exhibited by the dendrimer of the present invention is usually 10 ⁻³ cm ² / V · s or higher, preferably 10 ⁻² cm ² / V · s or higher, particularly preferably 10 ⁻¹ cm ² / V · s. V · s or more. Although an upper limit is not specifically limited, Usually, it is 10 cm < ² > / V * s or less. The mobility (μ ^FET ) increases as the mobility (μ ^TOF ) increases, and is usually 10 ⁻³ cm ² / V · s or more, preferably 10 ⁻² cm ² / V · s or more. Preferably, it is 10 ⁻¹ cm ² / V · s or more. Although an upper limit is not specifically limited, Usually, it is 10 cm < ² > / V * s or less. Thus, since the dendrimer of the present invention exhibits high mobility in both μ ^TOF and μ ^FET , it is very useful as an organic semiconductor material.

  The specific group introduced at the terminal of the polyalkyleneimine dendrimer is a so-called mesogenic group. The “mesogenic group” is a general term for groups showing an intermediate phase (liquid crystal phase) having a molecular orientation order positioned between a crystalline phase and an amorphous phase. The intermediate phase is classified into a nematic liquid crystal phase, a cholesteric liquid crystal phase, a smectic liquid crystal phase, an anisotropic plastic crystal phase, an optically isotropic liquid crystal phase, a discotic liquid crystal phase, and the like (Liquid Crystal Handbook: Edited by Liquid Crystal Handbook Editorial Committee).

  Among these, since the mobility increases as the degree of order increases, it is known that a smectic liquid crystal phase and an anisotropic plastic crystal phase are particularly preferable. The dendrimer of the present invention can form various liquid crystal phases depending on the type of the specific group. However, since the mobility increases as the molecular alignment order increases, the dendrimer preferably exhibits a smectic liquid crystal phase rather than a nematic liquid crystal phase. Further, among smectic liquid crystals, for example, SmE, SmH> SmB, SmG> SmB, SmF> SmA, and SmC are preferable in this order. If the dendrimer of the present invention is used, since it has good film forming properties even at room temperature, an organic semiconductor layer and an organic transistor having excellent carrier transportability and mobility can be produced.

  Various known film forming methods can be applied to the method for forming the organic semiconductor layer. Specifically, for example, by using a solution in which the dendrimer of the present invention is dissolved in a solvent, a film can be formed using any method such as a spin coating method, an ink jet method, a casting method, a dipping method, and the like. . As the solvent, either a polar solvent or a nonpolar solvent may be used.

  Specific examples of the solvent include chloroform, dichloromethane, trichloromethane, toluene, xylene, tetrahydrofuran, cyclohexylbenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene. By controlling the temperature of the solvent and the temperature of the substrate, an even better thin film can be formed. Moreover, a thin film can also be formed by melt | dissolving the compound of this invention directly by heating, without melt | dissolving in a solvent. The thin film is preferably produced in an environment where the influence of moisture and oxygen is as small as possible from the viewpoint of obtaining good FET element characteristics.

When the organic semiconductor layer obtained by using the dendrimer of the present invention is used as a constituent element, for example, as an element having a rectifying function or a signal processing function, by combining with an organic or inorganic substance having other semiconductor properties, An element such as a current-driven transistor or a thyristor, triac, or diac that performs a switching operation can be configured. Further, it can also be suitably used as a display element such as a liquid crystal display element or electronic paper.

  Moreover, an organic FET element can also be comprised using the organic-semiconductor layer obtained by using the dendrimer of this invention. An organic FET element is generally composed of a supporting substrate such as glass or plastic, a gate electrode, a source electrode, a drain electrode, a gate insulating film, and an organic semiconductor layer, and controls the voltage applied to the gate electrode to control the gate insulation. Carriers are induced in the organic semiconductor layer on the film, and a current flowing through the source electrode and the drain electrode is controlled to perform a switching operation. The organic FET element includes a bottom gate-bottom contact type, a bottom gate-top contact type, and a top gate type, and any of them may be adopted.

As a material of the gate electrode, for example, Al, Ta, Mo, Nb, Cu, Ag, Au, Pt, In, Ni, Nd, Cr, polysilicon, amorphous silicon, tin oxide, indium oxide, or indium tin compound ( An inorganic material such as Indium Tin Oxide (ITO) or an organic material such as a doped conductive polymer may be used, and any of them may be used. As a material for the gate insulating layer, an inorganic material such as SiO ₂ , SiN, Ta ₂ O ₅ or Al ₂ O ₃ , or a polymer material such as polyimide, polycarbonate or polyparaxylylene can be employed.

  The surface of the gate insulating film can be subjected to a known surface treatment such as HMDS treatment (hexamethyldisilazane treatment) to control the molecular orientation. As a material for the source electrode and the drain electrode, the same kind of material as that for the gate electrode can be used. The material may be the same as or different from the material for the gate electrode, or different kinds of materials may be stacked. In order to increase the carrier injection efficiency, these electrodes may be subjected to surface treatment.

  Furthermore, if the dendrimer of the present invention is used, the orientation can be controlled using a magnetic field or an electric field. The target of orientation control may be either a TOF cell or an organic FET element. Specifically, the temperature is increased until the dendrimer of the present invention exhibits an isotropic phase, a magnetic field is applied in a state of exhibiting the isotropic phase, and the temperature is decreased to room temperature via the liquid crystal phase while controlling the temperature drop time. Accordingly, most of the specific group (mesogen group) in the major axis direction can be parallel to the magnetic field. Since the normal direction of the surface of the TOF (Time of Flight) cell or the surface of the organic FET element and the application direction of the magnetic field can be set arbitrarily, the orientation can be controlled in any direction. The same effect can be obtained by an external field using an electric field by forming an electrode.

  For example, in the case of a cell for TOF, these effects can be confirmed by sandwiching the cell between crossed Nicol polarizing plates and observing the structure and its size and the result of X-ray diffraction. Further, in the case of an organic FET element, it can be confirmed by the observation result by AFM (atomic force microscope) or SEM (scanning electron microscope) and the result of X-ray diffraction.

  Therefore, if the dendrimer of the present invention is used, an organic semiconductor layer in which most of the specific group is oriented in the magnetic field direction can be obtained. By using this, an organic semiconductor and an organic transistor having higher mobility can be obtained. Can be realized.

Hereinafter, the present invention will be described in detail by way of examples. The present invention is not limited by these examples.
Measurement / calculation of each characteristic value and identification of the compound were performed according to the following methods.

(1) Evaluation of phase transition series:
The phase transition series was determined by the results of both DSC (Differential scanning calorimetry) and optical structure observation using a polarizing microscope with a hot stage. The evaluation start temperature was −40 ° C., and the temperature increase / decrease rate was 10 ° C./min. In addition, X-ray diffraction was used for higher-order structural analysis of the liquid crystal phase state.

(2) Measurement of mobility (μ ^TOF ) by TOF (Time of Flight) method:
The dendrimer of the present invention was dissolved in chloroform at a concentration of 1 wt%, spin-coated and dried, heated to an isotropic phase, and then gradually cooled to obtain an organic semiconductor layer. The cell for TOF measurement was configured such that the organic semiconductor layer having a thickness of 20 μm was sandwiched between glass substrates having ITO (Indium Tin Oxide) electrodes.

In addition, as for these electrodes, another type of electrode material can be appropriately selected depending on the carrier type and the work function of the organic semiconductor film. By irradiating pulsed light with the voltage (V) applied between the electrodes of the TOF measurement cell, generating a photocarrier, and converting the change in the current value due to carrier transport into a voltage, the photocurrent is converted into an oscilloscope. Measured with. Nitrogen laser (wavelength: 337 nm, pulse width: 5 ns) was used for the pulsed light. When measuring ^μTOF at different temperatures, the measurement was performed by sandwiching a TOF measurement cell between the METTLER. μ ^TOF is the above formula (
Calculated by i).

(3) Preparation of organic FET device and measurement of device parameters:
Use SiO ₂ (thickness: 500 nm) as the insulating film, n-type Si wafer (manufactured by Semitec Co., Ltd.) as the gate electrode, and Au (50 nm) on Cr (5 nm) as the source and drain electrodes using a metal mask Then, the dendrimer of the present invention was dissolved in chloroform at a concentration of 1 wt%, and an organic semiconductor film was formed by casting to produce a bottom contact type organic FET device.

The channel length (L) was 240 μm and the channel width (W) was 1.2 mm. The measurement temperature was room temperature (25 ° C.).
_< Measurement of mobility ( ^μFET ) and threshold voltage ( _VTH )>
Using a semiconductor parameter analyzer (4140B: HEWLETT PACKARD), the drain voltage (V _D = −50V) is fixed, and the gate voltage (V _G ) is changed from + 20V to −100V in increments of 1V to evaluate the transfer characteristics. Went. From this transfer characteristic curve, the mobility (μ ^FET ) and the threshold voltage (V _TH ) were calculated by the above equation (ii).

