JP2009224216A - Conductive material for electronic device containing indolocarbazole polymer substance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic conductive material for an electronic device which has high solubility and conductivity and is used in the field of organic electronics. <P>SOLUTION: This organic conductive material for an electronic device contains a polymer substance provided by oxidation polymerization of a 6, 12-diarylindolo [3, 2-b] carbazole derivative, or a doped organic conductive polymer substance provided by doping, in the polymer substance, an electron-accepting substance such as a halogen, protic acid, polymer protic acid, Lewis acid, transition metal salt, tetracyanoethylene, tetracyanoquinodimethane, chloranil or oxygen. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic conductive material for electronic devices having high conductivity and solvent solubility. Specifically, the present invention relates to a polymer obtained by oxidative polymerization of a diarylindolo [3,2-b] carbazole derivative and an organic conductive material for electronic devices obtained therefrom. Organic conductive materials for electronic devices with high conductivity and solvent solubility are organic semiconductor lasers, organic transistors, organic light emitting diodes, electroluminescence, organic solar cells, optical disk memories, antistatic agents, electromagnetic wave absorption shields, chemical sensors Suitable for applications such as display elements, nonlinear materials, conductive adhesives, transparent conductive films, and wiring.

  As organic conductive materials for electronic devices having high conductivity, conductive polymer materials having a π-conjugated system such as polyacetylene, polyaniline, polypyrrole, polythiophene, and polyphenylene vinylene are mainly known. The development of these conductive materials focuses on improving the conductivity of these materials, and as a result, antistatics, electrolytic capacitors, and the like have been developed according to the characteristics such as conductivity. On the other hand, it is expected to be applied to more uses by utilizing semiconducting characteristics, nonlinear optical effects, photoelectric conversion characteristics, thermoelectric conversion characteristics, etc. that organic conductive materials potentially have. There are still many challenges in this area.

  As a method for manufacturing an electronic device using an organic conductive material, there are known three types, that is, an electrolytic polymerization method, a vapor deposition method, and a coating method. The electrolytic polymerization method is a method of obtaining an element by polymerizing a conductive polymer monomer such as aniline or pyrrole on an electrode, and is used for manufacturing an electrolytic capacitor or the like. On the other hand, in order to obtain an element such as a transistor, a laser, or a solar cell, a vapor deposition method or a coating method is used. The vapor deposition method is a method of depositing a conductive material under vacuum, and is mainly used in the development stage of low molecular weight materials. If this method is to be implemented on a commercial production basis, there will be a problem of whether or not a vacuum deposition apparatus can be introduced for cost and equipment management. On the other hand, it is expected that a polymer material having a molecular structure in which a π-conjugated system further spreads will exhibit a higher conductivity than a low-molecular material. Since it is difficult, a coating method using a conductive polymer having solvent solubility has been proposed. The coating method is a method in which a solution in which an organic conductive material is dissolved in a solvent is prepared, and the obtained solution is coated by various methods and then dried to obtain an element. However, a conductive material having solvent solubility is used. Usually, the low conductivity is a problem, and there is a demand for the development of a material having a new chemical structure that can be applied to a coating method while maintaining high properties with respect to conductivity.

  Under such circumstances, development relating to solubilization of conductive polymers has been made in order to cope with the coating method. For example, in the case of polyaniline, which is a conductive polymer, a solution is prepared using a polyaniline emeraldine base that has solvent solubility but has an insulating property, and then molding is performed using this solution, followed by doping. It has been proposed to convert it into a conductive emeraldine salt (Patent Document 1). Further, as a solubilization method, it is known that solubility in an aqueous solvent can be imparted by introducing an alkyl sulfonic acid group into polyaniline, polythiophene or the like (Patent Document 2). Further, a method (non-patent document 1) by performing regioregular polymerization of alkylthiophene is known.

  On the other hand, among organic conductive materials, organic semiconductor materials focused on semiconductor characteristics are being developed for solubilization in the same manner as conductive polymers. As a low molecular weight material, it has been reported that an organic semiconductor material having solvent solubility can be obtained by introducing an alkyl group into a thiophene oligomer or indolocarbazole, but the solubility is not practically sufficient. Furthermore, there is no knowledge that the conductive properties are excellent (Patent Documents 3 and 4). As a polymer semiconductor material, it is known that a thiophene oligomer or indolocarbazole polymer into which an alkyl group is introduced becomes a solvent-soluble semiconductor material, but its solubility is not practically sufficient. Furthermore, there is no knowledge that the conductive properties are excellent (Patent Documents 5 and 6, Non-Patent Document 1).

