JPWO2008140087A1 - Conductive resin composition, conductive resin film, and method for forming conductive resin film - Google Patents

Abstract

Provided are a conductive resin film exhibiting high charge mobility, a resin composition thereof, and a method for forming a conductive resin film. The present invention relates to a resin composition for forming a conductive resin film, wherein the charge mobility of the conductive resin film is less than 1.0 × 10 −6 cm 2 V −1 s-1 to 1.0 × 10 − A resin composition that is improved to 5 cm2V-1s-1 or more, and a conductive resin film obtained from the resin composition, wherein the charge mobility of the resin film before light irradiation is 1.0 × 10 −6 cm2V A conductive resin film having a charge mobility of less than −1 s −1 and a charge mobility after light irradiation of 1.0 × 10 −5 cm 2 V −1 s −1 or more. The method of forming the conductive resin film includes a step of forming a coating film with a conductive resin film forming solution containing the resin composition for forming a conductive resin film, and light having a wavelength of 200 to 600 nm on the coating film. Irradiating.

Description

  The present invention relates to a conductive resin composition, a conductive resin film, and a method for forming a conductive resin film.

  Polyacetylene, polyphenylene, polyphenylene vinylene, polypyrrole, and the like known as conductive resins are used as materials for organic electroluminescence (organic EL), organic field effect transistors (organic FET), batteries, capacitors, and the like. These conductive resins are used as a thin film depending on the application, or after being formed into a thin film, they are patterned into a predetermined shape and used.

  For example, an organic EL element provided in an EL display has a structure including a light emitting layer made of a substance that emits light between an anode and a cathode, but increases luminous efficiency and produces a brighter and brighter image. For display, organic EL elements having a multilayer structure including a hole (electron) transport layer and a hole (electron) injection layer between the anode and the light-emitting layer or between the anode and cathode and the light-emitting layer are also employed. Yes.

The hole (electron) transport layer efficiently moves holes (electrons) from the anode (cathode) to the light emitting layer, and the electrons (holes) entering the light emitting layer transport holes (electrons). It has a function of preventing migration to the layer, and conductive resins such as polypyrrole and polythiophene have been used for the hole transport layer so far. In particular, polythiophene-based compounds are widely used. For example, in Patent Document 1, an aqueous dispersion obtained by blending an acid group-containing polymer with polythiophene is applied onto an anode to form a hole transport layer. Yes. Patent Document 2 proposes using poly (arylene vinylene) as a patterning material.
Special table 2000-514590 WO2005 / 049688 pamphlet

  However, since the polythiophene aqueous dispersion contains a large amount of impurities, it is originally not preferable as a material used for a delicate organic EL device. In addition, since water with a high boiling point must be completely volatilized, the cost of the drying process increases, and the acid groups of the acid group-containing polymer have the disadvantage of corroding the coating equipment and are soluble in organic solvents. Hole transport layer materials have been envied. In addition, demands for good response speed and high luminous efficiency tend to increase, and the development of a hole (electron) transport layer material capable of realizing higher mobility is desired. It was difficult to satisfy all requests, and there was still room for improvement.

  The present invention has been made paying attention to the above-described circumstances, and its purpose is to form a resin composition for forming a conductive resin film exhibiting high charge mobility, a conductive resin film, and a conductive resin film. Is to provide a method.

The conductive resin composition of the present invention that has solved the above problems is a resin composition for forming a conductive resin film, and the charge mobility of the conductive resin film is 1.0 × 10 ⁻⁶ when irradiated with light. It is characterized in that it improves from less than cm ² V ⁻¹ s ⁻¹ to 1.0 × 10 ⁻⁵ cm ² V ⁻¹ s ⁻¹ or more. The resin composition of the present invention is also characterized in that it contains poly (arylene vinylene). The poly (arylene vinylene) preferably has a thiophene skeleton, and the poly (arylene vinylene) preferably has a number average molecular weight of 7500 or more. In addition, it is preferable that the resin composition of the present invention contains 3% by mass or more of sulfur atoms.

  In the present invention, the term “conductivity” includes electrical conductivity of a semiconductor level.

The present invention also includes a conductive resin film obtained from the above conductive resin composition. That is, the conductive resin film of the present invention has a charge mobility of the resin film before light irradiation of less than 1.0 × 10 ⁻⁶ cm ² V ⁻¹ s ⁻¹ , and the charge mobility after light irradiation. Is 1.0 × 10 ⁻⁵ cm ² V ⁻¹ s ⁻¹ or more. The conductive resin film preferably has a trans-poly (arylene vinylene) structure.

  The present invention also includes a method for forming the conductive resin film. The formation method of the said conductive resin film is the process of forming a coating film with the conductive resin film forming solution containing the said resin composition, and the process of light-irradiating the said coating film with the light of wavelength 200-600 nm. Features include Moreover, it is preferable to perform a rinse process after the said light irradiation process.