<Calculation of on / off ratio>
From the measured transfer characteristics in the above conditions, the maximum value of I _D (I _D ^max) and minimum value (I _D ^min)
Was calculated and the ratio I _D ^max / I _D ^min was calculated as the on / off ratio.

(4) Identification of Synthetic Compound The synthetic compound is identified by nuclear magnetic resonance spectrum ( ¹ H-NMR) (equipment used: FT-NM).
R JMN-EX270 (manufactured by JEOL Co., Ltd.), solvent: CDCl ₃ ) measurement and elemental analysis were performed.

[Example 1]
<Synthesis of Dendrimer (1a)>

（Ｉ） １２−（６−ブロモ−ナフタレン−２−イロキシ）−ドデカン−１−オールの合成
窒素雰囲気下において、６−ブロモ−２−ナフトール（４．２２ｇ、１８．９ｍｍｏｌ:関東化学（株）製）と水酸化カリウム（１．２６ｇ、２２．６ｍｍｏｌ）をエタノール
（鹿一級）に溶解し、７８℃で１５分間攪拌した後、室温まで冷却し、エタノールに溶かした１２−ブロモ−１−ドデカノール（アルドリッチ製）を滴下し、再び７８℃にして、２４時間攪拌した。反応終了後、エタノールを留去してクロロホルムに溶解し、希塩酸で中和した後、蒸留水で洗浄した。さらに、硫酸マグネシウムで脱水し、クロロホルムを留去した。クロロホルムとｎ−ヘキサンで再結晶を行い、収率６６．１％で白色固体を得た。

(I) Synthesis of 12- (6-bromo-naphthalene-2-yloxy) -dodecan-1-ol Under a nitrogen atmosphere, 6-bromo-2-naphthol (4.22 g, 18.9 mmol: Kanto Chemical Co., Inc.) And potassium hydroxide (1.26 g, 22.6 mmol) dissolved in ethanol (deer grade 1), stirred at 78 ° C. for 15 minutes, cooled to room temperature, and 12-bromo-1-dodecanol dissolved in ethanol. (Manufactured by Aldrich) was dropped, and the mixture was again brought to 78 ° C. and stirred for 24 hours. After completion of the reaction, ethanol was distilled off, dissolved in chloroform, neutralized with dilute hydrochloric acid, and washed with distilled water. Furthermore, it dehydrated with magnesium sulfate, and chloroform was distilled off. Recrystallization from chloroform and n-hexane gave a white solid with a yield of 66.1%.

（II） １−（４，４，５，５−テトラメチル−１，３，２，ジオキサボロラン）−４−ｎ−オクチルベンゼンの合成
窒素雰囲気下において、１−ブロモ−４−ｎ−オクチルベンゼン（５ｇ、１８．６ｍｍｏｌ：東京化成工業製）をテトラヒドロフラン（１３６ｍＬ）に溶解し、クールニクスを用いて−７８℃に冷却し、ｎ−ブチルリチウム（９．６ｍＬ、２５．０ｍｍｏｌ：ｎ−ヘキサン溶液、２．６ｍｏｌ／Ｌ、関東化学（株）製）を加えた後、氷浴において０℃にし、１時間攪拌した後、再び−７８℃にした。

(II) Synthesis of 1- (4,4,5,5-tetramethyl-1,3,2, dioxaborolane) -4-n-octylbenzene In a nitrogen atmosphere, 1-bromo-4-n-octylbenzene ( 5 g, 18.6 mmol: manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in tetrahydrofuran (136 mL), cooled to −78 ° C. using COOLNICS, n-butyllithium (9.6 mL, 25.0 mmol: n-hexane solution, 2.6 mol / L, manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was brought to 0 ° C. in an ice bath, stirred for 1 hour, and then brought to −78 ° C. again.

  2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.88 mL, 29.1 mmol: manufactured by Aldrich) was added and stirred at room temperature for 24 hours. After the reaction, tetrahydrofuran was distilled off, dissolved in chloroform, and washed with brine. Purification by column chromatography (chloroform: n-hexane = 1: 2) gave a colorless and transparent liquid 1- (4,4,5,5-tetramethyl-1,3,2, dioxaborolane) -4-n. -Octylbenzene was obtained in a yield of 98.0%.

（III） ２−（４−オクチルフェニル）−６−ドデシルオキシナフトールの合成
窒素雰囲気下において、１２−（６−ブロモ−ナフタレン−２−イロキシ）−ドデカン−１−オール（３．７７ｇ、１０．０ｍｍｏｌ）と１−（４，４，５，５−テトラメチル−１，３，２，ジオキサボロラン）−４−ｎ−オクチルベンゼン（３．１６ｇ、１０．０ｍｍｏｌ）をテトラヒドロフラン（１１０ｍＬ）に溶解し、炭酸カリウム水溶液（１５１ｍｍｏｌ、蒸留水１０８ｍＬと炭酸カリウム２０．９ｇ）とテトラキス（トリフェニルホスフィン）パラジウム（０．４６８ｇ、０．４０５ｍｍｏｌ：関東化学（株）製）を加え、６０℃で２４時間攪拌した。

(III) Synthesis of 2- (4-octylphenyl) -6-dodecyloxynaphthol 12- (6-Bromo-naphthalen-2-yloxy) -dodecan-1-ol (3.77 g, 10.7 g) under nitrogen atmosphere. 0 mmol) and 1- (4,4,5,5-tetramethyl-1,3,2, dioxaborolane) -4-n-octylbenzene (3.16 g, 10.0 mmol) were dissolved in tetrahydrofuran (110 mL), Aqueous potassium carbonate (151 mmol, 108 mL of distilled water and 20.9 g of potassium carbonate) and tetrakis (triphenylphosphine) palladium (0.468 g, 0.405 mmol: manufactured by Kanto Chemical Co., Inc.) were added and stirred at 60 ° C. for 24 hours. .

  After completion of the reaction, impurities were filtered off and tetrahydrofuran was distilled off. Further, it was dissolved in ethanol and added to 1N dilute hydrochloric acid (hydrochloric acid: distilled water = 1: 10). Ethanol was distilled off, extracted with chloroform and washed with distilled water. After dehydration with magnesium sulfate, chloroform was distilled off. Recrystallization was performed with chloroform and n-hexane to obtain a white solid with a yield of 60.5%.

（IV） ２−（４−オクチルフェニル）−６−アクリロイルドデシルオキシナフタレンの合成
窒素雰囲気下において、２−（４−オクチルフェニル）−６−ドデシルオキシナフトール（１．０３ｇ、２．００ｍｍｏｌ）をジクロロメタンに溶解し、トリエチルアミン（０．５５８ｍＬ、４．００ｍｍｏｌ：関東化学（株）製）を加え、氷浴で３０分間攪拌した。

(IV) Synthesis of 2- (4-octylphenyl) -6-acryloyldodecyloxynaphthalene Under nitrogen atmosphere, 2- (4-octylphenyl) -6-dodecyloxynaphthol (1.03 g, 2.00 mmol) was dissolved in dichloromethane. Triethylamine (0.558 mL, 4.00 mmol: manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was stirred in an ice bath for 30 minutes.

  Acrylic acid croid (0.324 mL, 4.00 mmol: manufactured by Kanto Chemical Co., Inc.) and dichloromethane were mixed and added dropwise using a dropping funnel, followed by stirring at 0 ° C. for 12 hours. After completion of the reaction, impurities were filtered off and dichloromethane was distilled off. It melt | dissolved in chloroform and wash | cleaned in order of sodium hydroxide aqueous solution, dilute hydrochloric acid, and distilled water. After dehydration with magnesium sulfate, chloroform was distilled off. Purification by column chromatography (chloroform: n-hexane = 4: 3) gave a white solid in a yield of 92.2%.

得られた化合物の構造を¹Ｈ−ＮＭＲスペクトルで確認した。結果を図１に示す：
｛６．９〜７．９ｐｐｍ（１０Ｈ,Benzene）、５．８，６．１，６．４ｐｐｍ（３Ｈ，AcrylH）、４．０５，４．１５ｐｐｍ（４Ｈ，OH-CH₂）、１．２９〜２．６５ｐｐｍ（３４Ｈ，AlkylH）、２．３５ｐｐｍ（４Ｈ，OC-CH₂）、０．９６ｐｐｍ（３Ｈ），CH₃｝。

The structure of the obtained compound was confirmed by ¹ H-NMR spectrum. The results are shown in FIG.
{6.9~7.9ppm (10H, Benzene), 5.8,6.1,6.4ppm (3H, AcrylH), 4.05,4.15ppm (4H, OH-CH 2), 1.29 ~2.65ppm (34H, AlkylH), 2.35ppm (4H, OC-CH 2), 0.96ppm (3H), CH 3}.