Japanese Patent Laid-Open No. 03-28229 JP-A-7-330901 JP 2007-19294 A US Published Patent No. 2006-125209 JP 2006-183048 A JP 2006-193729 A The latest collection of latest conductive material technologies, Technical Information Association, 2007

  Under such circumstances, development of an organic conductive material having high solvent solubility has been eagerly desired. An object of the present invention is to provide an organic conductive material having high conductivity and solvent solubility used in the field of organic electronics.

  As a result of intensive investigations to solve the above-described problems of the prior art, the present inventors contain a polymer obtained by oxidative polymerization of a 6,12-diarylindolo [3,2-b] carbazole derivative. The present inventors have found that the material to be used has high conductivity and solvent solubility, and have reached the present invention.

  That is, the present invention is an organic conductive polymer for an electronic device, which is a polymer obtained by oxidative polymerization of a 6,12-diarylindolo [3,2-b] carbazole derivative.

（一般式（１）及び（２）において、６，１２−位のＡｒは、それぞれ独立に、置換基を有しても良い炭素数３〜２０のアリール基を示す。Ｒ¹は、それぞれ独立に、水素、アルキル基、アルケニル基、アシル基、スルホニル基又は置換基を有しても良い炭素数３〜２０のアリール基を示す。Ｒ²は、それぞれ独立に、水素、ハロゲン原子、アルキル基、アルケニル基、水酸基、アルコキシ基、アルコキシアルキル基、アシル基、アルコキシカルボニル基、アミド基、ニトロ基、シアノ基、スルホニル基、置換若しくは無置換のアミノ基又は置換基を有しても良い炭素数３〜２０のアリール基を示す。） The 6,12-diarylindolo [3,2-b] carbazole derivative is a derivative represented by the following general formula (1), and the polymer is a polymer represented by the following general formula (2). Preferably exemplified.

(In the general formula (1) and (2), 6,12-position of Ar are each independently, .R ¹ showing the aryl group of 3 to 20 carbon atoms which may have a substituent, each independently And hydrogen, an alkyl group, an alkenyl group, an acyl group, a sulfonyl group, or an aryl group having 3 to 20 carbon atoms which may have a substituent, each R ² independently represents a hydrogen atom, a halogen atom, or an alkyl group. , Alkenyl group, hydroxyl group, alkoxy group, alkoxyalkyl group, acyl group, alkoxycarbonyl group, amide group, nitro group, cyano group, sulfonyl group, substituted or unsubstituted amino group or carbon number that may have a substituent 3 to 20 aryl groups are shown.)

In the general formulas (1) and (2), R ¹ is preferably hydrogen, alkyl, or an aryl group having 3 to 20 carbon atoms which may have a substituent.

  In addition, the present invention is an organic conductive polymer for electronic devices, wherein the organic conductive polymer for electronic devices is doped with an electron accepting substance. Here, the electron accepting substance is preferably at least one selected from halogen, protonic acid, polymer protonic acid, Lewis acid, transition metal salt, tetracyanoethylene, tetracyanoquinodimethane, chloranil, or oxygen. It is done.

  Furthermore, this invention is an organic electroconductive material for electronic devices characterized by including said organic electroconductive polymer for electronic devices.

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroconductive material for electronic devices which has high electroconductivity and solvent solubility can be provided.

  The organic conductive polymer for electronic devices of the present invention is a polymer obtained by oxidative polymerization of a 6,12-diarylindolo [3,2-b] carbazole derivative. The organic conductive polymer for electronic devices of the present invention is a polymer obtained by doping the above polymer with an electron-accepting substance, and is an undoped polymer or an organic conductive polymer for electronic devices. When referred to as doped polymer or doped organic conductive polymer for electronic devices. And the organic conductive material for electronic devices of this invention contains the organic conductive polymer for electronic devices mentioned above, or the doped organic conductive polymer for electronic devices. Hereinafter, the organic conductive polymer for electronic devices may be abbreviated as a conductive polymer or polymer, and the organic conductive material for electronic devices may be abbreviated as a conductive material.

  The conductive polymer of the present invention can be obtained by oxidative polymerization of a 6,12-diarylindolo [3,2-b] carbazole derivative. As the 6,12-diarylindolo [3,2-b] carbazole derivative, a compound represented by the above general formula (1) is suitable. The conductive polymer obtained by oxidative polymerization of the compound represented by the general formula (1) is represented by the above general formula (2). In the general formula (1) and the general formula (2), it is understood that the same symbols have the same meaning, so both formulas will be described as a representative of the general formula (1).

  In the general formula (1), Ars at the 6,12-positions each independently represent an aryl group having 3 to 20 carbon atoms which may have a substituent. In the present specification, an aryl group is used to mean a heteroaryl group.