  A device including the conductive resin film is a preferred embodiment of the present invention.

  According to the present invention, a conductive resin film having high charge mobility can be obtained. The conductive resin film of the present invention is suitably used for materials such as organic EL (organic electroluminescence), organic FET (organic field effect transistor), batteries, capacitors, and photoelectric conversion elements (solar cells). For example, it is expected to produce a high-performance, high-brightness EL device using the conductive resin according to the present invention as a hole transport layer of the EL device.

6 is an ultraviolet-visible absorption spectrum showing the result of Synthesis Example 5. 10 is an ultraviolet-visible absorption spectrum showing the result of Synthesis Example 7. 10 is an ultraviolet-visible absorption spectrum showing the result of Synthesis Example 9.

First, a conductive resin film obtained from the resin composition that embodies the characteristics of the resin composition of the present invention will be described. The conductive resin film of the present invention is obtained by forming a conductive resin composition of the present invention, which will be described later, and irradiating with light, and the charge mobility before light irradiation is 1.0 × 10 ^−6. less than cm ² V ^-1 s ^-1, and has a feature where the charge mobility of post-irradiation is ^{1.0 × 10 -5 cm 2 V -1} s -1 or greater.

  The charge mobility is a parameter representing the ease of movement of electrons and holes, and indicates the charge transfer rate per unit electric field in the resin film according to the present invention. The charge mobility is also used as a measure of electric conductivity. When the charge mobility is high, it means that the electric conductivity is high, while when the charge mobility is low, the electric conductivity is high. Means low. The charge mobility can be measured by the method described in Examples described later.

The charge mobility of the conductive resin film of the present invention is preferably 1.0 × 10 ⁻⁴ cm ² V ⁻¹ s ⁻¹ or more, more preferably 1.0 × 10 ⁻³ cm ² V ⁻¹ s. ^-1 or higher. If the charge mobility is too small, it is difficult to obtain a good response speed in a device using the conductive resin film, and it is difficult to obtain high luminous efficiency when used in an organic EL element. May occur. On the other hand, the upper limit of charge mobility is not particularly limited, and it is preferably as large as possible.

  The conductive resin film of the present invention preferably has a trans-poly (arylene vinylene) structure. A compound having a poly (arylene vinylene) structure (hereinafter sometimes referred to as a poly (arylene vinylene) compound or simply poly (arylene vinylene)) is known as a conductive and light-emitting material. In addition, as described in Patent Document 2, poly (arylene vinylene) is irradiated with light in the visible-ultraviolet light region (200 to 600 nm), so that the vinylene moiety of the main chain of poly (arylene vinylene) is It has the property of isomerizing from a cis structure to a trans structure and decreasing the solubility. Thus, since the structure can be isomerized by irradiation with light of a specific wavelength, it is preferable that a cis isomer exists in the resin film before light irradiation. In addition, it is preferable that the ratio of cis / trans (mass ratio) in the resin film before light irradiation is 65 or more. More preferably, it is 80 or more, More preferably, it is 90 or more, Furthermore, 99 or more may be sufficient.

  The trans-poly (arylene vinylene) is preferably a polymer having a structure represented by the following general formula (I) as a repeating unit.

(In the general formula (I), Ar and Ar ′ are independent of each other and represent the same or different arylene groups, and n represents an integer of 1 or more.)

  Ar and Ar ′ (arylene group) are cyclic organic compounds having aromaticity, and even if they are carbocyclic compounds composed only of carbon, they contain heterocyclic atoms containing heteroatoms such as O, N, and S. It may be a compound. The arylene group may be a monocyclic compound having a single ring structure, a condensed ring compound having two or more ring structures, and may have a substituent. The arylene group preferably has 1 to 20 carbon atoms (more preferably 3 to 12 carbon atoms), and preferably a 5 to 6 membered ring. When hetero atoms such as O, N, and S are included, the number of such hetero atoms is preferably 1 to 4 (more preferably 1 to 2 hetero atoms). Specific examples of the structure of the arylene group (Ar, Ar ′) include, for example, those having structures represented by the following chemical formulas (1) to (19), derivatives thereof, and a plurality of these structures. Things.