(V) Synthesis of 2- (4-octylphenyl) -6-acryloyldodecyloxynaphthalene and polypropyleneimine dendrimer Under nitrogen atmosphere, 2- (4-octylphenyl) -6-acryloyldecyloxynaphthalene (200 mg, 0.350 mmol) ) Was added generation 2 polypropyleneimine dendrimer (manufactured by Aldrich) dissolved in tetrahydrofuran (0.8 mL), and the mixture was stirred at 45 ° C. for 2 weeks. After completion of the reaction, chloroform was added and methanol was added. The precipitate was suction filtered and chloroform and methanol were distilled off. After sufficiently drying, it was dissolved in as little chloroform as possible and poured into methanol. After the precipitate was suction filtered, chloroform and methanol were distilled off to obtain a cream colored solid.

得られた化合物の構造を¹Ｈ−ＮＭＲスペクトルで確認した。結果を図２に示す：
｛６．８３〜７．８６ｐｐｍ（１６０Ｈ，Benzene）、３．９４，４．０４，４．０８（
９６Ｈ，O-CH₂）、２．７５ｐｐｍ（３２Ｈ，OC-C-CH₂）、２．３６ｐｐｍ（５２Ｈ，N-CH₂）、２．３５ｐｐｍ（３２Ｈ，OC-CH₂）、１．５７，１．７１ｐｐｍ（９６Ｈ，O-C-CH₂）、１．４９ｐｐｍ（２８Ｈ，N-C-CH₂）、１．２９，１．３３ｐｐｍ（４１６Ｈ，AlkylH）、０．９６ｐｐｍ（４８Ｈ，CH₃）｝。

The structure of the obtained compound was confirmed by ¹ H-NMR spectrum. The results are shown in FIG.
{6.83 to 7.86 ppm (160H, Benzene), 3.94, 4.04, 4.08 (
96H, O—CH ₂ ), 2.75 ppm (32H, OC—C—CH ₂ ), 2.36 ppm (52H, N—CH ₂ ), 2.35 ppm (32H, OC—CH ₂ ), 1.57, _{1.71ppm (96H, OC-CH 2} ), 1.49ppm (28H, NC-CH 2), 1.29,1.33ppm (416H, AlkylH), 0.96ppm (48H, CH 3)}.

  Furthermore, as a result of elemental analysis, actual values (C: 79.33%, H: 9.81) were compared with theoretical values (C: 78.31%, H: 9.41%, N: 1.97%). %, N: 1.92%), confirming the synthesis of the target product.

<< Evaluation of phase transition series >>
As a result of evaluating the phase transition series of the obtained dendrimer (1a) at an evaluation start temperature of −40 ° C., the SmE phase was exhibited in a wide temperature range from low temperature to room temperature. The phase transition from SmE phase to SmB phase, phase transition from SmB phase to SmA phase at 111 ° C., and phase transition from SmA phase to isotropic phase at 126 ° C.

  In the temperature lowering process, the phase transition from the isotropic phase to the SmA phase at 119 ° C., the phase transition from the SmA phase to the SmB phase at 105 ° C., the phase transition from the SmB phase to the SmX phase at 86.6 ° C., and 68.5 ° C. Phase transition from SmX phase to SmE phase. Dendrimer (1a) showed an SmE phase at room temperature and did not crystallize to a low temperature region. From this, it was found that the dendrimer (1a) of the present invention has a liquid crystal phase temperature range expanded to room temperature (SmE phase at room temperature) and is not crystallized.

<< Measurement of mobility by TOF method >>
A cell for TOF measurement was prepared by the above-described method, and the mobility was measured at room temperature (25 ° C.) using the dendrimer (1a) of the present invention. As a result, the film formability was good. μ ^TOF (25 ° C.) = 2.0 × 10 ⁻³ cm ² / V · s.

  As a result, the dendrimer (1a) of the present invention has a low lower limit of the liquid crystal phase temperature range, can realize a liquid crystal state (SmE phase) at room temperature, has no crystal grain boundary even at room temperature, It was found that high mobility can be maintained because of good film properties.

《Orientation control using external field》
Orientation control was performed on the TOF cell using a magnetic field. The configuration of the apparatus used (electromagnet: TM-WV8615 MRC-156) is shown in FIG. The ceramic heater 16 once heated to an isotropic phase and held for 5 minutes, and then applied a magnetic field 10 (2.4 Tesla) in parallel to the surface of the TOF measurement cell, while the cooling rate was 0.1 ° C. / Min at room temperature.

As a result of observing the optical structure with a polarizing microscope, it was confirmed that the orientation was better than when no magnetic field was applied. As a result of measuring the mobility of the organic semiconductor layer produced while applying a magnetic field at room temperature, it was μ ^TOF = 3.1 × 10 ⁻³ cm ² / V · s. Thus, it was found that the mobility value can be further increased by forming an organic semiconductor layer in which most of the mesogenic groups of the dendrimer (1a) of the present invention are oriented in the magnetic field direction.

<< Production of organic FET elements and measurement of element parameters >>
According to the above-mentioned method, an organic FET element was produced using the dendrimer (1a) of the present invention as an organic semiconductor layer, and μ ^FET was evaluated at room temperature. As a result, μ ^FET = 1.2 × 10 ⁻³ cm ² / V · s. On-off ratio = 8 × 10 ³ and V _TH = −40V.

[Comparative Example 1]
<< Evaluation of phase transition series >>
A liquid crystal organic semiconductor material (Polymer Preprints, Japan Vol. 50. No12 (2001) 2879-2880) represented by the following formula (2a) was synthesized, and the evaluation start temperature was set to −40 ° C., and the phase transition series was evaluated. As a result, a crystalline phase was exhibited at room temperature, and during the heating process, the phase transitioned from the crystalline phase to the SmB phase at 79.4 ° C., the phase transition from the SmB phase to the SmA phase at 101 ° C. Phase transition from phase to isotropic phase.

《ＴＯＦ法による移動度の測定》
ＴＯＦ測定用セルを実施例１と同様の方法で作製し、２５℃と９０℃で評価を行った。上述したように２５℃では結晶状態であり、９０℃ではＳｍＢ相であった。結果を以下に示す。

<< Measurement of mobility by TOF method >>
A cell for measuring TOF was produced in the same manner as in Example 1 and evaluated at 25 ° C. and 90 ° C. As described above, it was in a crystalline state at 25 ° C., and was an SmB phase at 90 ° C. The results are shown below.

In μ ^TOF (25 ° C.), since the crystalline phase was exhibited at room temperature, the film forming property was poor, and a waveform indicating carrier transport was not observed.
μ ^TOF (90 ° C.) = 1.8 × 10 ⁻³ cm ² / Vs
From these results, although the SmB phase, which is a liquid crystal phase, shows good carrier (hole) transportability, the film formability is poor at room temperature (25 ° C.), and the influence of crystal grain boundaries is too great. It can be seen that disappeared. The evaluation results of Example 1 are shown in Table 1.

［実施例２］
＜本発明のデンドリマー（１ｂ）の合成＞

[Example 2]
<Synthesis of Dendrimer (1b) of the Present Invention>

（Ｉ） １２−（６−ブロモ−ナフタレン−２−イロキシ）−ドデカン−１−オールの合成
窒素雰囲気下において、６−ブロモ−２−ナフトール（４．２２ｇ、１８．９ｍｍｏｌ：関東化学（株）製）と水酸化カリウム（１．２６ｇ、２２．６ｍｍｏｌ）をエタノール（鹿一級）に溶解し、７８℃で１５分間攪拌した。室温まで冷却し、エタノールに溶かした１２−ブロモ−１−ドデカノール（アルドリッチ製）を滴下し、再び７８℃にして、２４時間攪拌した。反応終了後、エタノールを留去してクロロホルムに溶解し、希塩酸で中和し、その後、蒸留水で洗浄した。硫酸マグネシウムで脱水し、クロロホルムを留去した。クロロホルムとｎ−ヘキサンで再結晶を行い、収率９８．０％で白色固体を得た。

(I) Synthesis of 12- (6-bromo-naphthalen-2-yloxy) -dodecan-1-ol Under a nitrogen atmosphere, 6-bromo-2-naphthol (4.22 g, 18.9 mmol: Kanto Chemical Co., Inc.) And potassium hydroxide (1.26 g, 22.6 mmol) were dissolved in ethanol (deer grade 1) and stirred at 78 ° C. for 15 minutes. After cooling to room temperature, 12-bromo-1-dodecanol (manufactured by Aldrich) dissolved in ethanol was added dropwise, and the mixture was again brought to 78 ° C. and stirred for 24 hours. After completion of the reaction, ethanol was distilled off and dissolved in chloroform, neutralized with dilute hydrochloric acid, and then washed with distilled water. After dehydration with magnesium sulfate, chloroform was distilled off. Recrystallization was performed with chloroform and n-hexane to obtain a white solid with a yield of 98.0%.