  The Ar or aryl group includes a carbocyclic aromatic group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, or a heterocyclic aromatic group having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms. These carbocyclic aromatic groups or heterocyclic aromatic groups may have a substituent, and the substituent is included in the calculation of the carbon number. In the case of a heterocyclic aromatic group, there are nitrogen, sulfur, oxygen and the like as heteroatoms constituting the ring.

  Examples of the carbocyclic aromatic group include a phenyl group, a naphthyl group, a biphenylyl group, an anthranyl group, a terphenylyl group, a phenanthryl group, a fluorenyl group, a chrysenyl group, a pyrenyl group, a perylenyl group, and a coronenyl group.

  Heterocyclic aromatic groups include furyl, benzofuryl, thienyl, benzothienyl, thienothienyl, quinolyl, pyridyl, pyrazyl, pyrimidyl, prill, isoquinolyl, naphthyridyl, quinoxalyl, quinazolyl Group, pteridyl group, carbazolyl group, phenanthridyl group, acridyl group, perimidyl group, phenanthrolyl group, phenazinyl group, indolyl group, pyrrolyl group and the like.

  Examples of the substituent that these aryl groups may have include halogen atoms such as fluorine, chlorine, bromine and iodine, alkyl groups having 1 to 20 carbon atoms, hydroxyl groups, alkoxy groups having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Examples thereof include 20 alkoxyalkyl groups, nitro groups, cyano groups, alkoxycarbonyl groups having 1 to 20 carbon atoms, and substituted or unsubstituted amino groups. Examples of the amino group having a substituent include an alkylamino group, a dialkylamino group, and an aromatic substituted amino group. For example, an alkylamino group having a C1-C20 alkyl group and a C1-C20 dialkylamino group can be exemplified. Aromatic substituted amino groups include phenyl, naphthyl, biphenyl, anthranyl, terphenyl, phenanthryl, fluorenyl, chrysenyl, pyrenyl, triphenylenyl, perylenyl, coronenyl, furyl, benzofuryl , Thienyl group, benzothienyl group, thienothienyl group, quinolyl group, pyridyl group, pyrazyl group, pyrimidyl group, prill group, isoquinolyl group, naphthyridyl group, quinoxalyl group, quinazolyl group, pteridyl group, carbazolyl group, phenanthridyl group, acridyl group, Examples thereof include aromatic substituted amino groups having a perimidyl group, a phenanthrolyl group, a phenazinyl group, an indolyl group, a pyrrolyl group and the like as a substituent. Here, in a C1-C20 alkyl group, an alkoxy group, an alkoxyalkyl group, or a dialkylamino group, the preferable carbon number of alkyl or alkoxy is 1-6.

  Preferred examples of Ar include a phenyl group or a substituted phenyl group. In the case of a substituted phenyl group, preferred examples of the substituent include an alkyl group, an alkoxy group, an alkoxyalkyl group, an amino group or an alkylamino group, and a dialkylamino group. There is. Here, the number of carbon atoms of the substituent is preferably 1 to 4 (excluding the unsubstituted amino group).

R ¹ at the 5,11-position in the general formula (1) is each independently 3 to 20 carbon atoms which may have hydrogen, an alkyl group, an alkenyl group, an acyl group, a sulfonyl group or a substituent. An aryl group is shown.

  The alkyl group includes an alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, and the alkenyl group includes an alkenyl group having 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms. The acyl group includes an acyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and includes a formyl group, an acetyl group, a propionyl group, an n-butyryl group, an isobutyryl group, a sec-butyryl group, a benzoyl group, and a naphthyl group. Quinolylcarbonyl group, pyridylcarbonyl group and the like. As the sulfonyl group, an alkylsulfonyl group having an alkyl group having 1 to 20 carbon atoms, or an aromatic sulfonyl group such as benzenesulfonyl or toluenesulfonyl can be used.