（II） １−ブロモ−２−メチル−４−ｎ−オクチルオキシ−ベンゼンの合成
窒素雰囲気下において、４−ブロモ−３−メチルフェノール（５．００ｇ、２６．７ｍｍｏｌ：関東化学（株）製）と水酸化カリウム（１．７９ｇ、３１．９ｍｍｏｌ）をエタノール（２０ｍＬ）に溶解し、７８℃で１５分間攪拌した。室温に戻し、エタノールに溶解させた８−ブロモ−１−オクタン（５．１６ｇ、２６．７ｍｍｏｌ：アルドリッチ製）を滴下し、７８℃で２４時間攪拌した。

(II) Synthesis of 1-bromo-2-methyl-4-n-octyloxy-benzene In a nitrogen atmosphere, 4-bromo-3-methylphenol (5.00 g, 26.7 mmol: manufactured by Kanto Chemical Co., Inc.) And potassium hydroxide (1.79 g, 31.9 mmol) were dissolved in ethanol (20 mL) and stirred at 78 ° C. for 15 minutes. The temperature was returned to room temperature, and 8-bromo-1-octane (5.16 g, 26.7 mmol: manufactured by Aldrich) dissolved in ethanol was added dropwise, followed by stirring at 78 ° C. for 24 hours.

After completion of the reaction, ethanol was distilled off, dissolved in chloroform, neutralized with dilute hydrochloric acid, and washed with distilled water. After dehydration with magnesium sulfate, chloroform was distilled off. A white solid was obtained in a yield of 91.6%.

（III） １−（４，４，５，５−テトラメチル−１，３，２，ジオキサボロラン）−
２−メチル−４−ｎ−オクチルオキシベンゼンの合成
窒素雰囲気下において、１−ブロモ−２−メチル−４−オクチルオキシ−ベンゼン（５．５７ｇ、１８．６ｍｍｏｌ）をテトラヒドロフラン（１３６ｍＬ）に溶解し、クールニクスを用いて−７８℃に冷却し、ｎ−ブチルリチウム（９．６ｍＬ、２５．０ｍｍｏｌ：ｎ−ヘキサン溶液、２．６ｍｏｌ／Ｌ、関東化学（株）製）を加えた。氷浴において０℃にし、１時間攪拌した後、再び−７８℃にした。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（５．８８ｍＬ、２９．１ｍｍｏｌ：アルドリッチ製）を加え、室温において２４時間攪拌した。

(III) 1- (4,4,5,5-tetramethyl-1,3,2, dioxaborolane)-
Synthesis of 2-methyl-4-n-octyloxybenzene In a nitrogen atmosphere, 1-bromo-2-methyl-4-octyloxy-benzene (5.57 g, 18.6 mmol) was dissolved in tetrahydrofuran (136 mL). The mixture was cooled to −78 ° C. using COOLNICS, and n-butyllithium (9.6 mL, 25.0 mmol: n-hexane solution, 2.6 mol / L, manufactured by Kanto Chemical Co., Inc.) was added. The mixture was brought to 0 ° C. in an ice bath, stirred for 1 hour, and then brought to −78 ° C. again. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.88 mL, 29.1 mmol: manufactured by Aldrich) was added and stirred at room temperature for 24 hours.

  After completion of the reaction, tetrahydrofuran was distilled off, dissolved in chloroform, and washed with brine. Purification was performed by column chromatography (chloroform: n-hexane = 1: 2), and the yield of 87.6% was obtained as a colorless and transparent liquid 1- (4,4,5,5-tetramethyl-1,3,3). 2, Dioxaborolane) -2-methyl-4-n-octyloxybenzene was obtained.

（IV） ２−（２−メチル−４−オクチルオキシフェニル）−６−ドデシルオキシナフトールの合成
窒素雰囲気下において、１２−（６−ブロモ−ナフタレン−２−イロキシ）−ドデカン−１−オール（４．０７ｇ、１０．０ｍｍｏｌ）と１−（４，４，５，５−テトラメチル−１，３，２，ジオキサボロラン）−２−メチル−４−ｎ−オクチルオキシベンゼン（３．４６ｇ、１０．０ｍｍｏｌ）をテトラヒドロフラン（１１０ｍＬ）に溶解し、炭酸カリウム水溶液（１５１ｍｍｏｌ、蒸留水１０８ｍＬと炭酸カリウム２０．９ｇ）とテトラキス（トリフェニルホスフィン）パラジウム（０．４６８ｇ、０．４０５ｍｍｏｌ：関東化学（株）製）とを加え、６０℃で２４時間攪拌した。

(IV) Synthesis of 2- (2-methyl-4-octyloxyphenyl) -6-dodecyloxynaphthol In a nitrogen atmosphere, 12- (6-bromo-naphthalen-2-yloxy) -dodecan-1-ol (4 0.07 g, 10.0 mmol) and 1- (4,4,5,5-tetramethyl-1,3,2, dioxaborolane) -2-methyl-4-n-octyloxybenzene (3.46 g, 10.0 mmol) ) In tetrahydrofuran (110 mL), aqueous potassium carbonate solution (151 mmol, distilled water 108 mL and potassium carbonate 20.9 g) and tetrakis (triphenylphosphine) palladium (0.468 g, 0.405 mmol: manufactured by Kanto Chemical Co., Inc.) And stirred at 60 ° C. for 24 hours.

  After completion of the reaction, impurities were filtered off and tetrahydrofuran was distilled off. It was dissolved in ethanol and added to 1N dilute hydrochloric acid (hydrochloric acid: distilled water = 1: 10). Ethanol was distilled off, extracted with chloroform and washed with distilled water. After dehydration with magnesium sulfate, chloroform was distilled off. Recrystallization from chloroform and n-hexane gave white solid 2- (2-methyl-4-octyloxyphenyl) -6-dodecyloxynaphthol in a yield of 57.4%.

（Ｖ） ２−（２−メチル−４−オクチルオキシフェニル）−６−アクリロイルドデシルオキシナフタレンの合成
窒素雰囲気下において、２−（２−メチル−４−オクチルオキシフェニル）−６−ドデシルオキシナフトール（１．０９ｇ、２．００ｍｍｏｌ）をジクロロメタンに溶解し、トリエチルアミン（０．５５８ｍＬ、４．００ｍｍｏｌ：関東化学（株）製）を加え、氷浴で３０分間攪拌した。アクリル酸クロイド（関東化学（株）製）とジクロロメタンとを混合し、滴下ロートを用いて滴下し、０℃のまま１２時間攪拌した。

(V) Synthesis of 2- (2-methyl-4-octyloxyphenyl) -6-acryloyldodecyloxynaphthalene In a nitrogen atmosphere, 2- (2-methyl-4-octyloxyphenyl) -6-dodecyloxynaphthol ( 1.09 g, 2.00 mmol) was dissolved in dichloromethane, triethylamine (0.558 mL, 4.00 mmol: manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was stirred in an ice bath for 30 minutes. Acrylic acid croid (manufactured by Kanto Chemical Co., Inc.) and dichloromethane were mixed, dropped using a dropping funnel, and stirred at 0 ° C. for 12 hours.

  After completion of the reaction, impurities were filtered off and dichloromethane was distilled off. It melt | dissolved in chloroform and wash | cleaned using these in order of sodium hydroxide aqueous solution, dilute hydrochloric acid, and distilled water. After dehydration with magnesium sulfate, chloroform was distilled off. Purification by column chromatography (chloroform: n-hexane = 4: 3) gave white solid 2- (2-methyl-4-octyloxyphenyl) -6-acryloyldodecyloxynaphthalene in a yield of 31.4%. It was.

得られた化合物の構造を¹Ｈ−ＮＭＲスペクトルで確認した。結果を図４に示す:
｛６．６３〜７．９ｐｐｍ（９Ｈ，Benzene）、５．８０，６．０５，６．４３（３Ｈ，AcrylH）、３．５３，３．９４，４．０４ｐｐｍ（６Ｈ，O-CH₂）、２．３５ｐｐｍ（３Ｈ，Benzene-CH₃）、１．２９〜１．７１ｐｐｍ（３２Ｈ，AlkylH）、０．９６ｐｐｍ（３
Ｈ，C-CH₃）｝。

The structure of the obtained compound was confirmed by ¹ H-NMR spectrum. The results are shown in FIG.
{6.63 to 7.9 ppm (9H, Benzene), 5.80, 6.05, 6.43 (3H, AcrylH), 3.53, 3.94, 4.04 ppm (6H, O—CH ₂ ) 2.35 ppm (3H, Benzene-CH ₃ ), 1.29 to 1.71 ppm (32H, AlkylH), 0.96 ppm (3
_{H, C-CH 3)}} .

(VI) Synthesis of 2- (2-methyl-4-octyloxyphenyl) -6-acryloyl decyloxynaphthalene and polypropyleneimine dendrimer In a nitrogen atmosphere, 2- (2-methyl-4-octyloxyphenyl) -6 To acryloyl decyloxynaphthalene (210.3 mg, 0.350 mmol) was added a second generation polypropylene imine dendrimer (5.6 mg, 0.00723 mmol: manufactured by Aldrich) dissolved in tetrahydrofuran (0.8 mL). Stir for a week.

  After completion of the reaction, chloroform was added and poured into methanol. The precipitate was suction filtered and chloroform and methanol were distilled off. After sufficiently drying, it was dissolved in as little chloroform as possible and poured into methanol. After the precipitate was suction filtered, chloroform and methanol were distilled off to obtain a cream colored solid.

得られた化合物の構造を¹Ｈ−ＮＭＲスペクトルで確認した。結果を図５に示す:
｛６．６３〜７．６６ｐｐｍ（１４４Ｈ，Benzene）、３．９４，４．０４，４．０８ｐ
ｐｍ（９６Ｈ，O-CH₂）、２．７５ｐｐｍ（３２Ｈ，OC-C-CH₂）、２．３６ｐｐｍ（５２
Ｈ，N-CH₂）、２．３５ｐｐｍ（８０Ｈ，Benzene-CH₃，OC-CH₂）１．５７，１．７１ｐｐｍ（９６Ｈ，O-C-CH₂）、１．４９ｐｐｍ（２８Ｈ，N-C-CH₂）、１．２９，１．３３ｐｐｍ（４１６Ｈ，AlkoxyH）、０．９６ｐｐｍ（４８Ｈ，CH₃）｝。

The structure of the obtained compound was confirmed by ¹ H-NMR spectrum. The results are shown in FIG.
{6.63-7.66 ppm (144H, Benzene), 3.94, 4.04, 4.08p
pm (96H, O—CH ₂ ), 2.75 ppm (32H, OC—C—CH ₂ ), 2.36 ppm (52
H, N-CH ₂ ), 2.35 ppm (80H, Benzene-CH ₃ , OC-CH ₂ ) 1.57, 1.71 ppm (96H, OC-CH ₂ ), 1.49 ppm (28H, NC-CH ₂₎ ), 1.29,1.33ppm (416H, AlkoxyH) , 0.96ppm (48H, CH 3)}.

  Furthermore, as a result of elemental analysis, actual values (C: 78.56%, H: 9.70) were compared with theoretical values (C: 78.47%, H: 9.52%, N: 1.93%). %, N: 2.00%), and it was confirmed that the target product was synthesized.

<< Evaluation of phase transition series >>
As a result of evaluating the phase transition series of the obtained dendrimer (1b) at an evaluation start temperature of −40 ° C., the smectic phase was exhibited in a wide temperature range including low temperature (−5 ° C.) to room temperature. The phase transition from the SmE phase to the SmX phase at 36.2 ° C., the phase transition from the SmX phase to the SmA phase at 42.2 ° C., and the phase transition from the SmA phase to the isotropic phase at 64.7 ° C. In the temperature lowering process, the phase transitioned from the isotropic phase to the SmA phase at 61.2 ° C., and into the glass state at −5 ° C.

As a result, it was confirmed that the dendrimer (1b) of the present invention exhibited an Sm phase at room temperature.
<< Measurement of mobility by TOF method >>
The mobility of the dendrimer (1b) of the present invention was measured according to the same method as in Example 1. As a result, the film forming property was good and μ ^TOF (25 ° C.) = 4.7 × 10 ⁻³ cm ² / V · The value was as high as s.

《Orientation control using external field》
According to the same method as in Example 1, the TOF cell was subjected to orientation control using a magnetic field. As a result of observing the optical structure with a polarizing microscope, it was confirmed that the orientation was better than when no magnetic field was applied. As a result of measuring the mobility of the organic semiconductor layer produced while applying a magnetic field at room temperature, μ ^TOF (25 ° C.) = 5.5 × 10 ⁻³ cm ² / V · s, and the mobility value is further increased. We were able to. The evaluation results of Example 2 are shown in Table 2.

［実施例３］
＜本発明のデンドリマー（１ｃ）の合成＞
ポリプロピレンイミンデンドリマーの末端基となる式（１ｃ）におけるＭを、ＷＯ２００６／０２２０４０号公報に記載の方法で合成した以外は、実施例１と同様の方法に従い、式（１ｃ）で表される本発明のデンドリマー（１ｃ）を得た。

[Example 3]
<Synthesis of Dendrimer (1c) of the Present Invention>
The present invention represented by the formula (1c) according to the same method as in Example 1 except that M in the formula (1c) serving as the terminal group of the polypropyleneimine dendrimer was synthesized by the method described in WO2006 / 022040. The dendrimer (1c) was obtained.

《ＴＯＦ法による移動度の測定》
実施例１と同様の方法に従って、本発明のデンドリマー（１ｃ）の移動度の測定を行った結果、室温下で液晶相を示し、良好な成膜性を有し、μ^TOF（２５℃）＝１．０×１０^-2ｃｍ² / Ｖ・ｓと高い値を示した。

<< Measurement of mobility by TOF method >>
The mobility of the dendrimer (1c) of the present invention was measured according to the same method as in Example 1. As a result, it showed a liquid crystal phase at room temperature, had good film formability, and μ ^TOF (25 ° C.) = A high value of 1.0 × 10 ⁻² cm ² / V · s was shown.

[Comparative Example 2]
A liquid crystal organic semiconductor material (Chem. Commun., 2005, 5337-5339, K. Oikawa, Y. Shimizu) represented by the following formula (2b) was synthesized, and evaluation of the phase transition series was performed at an evaluation start temperature of −40 ° C. As a result, it was a crystalline phase at room temperature, and during the temperature rising process, the phase transitioned from the crystalline phase to the intermediate phase (M3) at 47.5 ° C., and from the intermediate phase (M3) to the intermediate phase (M2) at 71.4 ° C. ), The phase transition from the intermediate phase (M2) to the intermediate phase (M1) at 87 ° C., and the phase transition from the intermediate phase (M1) to the isotropic phase at 146 ° C.

Next, as a result of measuring the mobility at room temperature (25 ° C.) using the TOF method, the film formability was poor, and a waveform indicating carrier transport was not observed at μ ^TOF (25 ° C.).

実施例３の評価結果を表３に示す。

The evaluation results of Example 3 are shown in Table 3.

［実施例４］
＜本発明のデンドリマー（１ｄ）の合成＞
ポリプロピレンイミンデンドリマーの末端基となる式（１ｄ）におけるＭを、特開２００５−１４２５２６号公報に記載の方法で合成したした以外は、実施例１と同様の方法に従い、式（１ｄ）で表される本発明のデンドリマー（１ｄ）を得た。

[Example 4]
<Synthesis of Dendrimer (1d) of the Present Invention>
According to the same method as in Example 1 except that M in the formula (1d) serving as the terminal group of the polypropyleneimine dendrimer was synthesized by the method described in JP-A-2005-142526, it was represented by the formula (1d). The dendrimer (1d) of the present invention was obtained.

《ＴＯＦ法による移動度の測定》
実施例１と同様の方法に従って、本発明のデンドリマー（１ｄ）の移動度の測定を行った結果、室温下で液晶相を示し、良好な成膜性を有するためμ^TOF（２５℃）＝５．１×
１０^-2ｃｍ² / Ｖ・ｓと高い値を示した。

<< Measurement of mobility by TOF method >>
The mobility of the dendrimer (1d) of the present invention was measured according to the same method as in Example 1, and as a result, it showed a liquid crystal phase at room temperature and had good film formability, so that μ ^TOF (25 ° C.) = 5 .1x
The value was as high as 10 ⁻² cm ² / V · s.

[Comparative Example 3]
A liquid crystal organic semiconductor material represented by the following formula (2c) (53rd Applied Physics Related Conference Lecture Proceedings, p1408) was synthesized, and the phase transition series was evaluated at an evaluation start temperature of −40 ° C. As a result, it was a crystalline phase at room temperature, and during the temperature rising process, the phase transitioned from the crystalline phase to the intermediate phase (M) at 92.4 ° C., and from the intermediate phase (M) to the isotropic phase at 181 ° C.

Next, as a result of measuring the mobility μ ^TOF (25 ° C.) at room temperature (25 ° C.) using the TOF method, the film formation was poor because it was a crystalline phase at room temperature, and a waveform indicating carrier transport was not observed. .

実施例４の評価結果を表４に示す。

The evaluation results of Example 4 are shown in Table 4.

［実施例５］
＜本発明のデンドリマー（０ｅ）、（１ｅ）、（０ｆ）、（１ｆ）の合成＞

[Example 5]
<Synthesis of Dendrimer (0e), (1e), (0f), (1f) of the Present Invention>

化合物(２)は、文献P. Wilson et al., Mol.Cryst. and Liq. Cryst., 2001, 368, 279-292に従って得た。２−ヘキシルチオフェン(１)（Lancaster社製、5ｇ、29.7mmol）を脱水THF50ｍｌに溶かした。その溶液をドライアイス/アセトンによって、−７８℃にまで冷却した。そこに1.6Mノルマルブチルリチウムヘキサン溶液（関東化学社製、19ｍｌ、30mmol）を滴下した。滴下後、１５分間その温度で攪拌した後、さらに室温で1時間攪拌し、
再び、−７８℃に冷却して、塩化トリブチルスズ（東京化成社製、10ｇ、30.7mmol）を加
えた。室温に戻して一晩攪拌した。その混合物に水を加え、有機物をジクロロメタンで抽出した。有機層を無水硫酸マグネシウムで乾燥させた後、溶媒を留去して、目的物の粗製体を得た。精製は真空蒸留によって行った。

Compound (2) was obtained according to the document P. Wilson et al., Mol. Cryst. And Liq. Cryst., 2001, 368, 279-292. 2-Hexylthiophene (1) (Lancaster, 5 g, 29.7 mmol) was dissolved in 50 ml of dehydrated THF. The solution was cooled to -78 ° C with dry ice / acetone. A 1.6 M normal butyl lithium hexane solution (manufactured by Kanto Chemical Co., 19 ml, 30 mmol) was added dropwise thereto. After dropping, the mixture was stirred at that temperature for 15 minutes, and further stirred at room temperature for 1 hour.
Again, it cooled to -78 degreeC and the tributyltin chloride (The Tokyo Chemical Industry company make, 10 g, 30.7 mmol) was added. It returned to room temperature and stirred overnight. Water was added to the mixture and the organics were extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain a crude product of the desired product. Purification was performed by vacuum distillation.