  Examples of the aryl group that may have a substituent include the same aryl groups as those described above for Ar. That is, a C6-C20 carbocyclic aromatic group which may have a substituent, or a carbon group which may have a substituent composed of heteroatoms such as carbon, nitrogen, sulfur and oxygen There are ~ 20 heterocyclic aromatic groups. Examples of the carbocyclic aromatic group include a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group, a terphenyl group, a phenanthryl group, a fluorenyl group, a chrysenyl group, a pyrenyl group, a triphenylyl group, a perylenyl group, and a coronenyl group. In addition, the heterocyclic aromatic group includes a furyl group, a benzofuryl group, a thienyl group, a benzothienyl group, a thienothienyl group, a quinolyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, a prill group, an isoquinolyl group, a naphthyridyl group, a quinoxalyl group. Quinazolyl group, pteridyl group, carbazolyl group, phenanthridyl group, acridyl group, perimidyl group, phenanthrolyl group, phenazinyl group, indolyl group, pyrrolyl group, triazinyl group and the like. Examples of the substituent that the aryl group which may have a substituent may have include a halogen atom such as fluorine, chlorine, bromine and iodine, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, and an alkoxy having 1 to 20 carbon atoms. Group, an alkoxyalkyl group having 1 to 20 carbon atoms, a nitro group, a cyano group, an alkoxycarbonyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted amino group. Examples of the amino group having a substituent include an alkylamino group, a dialkylamino group, and an aromatic substituted amino group. For example, an alkylamino group having a C1-C20 alkyl group and a C1-C20 dialkylamino group can be exemplified. Aromatic substituted amino groups include phenyl, naphthyl, biphenyl, anthranyl, terphenyl, phenanthryl, fluorenyl, chrysenyl, pyrenyl, triphenylenyl, perylenyl, coronenyl, furyl, benzofuryl , Thienyl group, benzothienyl group, thienothienyl group, quinolyl group, pyridyl group, pyrazyl group, pyrimidyl group, prill group, isoquinolyl group, naphthyridyl group, quinoxalyl group, quinazolyl group, pteridyl group, carbazolyl group, phenanthridyl group, acridyl group, Examples thereof include aromatic substituted amino groups having a perimidyl group, a phenanthrolyl group, a phenazinyl group, an indolyl group, a pyrrolyl group and the like as a substituent.

R ² in the general formula (1) is independently hydrogen, halogen atom, alkyl group, alkenyl group, hydroxyl group, alkoxy group, alkoxyalkyl group, acyl group, alkoxycarbonyl group, amide group, nitro group, cyano. A group, a sulfonyl group, a substituted or unsubstituted amino group, and an aryl group having 3 to 20 carbon atoms which may have a substituent;

Examples of the halogen include halogen atoms such as fluorine, chlorine, bromine and iodine. Examples of the alkyl group, alkenyl group, alkoxy group, acyl group, and sulfonyl group include the same alkyl group, alkenyl group, alkoxy group, acyl group, and sulfonyl group as described for R ¹ above. Examples of the amide group include aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, phenylaminocarbonyl, diphenylaminocarbonyl and the like. The aryl group which may have a substituent includes an aryl group which may have a substituent similar to that described for Ar or R ¹ above.

Table 1 shows preferred specific examples of the 6,12-diarylindolo [3,2-b] carbazole derivative represented by the general formula (1). In Table 1, Ar, R ^1, R ² is Ar in the general formula (1), means R ^1, R ^2.

  The 6,12-diarylindolo [3,2-b] carbazole derivative represented by the general formula (1) is, for example, EP908787, Tetrahedron, vol51, No43, pp11801-11808 (1995) or Tetrahedron, vol55. , No43, pp12577-12594 (1999).

Specifically, it can be synthesized by the method shown in the following formula.

  That is, the substituted or unsubstituted indole is dissolved in an appropriate solvent, and an appropriate acid is added, followed by condensation and dehydrogenation with an aldehyde (Ar-CHO) at an appropriate reaction temperature for a certain period of time. Thus, a 6,12-diarylindolo [3,2-b] carbazole derivative having no substituent can be obtained. Then, a desired compound can be obtained by performing functional group modification to the 5th and 11th positions as necessary. In addition, the target product can be obtained in a single step by performing a condensation reaction of N-substituted indole and aldehyde (Ar-CHO).

By the oxidative polymerization reaction of the 6,12-diarylindolo [3,2-b] carbazole derivative represented by the general formula (1) obtained by such a method, a polymer represented by the general formula (2) is obtained. be able to. As described above, the symbols (Ar, R ¹ and R ² ) in the general formula ( ² ) have the same meaning as the Ar, R ¹ and R ² described in the general formula (1). Note that n represents the number of repetitions, and the average value is 10 to 1000, preferably 50 to 500. Further, the number average molecular weight Mw of the polymer may be in the range of 5,000 to 1,000,000, preferably 10,000 to 500,000. When the molecular weight is less than 5,000, the conductivity decreases.

  Various reactions can be used for the oxidative polymerization reaction, and examples thereof include a method based on an oxidative coupling reaction using an oxidation catalyst such as iron chloride.

  In the case of an oxidative coupling reaction using an oxidation catalyst, a polymer is obtained by reacting a 6,12-diarylindolo [3,2-b] carbazole derivative with an oxidizing agent in the presence of an oxidation catalyst. Obtainable.

  The oxidizing agent used for the polymerization is not particularly limited. For example, iron (III) chloride anhydrous, iron chloride (III) hexahydrate, iron sulfate (III) n hydrate, iron nitrate (III) nonahydrate , Ammonium iron (III) sulfate 12 hydrate, iron (III) perchlorate n hydrate, copper (II) chloride anhydrous, copper (II) sulfate, copper (II) nitrate, copper (II) tetrafluoroborate , Hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, and the like. Of these, anhydrous iron (III) chloride and iron (III) chloride hexahydrate are preferred.

  The molar ratio of the 6,12-diarylindolo [3,2-b] carbazole derivative (a) and the oxidizing agent (b) used in the polymerization reaction is preferably (a) :( b) = 1: 1 to 10, preferably Is in the range of 1: 1 to 1: 5. Here, when the ratio of the oxidizing agent is low, the reaction rate is lowered and the raw material remains.

  The polymerization reaction temperature is preferably in the range of -20 ° C to 200 ° C. More preferably, it is the range of 0 degreeC to 160 degreeC. The reaction solvent is not limited as long as the 6,12-diarylindolo [3,2-b] carbazole derivative used as a raw material at the reaction temperature exhibits a certain solubility and does not affect the reaction. Halogen solvents such as chloroform, dichloromethane, chlorobenzene and dichlorobenzene, aromatic solvents such as toluene, xylene and mesitylene, and ether solvents such as isopropyl ether and dimethoxyethane.

  Polymers of 6,12-diarylindolo [3,2-b] carbazole derivatives exhibit solubility in various solvents. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, aromatic solvents such as benzene, toluene, xylene, mesitylene, dimethylformamide Amide aprotic solvents such as dimethylacetamide and dimethylimidazolidinone, ester solvents such as ethyl acetate and methyl benzoate, nitrile solvents such as acetonitrile, butyronitrile, adiponitrile, chloroform, dichloromethane, tetrachloroethane, chlorobenzene, diene It is soluble in chlorinated solvents such as chlorobenzene, nitro solvents such as nitromethane and nitrobenzene, and solvents such as water. By using such a solvent, a solution of the polymer can be obtained.

  In addition, a polymer obtained by oxidative polymerization of a 6,12-diarylindolo [3,2-b] carbazole derivative has conductivity, but the conductivity is improved by doping an electron accepting substance. Will improve. Note that the electron-accepting substance is also referred to as an electron-accepting compound or an electron acceptor.

Examples of the electron accepting substance include halogens such as bromine and iodine, PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , SO ₃ , GaCl ₃ , NbF ₅ , TaF ₅ , MoF ₅ , WF ₅ , RuF _{5. , BiF 5, TiCl 4, ZrCl} 4, HfCl 4, NbCl 5, TaCl 5, MoCl 5, FeCl 3, MoCl 3, WCl 5, SnCl 4, TeCl 4, SeCl 4, FeBr 3, TaBr 3, TeI 4, TaI _5, SnI _5, AuCl _3, etc. Lewis _{acids, AgClO 4, AgBF 4, H} 2 IrCl 6, Ce (NO 3) 3, Dy (NO 3) 3, La (NO 3) 3, Pr (NO 3) 3 , Transition metal salts such as Sm (NO ₃ ) ₃ , Yb (NO ₃ ) ₃ , hydrogen chloride, sulfuric acid, nitric acid, perchloric acid, tetrafluoroboric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, Protonic acids such as trifluoroacetic acid and trifluoromethanesulfonic acid, polymeric protonic acids such as tetracyanoethylene, tetracyanoquinodimethane, chloranil, oxygen, polystyrene sulfonic acid, polyvinyl sulfonic acid, polybutadiene sulfonic acid, and polyhydroxy ether sulfonic acid Etc. can be illustrated.

  Among these, at least one selected from halogen, proton acid, polymer proton acid, Lewis acid, transition metal salt, tetracyanoethylene, tetracyanoquinodimethane, chloranil, or oxygen can be exemplified as a preferable electron accepting substance.

  The method of doping the polymer with an electron accepting substance can be performed in a gas phase and a liquid phase. For example, when carried out in the gas phase, it can be carried out by exposing the polymer to a gas of the desired electron accepting compound. In the case of carrying out in a liquid phase, it can be carried out by preparing an electron accepting compound solution by dissolving a desired electron accepting compound in an appropriate solvent and dissolving or immersing the polymer in this solution.

  By increasing the doping rate of the electron acceptor with respect to the polymer, an organic conductive material having high conductivity can be obtained. The doping ratio varies depending on the type of electron acceptor to be doped, but is 1 wt% to 500 wt%, preferably 10 wt% to 300 wt% with respect to the polymer.

  A polymer obtained by oxidative polymerization of a 6,12-diarylindolo [3,2-b] carbazole derivative or a doped polymer obtained by doping this polymer with an electron-accepting substance is a conductive material of the present invention. Can be used as material.