A dehydrated dimethylformamide mixture (20 ml) of compound (2) (1 g, 2.19 mmol), 5-bromo-2,2′-bithiophene (Aldrich, 0.5 g, 2.04 mmol) was exposed to a stream of nitrogen for 30 minutes. Bis (triphenylphosphine) palladium (II) dichloride (manufactured by Tokyo Chemical Industry Co., Ltd., 20 mg, 0.03 mmol), triphenylphosphine (manufactured by Wako Pure Chemical Industries, 26 mg, 0.1 mmol)
) And stirred at 100 ° C. for 20 hours. After cooling to room temperature, water was added and the organic layer was extracted with dichloromethane. After the dichloromethane solution was dried over anhydrous magnesium sulfate, the solvent was distilled off. Column purification and recrystallization were performed to obtain the desired product (3).

  Under a nitrogen atmosphere, 2.77M n-BuLi (manufactured by Kanto Chemical Co., 1.1 ml, 3.0 mmol) was added dropwise to a dehydrated THF solution (100 ml) of (3) (0.9 g, 2.8 mmol) at -78 ° C. The mixture was returned to room temperature, stirred for 30 minutes, cooled to −78 ° C., and 6-bromohexyloxy-tert-butyldimethylsilane (Aldrich, 0.84 g, 2.8 mmol) was added. It returned to room temperature and stirred for further 2 hours. After adding water to stop the reaction, the organic layer was extracted with dichloromethane. The organic layer was washed with brine and dried over anhydrous magnesium sulfate, and then the solvent was distilled off. Column purification and recrystallization were performed to obtain the desired product (4).

  Under a nitrogen atmosphere, 1.0 M tetrabutylammonium fluoride (Aldrich, 14 ml, 14 mmol) was added to a dehydrated THF solution (5 ml) of the crude product (4) (1.0 g, 1.8 mmol) and stirred at room temperature for 24 hours. Water was added to stop the reaction, and the organic layer was extracted with ethyl acetate. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off. The column was purified using ethyl acetate as a developing solvent, and then recrystallized from hexane to obtain the desired product (5).

Under a nitrogen atmosphere, a solution of acroyl chloride in dichloromethane (10 ml) at 0 ° C in a dichloromethane solution (30 ml) in which (5) (0.56 g, 1.3 mmol) and triethylamine (0.26 g, 2.6 mmol) were dissolved. And stirred at that temperature for 12 hours. Water was added to stop the reaction, and the organic layer was extracted with dichloromethane. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off. Column purification yielded the desired product (6).

Compound (6) (1 g, 2.0 mmol) and 1,3-diaminopropane (manufactured by Kanto Kagaku, 18 mg, 0.25 mmol) were refluxed in dehydrated THF for 2 weeks under a nitrogen atmosphere. After completion of the reaction, THF was distilled off to obtain a crude product as a powder. The obtained solid was dissolved in a small amount of chloroform, n-hexane was added, and the target product (0e) was reprecipitated. This operation was repeated until the NMR peak of the acrylic group disappeared.

Compound (6) (1 g, 2.0 mmol) and polypropyleneimine dendrimer first generation (PPID G1.0) (Aldrich, 40 mg, 0.13 mmol) were refluxed in dehydrated THF for 2 weeks under a nitrogen atmosphere. After completion of the reaction, THF was distilled off to obtain a crude product as a powder. The obtained solid was dissolved in a small amount of chloroform, n-hexane was added, and the target product (1e) was reprecipitated. This operation was repeated until the NMR peak of the acrylic group disappeared.

Under a nitrogen atmosphere, N-bromosuccinimide (manufactured by Kanto Chemical Co., 0.53 g, 3.0 mmol) was slowly added dropwise to a dehydrated dimethylformamide solution (30 ml) of (3) (1.0 g, 3.0 mmol). It returned to room temperature and stirred for 10 hours. After adding water to stop the reaction, the organic layer was extracted with dichloromethane. The organic layer was washed with brine and dried over anhydrous magnesium sulfate, and then the solvent was distilled off. Purification was performed using column chromatography to obtain the desired product (9).

Under a nitrogen atmosphere, compound (9) (1.0 g, 2.4 mmol), 2-thiopheneboronic acid (manufactured by Tokyo Chemical Industry, 0.31 g, 2.4 mmol), and cesium carbonate (manufactured by Kanto Chemical, 1 g) are added to 50 ml of diethylene glycol dimethyl ether. And exposed to a nitrogen stream for 30 minutes. Tetrakis (triphenylphosphonium) palladium (manufactured by Tokyo Chemical Industry Co., Ltd., 0.1 g, 0.09 mmol) was added to this mixture, and the mixture was stirred at 85 ° C. for several hours. The reaction mixture returned to room temperature was poured into a saturated aqueous ammonium chloride solution (100 ml), and the precipitate was filtered. The precipitate was vacuum-dried and purified by column purification to obtain the desired product (10).

Under a nitrogen atmosphere, 2.77M n-BuLi (manufactured by Kanto Chemical Co., 1.1 ml, 3.0 mmol) was added dropwise to a dehydrated THF solution (100 ml) of (10) (1.16 g, 2.8 mmol) at −78 ° C. It returned to room temperature and stirred for 30 minutes.
The mixture was cooled again to −78 ° C., and 6-bromohexyloxy-tert-butyldimethylsilane (Aldrich, 0.84 g, 2.8 mmol) was added. After returning to room temperature and stirring for 2 hours and adding water to stop the reaction, the organic layer was extracted with dichloromethane. The organic layer was washed with brine and dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The obtained crude product was purified by column to obtain the desired product (11).

Under a nitrogen atmosphere, 1.0 M tetrabutylammonium fluoride (Aldrich, 14 ml, 14 mmol) was added to a dehydrated THF solution (5 ml) of the crude product (11) (1.13 g, 1.8 mmol), and the mixture was stirred at room temperature for 24 hours. Water was added to stop the reaction, and the organic layer was extracted with ethyl acetate. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off. The obtained crude product was purified by column to obtain the desired product (12).

Under nitrogen atmosphere, dichloromethane solution (30 ml) in which (12) (0.67 g, 1.3 mmol) and triethylamine (0.26 g, 2.6 mmol) were dissolved in a solution of acroyl chloride in dichloromethane (10 ml) at 0 ° C. And stirred at that temperature for 12 hours. Water was added to stop the reaction, and the organic layer was extracted with dichloromethane. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off. The obtained crude product was purified by column to obtain the desired product (13).

Compound (13) (1.13 g, 2.0 mmol) and 1,3-diaminopropane (manufactured by Kanto Chemical, 18 mg, 0.25 mmol) were refluxed in dehydrated THF for 2 weeks under a nitrogen atmosphere. After completion of the reaction, THF was distilled off to obtain a crude product as a powder. The obtained solid was dissolved in a small amount of chloroform, and n-hexane was added to reprecipitate the target product (0f). This operation was repeated until the NMR peak of the acrylic group disappeared.

Compound (13) (1.13 g, 2.0 mmol) and polypropyleneimine dendrimer first generation (PPID G1.0) (Aldrich, 40 mg, 0.13 mmol) were refluxed in dehydrated THF for 2 weeks under a nitrogen atmosphere. After completion of the reaction, THF was distilled off to obtain a crude product as a powder. The obtained solid was dissolved in a small amount of chloroform, n-hexane was added, and the target product (1f) was reprecipitated. This operation was repeated until the NMR peak of the acrylic group disappeared.

《ＴＯＦ法による移動度の測定》
実施例１と同様の方法に従って、本発明のデンドリマー（０e）、（１e）、（０ｆ）および（１ｆ）の移動度の測定を行った結果、それぞれ、μ^TOF（２５℃）＝４．５×１０^-3ｃｍ² / Ｖ・s、６．１×１０^-3ｃｍ² / Ｖ・s、８．５×１０^-3ｃｍ² / Ｖ・s、１．０×１０^-2ｃｍ² / Ｖ・sと高い値を示した。

<< Measurement of mobility by TOF method >>
According to the same method as in Example 1, the mobility of the dendrimers (0e), (1e), (0f) and (1f) of the present invention was measured. As a result, μ ^TOF (25 ° C.) = 4.5 × 10 ⁻³ cm ² / V · s, 6.1 × 10 ⁻³ cm ² / V · s, 8.5 × 10 ⁻³ cm ² / V · s, 1.0 × 10 ⁻² cm ² / V -It showed a high value with s.