  In order to use it as a conductive material, it can be molded into a desired form, for example, a tablet, a film, a thin film, or the like, if necessary. For example, when a tablet is to be obtained, a molded product can be obtained by filling the above-mentioned polymer or doped polymer powder in a mold, followed by pressure molding. When trying to obtain a film or thin film, after dissolving the polymer or doped polymer in a solvent, cast or spin coat the solution on a glass plate, etc., and then remove the solvent by drying. Can do.

  In addition to the polymer or doped polymer, the conductive material of the present invention may contain a colorant, an adhesive, a filler, another polymer, or the like, if necessary.

  The organic conductive material for an electronic device of the present invention includes an organic semiconductor laser, an organic transistor, an organic light emitting diode, electroluminescence, an organic solar cell, an optical disk memory, an antistatic agent, an electromagnetic wave absorption shield, a chemical sensor, a display element, a nonlinear material, It can be used for conductive adhesives, transparent conductive films, wirings and the like. The organic conductive material for electronic devices of the present invention is mixed with a thermoplastic resin such as polyethylene and then molded into a desired form, thereby making use of conductivity, for example, a conductive resin sheet, charging It can be used for an inhibitor, electromagnetic wave shield and the like. Moreover, the transparent conductive film which provided the electroconductivity to the surface of a transparent film can be obtained by casting the solution of the electroconductive material of this invention to transparent films, such as polyethylene, a polypropylene, a polyethylene naphthalate, a polystyrene, and a polymethacrylate. it can.

  Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the description of the following examples, and can be implemented with appropriate modifications without departing from the scope of the present invention. is there.

Unless otherwise stated, analysis data of synthesized compounds are as follows. ^{For 1} H-NMR, JNM-LA400 (400 MHz) manufactured by JEOL Ltd. was used. For mass spectrum, JMS-AX505HA manufactured by JEOL Ltd. was used. The conductivity was measured with a Lorester meter MCP-T610 manufactured by Mitsubishi Chemical (4-terminal method: distance between electrodes: 1.5 mm).

  The polymer (21) is poly (6,12-diphenyl-indolo [3,2-b] carbazole-2,8-diyl) represented by the following formula (21), and the polymer (22) is Poly (6,12-diphenyl-5,11-octylindolo [3,2-b]) carbazole-2,8-diyl) represented by the formula (22).

Example 1
A 500 ml three-necked flask was charged with 11.7 g (0.1 mol) of indole, 10.6 g (0.1 mol) of benzaldehyde and 200 g of methanol at room temperature, and then 15.0 g (0.15 mol) of sulfuric acid with stirring. Was added dropwise over 15 minutes. Heated to reflux for 3 hours. After cooling to room temperature, the produced precipitate was filtered off and dried under reduced pressure at 50 ° C. This precipitate was washed with 100 g of ethyl acetate, and the residue was dried under reduced pressure at 50 ° C. to obtain 7.4 g of 6,12-diphenyl-5,6,11,12-4H-indolo [3,2-b] carbazole. .
1H-NMR (DMSO-d6) δ (ppm): 10.69 (2H, brs), 7.33 (4H, d, J = 7 Hz), 7.27 (4H, t, J = 7 Hz), 7. 23 (2H, d, J = 7 Hz), 7.18 (2H, t, J = 7 Hz), 7.07 (2H, d, J = 8), 6.94 (2H, dt, J = 1, 8 Hz) ), 6.78 (2H, dt, J = 1, 8 Hz), 5.69 (2H, s)
FD-MS (M / z): 410 (M +)

The obtained 6,12-diphenyl-5,6,11,12-4H-indolo [3,2-b] carbazole 3.3 g (8.0 mmol) and chloranil 2.07 g (8.43 mmol) were converted into 66 g of xylene. Suspended, heated to reflux for 5 hours, and dehydrogenated. After cooling to room temperature, the reaction mixture was filtered, and the resulting precipitate was washed with 50 g of methanol. The obtained residue was dried at 50 ° C. under reduced pressure to obtain 2.73 g of 6,12-diphenyl-indolo [3,2-b] carbazole.
1H-NMR (DMSO-d6) δ (ppm): 10.61 (2H, brs), 7.43 (4H, d, J = 7 Hz), 7.15-7.34 (8H, m), 7. 05 (2H, d, J = 8 Hz), 7.05 (2H, d, J = 8 Hz), 6.93 (2H, t, J = 8 Hz), 6.80 (2H, t, J = 8 Hz)
FD-MS (M / z): 408 (M +)

The obtained 6,12-diphenyl-indolo [3,2-b] carbazole was placed in a petri dish and allowed to stand in a desiccator containing iodine for one day. Iodine-treated (doping) was pressure-molded with a tablet molding machine, cut into a circle with a diameter of 13 mm, and the conductivity was measured by the four-terminal method. It was 2.3 × 10 ⁻² S / cm. It was.