[Comparative Example 4]
Results of synthesizing a liquid crystal organic semiconductor material (J. Mater. Chem., 2003, 13, 197-202) represented by the following formula (2d) and evaluating the phase transition series at an evaluation start temperature of −40 ° C. The crystal phase was at room temperature, and during the temperature rising process, the phase transitioned from the crystal phase to the SmF phase at 54.1 ° C., and the phase transition from the SmF phase to the isotropic phase at 84.3 ° C.

  Next, as a result of measuring the mobility at room temperature (25 ° C.) using the TOF method, film formation was poor because it was a crystal at room temperature, and a waveform indicating carrier transportability was not observed.

実施例５の評価結果を表５に示す。

The evaluation results of Example 5 are shown in Table 5.

[実施例６]
＜本発明のデンドリマー（１ｇ）の合成＞

[Example 6]
<Synthesis of Dendrimer (1 g) of the Present Invention>

化合物（１）（1g, 3.7mmol）、水（30ml）、および硫酸（2ml）を混合し、５℃以下に冷却した混合物に、別途、亜硝酸ナトリウム（関東化学製）（630mg, 9.1mmol）と水（10ml）とで調整した溶液を、５℃以下に保ちながら滴下した。滴下終了後30分攪拌したのち、ホスフィン酸（関東化学製）(20ml)、エタノール（20ml）を加え、三時間還流した。室温まで冷却後、沈殿した固体をろ過によって回収した。固体を乾燥させた後、展開溶媒として、クロロホルムを用い、カラムクロマトグラフィーによって精製を行い、収率47％で目的物(２)を得た。

Compound (1) (1 g, 3.7 mmol), water (30 ml), and sulfuric acid (2 ml) were mixed and cooled to 5 ° C. or lower. Separately, sodium nitrite (manufactured by Kanto Chemical) (630 mg, 9.1 mmol) And a solution prepared with water (10 ml) were added dropwise while maintaining the temperature at 5 ° C. or lower. After completion of the dropwise addition, the mixture was stirred for 30 minutes, phosphinic acid (manufactured by Kanto Chemical) (20 ml) and ethanol (20 ml) were added, and the mixture was refluxed for 3 hours. After cooling to room temperature, the precipitated solid was collected by filtration. After drying the solid, purification was performed by column chromatography using chloroform as a developing solvent, and the target product (2) was obtained in a yield of 47%.

The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ HNMR (500MHz, CDCl ₃ ) δ7.93 (d, J = 8.6Hz, 1H), 7.89 (d, J = 7.8Hz, 1H), 7.46 (t, J = 1.5Hz, 2H), δ: 0.18 ( s, 18H, CH _3).

Compound (2) (1.0 g, 4.2 mmol) was added to dehydrated dichloromethane (100 ml) and cooled to −20 ° C. using an acetone / dry ice bath. Aluminum chloride (Wako Pure Chemicals, 1.9 g, 14.2 mmol) was added thereto, and the mixture was stirred for 1 hour. Furthermore, it cooled to -78 degreeC to temperature, and octanoyl chloride (product made from Tokyo Chemical Industry, 1.1g, 6.7mmol) was added there, and it stirred at the temperature for 1 hour.
After 1 hour, the mixture was returned to room temperature and stirred for another 4 hours. After the reaction, water was added to complete the reaction. Organic matter (9) was extracted with chloroform. The extracted solution was dried over magnesium sulfate and then dried under reduced pressure. The obtained solid was subjected to column purification using toluene as a developing solvent. The target product (3) was obtained with a yield of 64%.

The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ HNMR (500MHz, CDCl ₃ ) δ8.09 (d, J = 1.5Hz, 2H), 7.91 (d, J = 8.1Hz, 2H), 7.69 (d, J = 1.5Hz, 2H), δ: 0.18 ( s, 18H, CH _3).

A mixture of compound (3) (1.0 g, 2.7 mmol), hydrazine monohydrate (manufactured by Tokyo Chemical Industry, 1.0 g, 20 mmol) and potassium hydroxide (manufactured by Wako Pure Chemical Industries, 0.5 g, 8.91 mmol) was heated at 110 ° C. Stir for minutes. Thereafter, the temperature was raised to 200 ° C. and further stirred for 5 hours. After cooling to room temperature, the solid was filtered and washed with methanol. After drying the solid, purification was performed by column chromatography using hexane / toluene as a developing solvent, and the target product (4) was obtained in a yield of 90%.

The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ HNMR (500MHz, CDCl ₃ ) δ8.09 (d, J = 1.5Hz, 2H), 7.91 (d, J = 8.1Hz, 2H), 7.69 (d, J = 1.5Hz, 2H), δ: 0.18 ( s, 18H, CH _3).

Under a nitrogen atmosphere, 2.77M n-BuLi (manufactured by Kanto Chemical Co., Ltd., 1.1 ml, 3.0 mmol) was added dropwise to a dehydrated THF solution (100 ml) of (4) (1.0 g, 2.8 mmol) at −78 ° C. The mixture was returned to room temperature, stirred for 30 minutes, cooled again to −78 ° C., and 6-bromohexyloxy-tert-butyldimethylsilane (Aldrich, 0.84 g, 2.8 mmol) was added. It returned to room temperature and stirred for 2 hours. After adding water to stop the reaction, the organic layer was extracted with dichloromethane. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and dried. The obtained crude product (5) was used in the next reaction without purification.
¹ HNMR (500MHz, CDCl ₃ ) δ8.09 (d, J = 1.5Hz, 2H), 7.91 (d, J = 8.1Hz, 2H), 7.69 (d, J = 1.5Hz, 2H), δ: 0.18 ( s, 18H, CH _3).

Under a nitrogen atmosphere, 1.0 M tetrabutylammonium fluoride (Aldrich, 14 ml, 14 mmol) was added to a dehydrated THF solution (5 ml) of the crude product (5) (1.0 g, 1.8 mmol), and the mixture was stirred at room temperature for 24 hours. Water was added to stop the reaction, and the organic layer was extracted with ethyl acetate. The organic layer is dried over anhydrous magnesium sulfate and then dried. Column purification using ethyl acetate as a developing solvent was followed by recrystallization from hexane to obtain the desired product (6) in a yield of 80%. The structure of the obtained compound was analyzed by ¹ H-NMR.
The spectrum was confirmed.
¹ HNMR (500MHz, CDCl ₃ ) δ8.09 (d, J = 1.5Hz, 2H), 7.91 (d, J = 8.1Hz, 2H), 7.69 (d, J = 1.5Hz, 2H), δ: 0.18 ( s, 18H, CH _3).

Under a nitrogen atmosphere, dichloromethane solution (30 ml) in which (6) (0.59 g, 1.3 mmol) and triethylamine (manufactured by Wako Pure Chemicals, 0.26 g, 2.6 mmol) are dissolved in dichloromethane solution (10 ml at 0 ° C). ) And stirred at that temperature for 12 hours. Water was added to stop the reaction, and the organic layer was extracted with dichloromethane. The organic layer is dried over anhydrous magnesium sulfate and then dried. Column purification was performed using toluene as a developing solvent, and the target product (
7) was obtained. The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ HNMR (500MHz, CDCl ₃ ) δ8.09 (d, J = 1.5Hz, 2H), 7.91 (d, J = 8.1Hz, 2H), 7.69 (d, J = 1.5Hz, 2H), δ: 0.18 ( s, 18H, CH _3).

Compound (7) (1 g, 2.0 mmol) and 1,3-diaminopropane (manufactured by Kanto Chemical, 18 mg, 0.25 mmol) were refluxed in dehydrated THF for 2 weeks under a nitrogen atmosphere. After completion of the reaction, THF was distilled off to obtain a crude product as a powder. The obtained solid was dissolved in a small amount of chloroform, and n-hexane was added to reprecipitate the target product (7). This operation was repeated until the NMR peak of the acrylic group disappeared. The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ HNMR (500MHz, CDCl ₃ ) δ8.09 (d, J = 1.5Hz, 2H), 7.91 (d, J = 8.1Hz, 2H), 7.69 (d, J = 1.5Hz, 2H), δ: 0.18 ( s, 18H, CH _3).

Compound (7) (1 g, 2.0 mmol) and polypropyleneimine dendrimer first generation (PPID G1.0) (Aldrich, 40 mg, 0.13 mmol) were refluxed in dehydrated THF for 2 weeks under a nitrogen atmosphere. After completion of the reaction, THF was distilled off to obtain a crude product as a powder. The obtained solid was dissolved in a small amount of chloroform, n-hexane was added, and the target product (1 g) was reprecipitated. This operation was repeated until the NMR peak of the acrylic group disappeared. The structure of the obtained compound was confirmed by ¹ H-NMR spectrum.
¹ HNMR (500MHz, CDCl ₃ ) δ8.09 (d, J = 1.5Hz, 2H), 7.91 (d, J = 8.1Hz, 2H), 7.69 (d, J = 1.5Hz, 2H), δ: 0.18 ( s, 18H, CH _3).