  In a 300 ml three-necked flask, 3.01 g (7.33 mmol) of 6,12-diphenyl-indolo [3,2-b] carbazole, 160 g of dimethoxyethane, 6.43 g (39.6 mmol) of iron (III) chloride were added. Added at room temperature under nitrogen atmosphere. The reaction was carried out at room temperature for 5 hours and then under reflux for 3 hours. After the reaction, the mixture was cooled to room temperature and suction filtered. The solid on the filter paper obtained by filtration was washed with 130 ml of 6N hydrochloric acid, then twice with 150 g of distilled water, and finally with 20 g of methanol. The obtained residue was dried at 60 ° C. under reduced pressure to obtain 1.53 g of a polymer (21). The solubility of this product in chloroform at room temperature was 0.8 wt%. As a result of GPC measurement of this precipitate, the molecular weight was 35,000.

The obtained polymer (21) was press-molded with a tablet molding machine, cut into a circular shape with a diameter of 13 mm, and the conductivity was measured by the four-terminal method. It was 2.7 × 10 ⁻² S / cm. It was.
On the other hand, 1.5 g of the polymer (21) powder was placed in a petri dish and allowed to stand in a desiccator containing iodine for iodine doping. One day later, since the weight of the powder was 2.7 g, it was found that the dope amount was 1.2 g and the dope ratio was 80 wt% with respect to the polymer (21). The iodine-doped powder was pressure-molded with a tablet molding machine to prepare a tablet, and the electrical conductivity was measured by the direct current four-terminal method. As a result, it was 6.0 S / cm. The solubility of the powder obtained by pulverizing the tablet in a mortar with respect to chloroform was 1.2 wt%.
The conductivity of iodine-doped polymer of monomer is significantly improved to 6.0 S / cm compared to the conductivity of monomer-iodine-doped 2.3 × 10 ^-2 S / cm. The effect of became clear.

Example 2
A 100 ml three-necked flask was charged with 0.68 g (17.7 mmol) of sodium hydride and 10 ml of N, N-dimethylformamide at room temperature and stirred for 10 minutes under a nitrogen atmosphere. To the obtained suspension, a solution of 3.02 g (7.35 mmol) of 6,12-diphenyl-indolo [3,2-b] carbazole in 40 ml of N, N-dimethylformamide was added dropwise over 3 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and 3.41 g (17.7 mmol) of n-octyl bromide was charged into the resulting solution. The reaction was performed at 50 ° C. for 62 hours. After the reaction, the mixture was cooled to room temperature, 35 ml of water was added, and the mixture was stirred for 30 minutes. The reaction solution was filtered off, and the solid on the filter paper was washed with 90 g of water and then with 15 g of hexane. The washed solid was dried under reduced pressure at 60 ° C. to obtain 1.59 g of 6,12-diphenyl-5,11-octyl-indolo [3,2-b] carbazole.
1H-NMR (DMSO-d6) δ (ppm): 7.70-7.65 (10H, m), 7.40 (2H, d, J = 8 Hz), 7.29 (2H, t, J = 8 Hz) ), 6.75 (2H, t, J = 8 Hz), 6.34 (2H, d, J = 8 Hz), 3.78 (4H, t, J = 8 Hz), 1.40-0.83 (30H) , M)
FD-MS (M / z): 633 (M +)

The obtained 6,12-diphenyl-5,11-octyl-indolo [3,2-b] carbazole was placed in a petri dish and allowed to stand for one day in a desiccator containing iodine. The iodine-treated product was pressure-molded with a tablet molding machine, cut into a circular shape with a diameter of 13 mm, and the conductivity was measured by the four-terminal method. As a result, it was 7.1 × 10 ⁻² S / cm.

To a 200 ml three-necked flask, 1.33 g (8.19 mmol) of iron (III) chloride and 44 g of monochlorobenzene were added at room temperature under a nitrogen atmosphere. The reactor was immersed in an ice bath and stirred and cooled to 2 ° C. Thereto was added dropwise a solution of 22 g of monochlorobenzene in 1.27 g (2.00 mmol) of 6,12-diphenyl-5,11-octyl-indolo [3,2-b] carbazole over 10 minutes. After the dropwise addition, the ice bath was removed, and the reaction was carried out at room temperature for 22 hours and then at 110 ° C. for 72 hours. After the reaction, the mixture was cooled to room temperature and suction filtered. The solid on the filter paper obtained by filtration was washed with 35 ml of 6N hydrochloric acid, then twice with 60 g of distilled water, and finally with 20 g of methanol. The obtained residue was dried under reduced pressure at 60 ° C. to obtain 0.87 g of a polymer (22). The solubility of this product in chloroform at room temperature was 1.3 wt%. As a result of GPC measurement of this precipitate, the molecular weight was 33,000.
1H-NMR (CDCl3) δ (ppm): 7.66-7.63 (12H, m), 7.27 (2H, dd, J = 8, 2 Hz), 7.14 (2H, d, J = 8 Hz) ), 6.35 (2H, d, J = 2 Hz), 3.75 (4H, t, J = 8 Hz), 1.5
0-0.84 (30H, m)

The obtained polymer (22) was pressure-molded with a tablet molding machine, cut into a circle having a diameter of 13 mm, and the conductivity was measured by a four-terminal method. The result was 5.4 × 10 ⁻³ S / cm. It was.
Iodine doping was performed by placing 0.5 g of the polymer (22) powder obtained here in a petri dish and standing in a desiccator containing iodine. One day later, since the weight of the powder was 0.85 g, it was found that the dope amount was 0.35 g and the dope ratio was 70 wt% with respect to the polymer (22). The iodine-doped powder was pressure-molded with a tablet molding machine to produce a tablet, and the electrical conductivity was measured by the direct current four-terminal method. As a result, it was 3.0 S / cm. The solubility of the powder obtained by pulverizing the tablet in a mortar with respect to chloroform was 2.2 wt%.

Comparative Example 1
Poly (5,11-octylindolo [3,2-b] carbazole-2,8-diyl) was synthesized by the method described in JP-A-2006-193729. This polymer did not show solubility in chloroform at room temperature. This was pressure-molded with a tablet molding machine, cut into a circular shape with a diameter of 13 mm, and the conductivity was measured by the four-terminal method, but the conductivity could not be confirmed.
Iodine doping was performed by putting 1.0 g of the polymer powder obtained here in a petri dish and allowing it to stand in a desiccator containing iodine. One day later, since the weight of the powder was 1.5 g, it was found that the dope amount was 0.5 g and the dope ratio was 50 wt% with respect to the polymer. The iodine-doped powder was pressure-molded with a tablet molding machine to produce tablets, and the conductivity was measured by the direct current four-terminal method. As a result, it showed 4.6 × 10 ⁻⁵ S / cm. The iodine iodine product showed no solubility in chloroform at room temperature.

The results of Examples and Comparative Examples are shown in Table 2.

  As shown in the examples and comparative examples. It has been clarified that a polymer of 6,12-diarylindolo [3,2-b] carbazole derivative and a polymer doped with an electron accepting material have high conductivity and solvent solubility.

The NMR chart of the polymer obtained in Example 2 is shown.

Claims (6)

  An organic conductive polymer for electronic devices, which is a polymer obtained by oxidative polymerization of a 6,12-diarylindolo [3,2-b] carbazole derivative. A 6,12-diarylindolo [3,2-b] carbazole derivative is represented by the following general formula (1), and a polymer obtained by oxidative polymerization thereof is a polymer represented by the following general formula (2): Item 10. An organic conductive polymer for an electronic device according to Item 1.

(In the general formula (1) and (2), 6,12-position of Ar are each independently, .R ¹ showing the aryl group of 3 to 20 carbon atoms which may have a substituent, each independently And hydrogen, an alkyl group, an alkenyl group, an acyl group, a sulfonyl group, or an aryl group having 3 to 20 carbon atoms which may have a substituent, each R ² independently represents a hydrogen atom, a halogen atom, or an alkyl group. , Alkenyl group, hydroxyl group, alkoxy group, alkoxyalkyl group, acyl group, alkoxycarbonyl group, amide group, nitro group, cyano group, sulfonyl group, substituted or unsubstituted amino group or carbon number that may have a substituent 3 to 20 aryl groups are shown.) The organic conductive polymer for electronic devices according to claim 2, wherein in general formula (1), R ¹ is hydrogen, alkyl, or an aryl group having 3 to 20 carbon atoms which may have a substituent.   An organic conductive polymer for electronic devices, wherein the organic conductive polymer for electronic devices according to claim 1 is doped with an electron accepting substance.   The electron-accepting substance is at least one selected from halogen, proton acid, polymer proton acid, Lewis acid, transition metal salt, tetracyanoethylene, tetracyanoquinodimethane, chloranil, or oxygen. Organic conductive polymer for electronic devices.   An organic conductive material for electronic devices, comprising the organic conductive polymer for electronic devices according to any one of claims 1 to 5.

Images