《ＴＯＦ法による移動度の測定》
実施例１と同様の方法に従って、本発明のデンドリマー（１ｇ）の移動度を測定した結果、塗布法による成膜性が良好でありμ^TOF（２５℃）＝１．１×１０^-2ｃｍ²/Ｖ・ｓと
高い値を示した。

<< Measurement of mobility by TOF method >>
The mobility of the dendrimer (1 g) of the present invention was measured according to the same method as in Example 1. As a result, the film-forming property by the coating method was good, and μ ^TOF (25 ° C.) = 1.1 × 10 ⁻² cm ² A high value of / V · s was shown.

[Example 7]
<Synthesis of Dendrimer (1h) of the Present Invention>
It is represented by the formula (1h) according to the same method as in Example 1 except that M in the formula (1h) serving as the terminal group of the polypropyleneimine dendrimer was synthesized by the method described in JP-A-2006-339474. The dendrimer (1h) of the present invention could be obtained. The dendrimer is also expected to show good film formability and high mobility.

2 is a ¹ H-NMR spectrum of 2- (4-octylphenyl) -6-acryloyldecyloxynaphthalene obtained in Example 1. 2 is a ¹ H-NMR spectrum of the polypropylene imine dendrimer (1a) of the present invention obtained in Example 1. It is a block diagram of the apparatus used when orientation control was performed with respect to the cell for TOF using a magnetic field. 2 is a ¹ H-NMR spectrum of 2- (2-methyl-4-octyloxyphenyl) -6-acryloyldecyloxynaphthalene obtained in Example 2. FIG. 2 is a ¹ H-NMR spectrum of the polypropyleneimine dendrimer (1b) of the present invention obtained in Example 2.

Explanation of symbols

10 Magnetic field 12 Sample 14 ITO
16 Ceramic heater

Claims (16)

A dendrimer derived from a polyalkyleneimine dendrimer, wherein at least some of the terminal groups are groups selected from the group consisting of groups represented by formulas (B1) to (B5)

(In the formulas (B1) to (B5), Y ¹ is hydrogen, halogen, cyano, alkyl having 1 to 20 carbons or alkyl halide having 1 to 20 carbons, and Y ¹ is alkyl having 1 to 20 carbons. Or in the case of an alkyl halide having 1 to 20 carbon atoms, it is either a linear alkyl group or a branched alkyl group, and at least one —CH ₂ — in the group is —O—, —S—.
, -COO-, -OCO-, -CH = CH-, or -C≡C-, and the carbon in the group may be replaced by Si;
Z ¹ is alkylene having 1 to 30 carbon atoms, and at least one —CH ₂ — in the group is —CO—, —O—, —COO—, —OCO—, —CH═CH—, or —C ≡C— may be substituted, Z ² , Z ³ and Z ⁴ are independently a single bond, —CH═CH—, —C≡C
—, —CH ₂ —O—, —O—CH ₂ —, —COO—, or —OCO—, wherein Z ⁵ and Z ⁶ are independently a single bond or —C≡C—, Z ⁷ and Z ⁸ is independently a single bond, —CO
—, —O—, —CH═CH—, —C≡C—, —CH ₂ —O—, —O—CH ₂ —, —COO—, or —OCO—;
A ¹ , A ² , A ³ and A ⁴ are each independently a single bond, 1,4-cyclohexylene, 1,4-phenylene, 2,6-naphthalene, 2,5-pyrimidine, 2,5-pyridine, 2,6-benzothiazole or 2,5-oxadiazole (provided that A ¹ , A ² , A ³ and A ⁴
Of which at least three are independently 1,4-phenylene, 2,6-naphthalene, 2,5-pyrimidine, 2,5-pyridine, or 2,5-oxadiazole);
A ⁵ and A ⁷ are independently a single bond, 1,4-phenylene or 2,5-thiophene, A ⁶ is 1,4-phenylene or 2,6-naphthalene, and A ⁸ and A ⁹ are independently Single bond, 1,4-phenylene or 2,5-thiophene, and A ¹⁰ , A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are independently a single bond, fused thiophene, 2,5-thiophene, 2 , 2′-dithiophene, thiazolothiazole, fluorene, carbazole, or 1,4-phenylene (wherein at least one of A ¹⁰ , A ¹¹ , A ¹² , A ¹³ and A ¹⁴ is independently Condensed thiophene, thiazolothiazole, fluorene or carbazole);
p is an integer of 1 to 5. In the formulas (B1) to (B5), at least one hydrogen in the side orientation of 1,4-phenylene, 2,6-naphthalene, 2,5-thiophene, condensed thiophene, fluorene, and carbazole is halogen, cyano, It may be substituted with alkyl having 1 to 20 carbon atoms, or alkyl halide having 1 to 20 carbon atoms, and when substituted with alkyl having 1 to 20 carbon atoms or alkyl halide having 1 to 20 carbon atoms, At least one —CH ₂ — represents —O—, —S—, —CH═CH— or —.
C≡C— may be substituted. ). In the formulas (B1) to (B5), Y ¹ is a linear or branched alkyl having 1 to 20 carbon atoms (provided that at least one —CH ₂ — in the group is —O—, —COO—). , -OCO-
, -CH = CH- or -C≡C-), Z ² to Z ⁸ are single bonds. Formulas (B1) to (B5) of the end groups are represented by formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), The dendrimer according to claim 1, which is a group represented by (B4-b), (B5-a), (B5-b) or (B5-c);

(Formula (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a), In (B5-b) and (B5-c), Y ² is halogen or alkyl having 1 to 20 carbons, and when Y ² is alkyl having 1 to 20 carbons, linear alkyl or branched Any of the alkyls, wherein at least one —CH ₂ — in the group is —O—, —COO—, —OCO—, —CH═CH—, or —C≡C;
May be replaced by-;
Z ¹ is alkylene having 1 to 30 carbon atoms, and at least one —CH ₂ — in the group is —CO—, —O—, —COO—, —OCO—, —CH═CH—, or —C May be replaced by ≡C-;
A ¹⁵ and A ¹⁶ are each independently a single bond, 1,4-phenylene, 4,4′-biphenyl, or 2,6-naphthalene (provided that both A ¹⁵ and A ¹⁶ are single bonds, And A ¹⁵ and A ¹⁶ are both 4,4′-biphenyl);
A ¹⁷ , A ¹⁸ , A ¹⁹ and A ²⁰ are independently a single bond or 1,4-phenylene, and A ²¹ and A ²² are independently 1,4-phenylene, 2,5-thiophene, or 2 , 2′-bithiophene, and A ²³ and A ²⁴ are independently a single bond, 2,5-thiophene, or 1,4-phenylene;
q is an integer from 3 to 7;
Also, the formulas (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a) , (B5-b) and (B5-c), at least one hydrogen in the side orientation of 1,4-phenylene, 2,6-naphthalene, 4,4′-biphenyl and 2,5-thiophene is halogen, May be replaced with methyl or ethyl. ). Formula (B1-a), (B1-b), (B2-a), (B3-a), (B3-b), (B4-a), (B4-b), (B5-a), In (B5-b) and (B5-c), Y ² is linear or branched alkyl having 1 to 20 carbon atoms (provided that at least one —CH ₂ — in the group is —O—, — COO—, —OCO—, —CH═CH— or —C≡C— may be substituted), A ¹⁵ is a single bond, A ¹⁶ is 1,4-phenylene, A ¹⁷ and A ¹⁸ is a single bond, A ¹⁹ and A ²⁰ are single bonds, A ²¹ and A ²² are 2,2′-bithiophene, and A ²³ and A ²⁴ are independently a single bond or 2,5-thiophene. The dendrimer according to claim 3.   The terminal group is represented by the formula (B1-a), (B2-a), (B3-a), (B3-b), (B4-b), (B5-b) or (B5-c). The dendrimer according to claim 3 or 4, which is a group.   The dendrimer according to claim 3 or 4, wherein the terminal group is a group represented by the formula (B1-a).   The dendrimer according to claim 3 or 4, wherein the terminal group is a group represented by the formula (B2-a).   The dendrimer according to claim 3 or 4, wherein the terminal group is a group represented by the formula (B4-b).   The dendrimer according to any one of claims 1 to 8, wherein the polyalkyleneimine dendrimer is a polypropylene imine dendrimer.   The dendrimer according to any one of claims 1 to 9, wherein the generation number is 0 to 5.   The dendrimer according to any one of claims 1 to 10, which has a liquid crystal phase at 25 ° C.   The dendrimer according to claim 11, wherein the liquid crystal phase is a smectic phase.   The organic semiconductor using the dendrimer in any one of Claims 1-12.   The organic semiconductor according to claim 13, wherein the orientation is increased by using a magnetic field.   An organic transistor using the organic semiconductor according to claim 13.   An organic transistor using the organic semiconductor according to claim 14.

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