  Here, the positional relationship on the aromatic ring or heterocyclic ring of the two vinyl groups (described in the general formula (I)) bonded to the arylene group is not particularly limited. For example, when Ar and Ar ′ are benzene, the two vinyl groups may have any positional relationship of ortho, meta, and para. In addition, the derivative having the structure of the chemical formula (1) to the chemical formula (19) is an alkyl group, an aryl group, an alkoxy group, a carbonyl group, an amino group instead of a hydrogen atom on the aromatic ring or heterocyclic ring of the arylene group. It means a group to which a substituent such as a group, a nitro group, a cyano group or a fluorine group is bonded. From the viewpoint of improving the solubility of the poly (arylene vinylene) compound in an organic solvent, the poly (arylene vinylene) compound preferably has an alkyl group having 3 or more carbon atoms or an alkoxy group. Among the arylene groups, those having a structure represented by chemical formulas (1), (3), (10), (11), (15), (17), (18), (19), or derivatives thereof preferable. A substituent having an alkoxy group is preferred. Among the preferable structures exemplified above, those having a thiophene structure represented by the chemical formulas (10), (18), and (19) or derivatives thereof (requirement (2) below) are particularly preferable.

The conductive resin film of the present invention that satisfies the above-described charge mobility preferably satisfies one or both of the following requirements (1) and (2).
(1) It is obtained from a resin composition containing poly (arylene vinylene) having a number average molecular weight of 7500 or more.
(2) A poly (arylene vinylene) structure contains a thiophene skeleton.

  When the requirements (1) and / or (2) are satisfied, a conductive resin film having high charge mobility can be obtained.

  The number average molecular weight is measured by gel permeation chromatography (GPC, standard substance: polystyrene). As described above, the conductive resin film of the present invention is preferably obtained from a resin composition containing a poly (arylene vinylene) compound having a number average molecular weight of 7500 or more (requirement (1)). More preferably, it is 10,000 or more, More preferably, it is 30,000 or more. If the molecular weight is too small, insolubilization by light irradiation may be insufficient. Although there is no limitation on the upper limit of the molecular weight, it is preferably 10 million or less, more preferably 1 million or less, from the viewpoint of solubility in an organic solvent (workability during film formation), More preferably, it is 100,000 or less, and may be 50,000 or less.

  In addition, when the thiophene skeleton is included in the poly (arylene vinylene) structure, the orientation of the molecular chain of the resin constituting the conductive resin film is improved, so that the charge mobility of the conductive resin film is improved. it is conceivable that. In addition, when the thiophene skeleton is included in the poly (arylene vinylene) structure, the structure represented by the above chemical formula (10) or (18) is included as the arylene group, the structure of the chemical formulas (1) to (19) When the structure of chemical formula (10) is included in a series of a plurality of (when a part or all of the condensed heterocyclic ring is composed of a thiophene skeleton, for example, the structure of chemical formula (19), etc.).

  The thickness of the conductive resin film of the present invention is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more. Although the upper limit of a film thickness is not specifically limited, It is preferable to set it as 5 micrometers or less, More preferably, it is 1 micrometer or less. If the film thickness is too thick, the resistance becomes too high and the current during device operation may be reduced. On the other hand, if it is too thin, there is a risk of causing a short circuit.

The conductive resin film of the present invention is formed from the conductive resin composition of the present invention, and the conductive resin composition of the present invention is characterized in that it contains the poly (arylene vinylene) compound described above. Have. In addition, the conductive resin film formed from the resin composition of the present invention has a charge mobility of less than 1.0 × 10 ⁻⁶ cm ² V ⁻¹ s ⁻¹ to 1.0 × 10 ^{−5 when} irradiated with light. Improved to cm ² V ^-1 s ^-1 or higher.

  About the structure of poly (arylene vinylene) according to the resin composition of the present invention, the structure represented by the above formula (I) (trans form) and / or the structure represented by the following general formula (II) ( and a structure containing (cis form) as a repeating unit.

  In the general formula (II), examples of Ar and Ar ′ (arylene group) are the same as those in the chemical formulas (1) to (19).

  The substituent bonded to the arylene group represented by the general formulas (I) and (II) may be a photoinsolubilizable group such as a haloethenyl group or a boronic acid derivative group described later. That is, in the conductive resin composition according to the present invention, in addition to poly (arylene vinylene) having a photoinsolubilizable group as a terminal group, poly (arenyl group bonded to Ar, Ar ′ in the middle of the polymer chain) Arylene vinylene).

  The photoinsolubilizable group preferably has a formula weight of 300 or less. More preferably, it is 200 or less. When the conductive resin film or conductive resin composition having a poly (arylene vinylene) structure contains poly (arylene vinylene) having such a photoinsoluble group, the present inventors have changed from a cis isomer to a trans isomer. In addition to the isomerization to, it has been found that the solubility of the trans-poly (arylene vinylene) thin film produced by light irradiation decreases. The detailed reason why the solubility is lowered when a photoinsolubilizable group having a formula weight of 300 or less is present is not clear, but by photoirradiation, the above-mentioned photoinsolubilizable group and cis-poly (arylene) It is considered that some reaction occurs between vinylene) and trans-poly (arylene vinylene), and as a result, poly (arylene vinylene) is further increased in molecular weight, resulting in a decrease in solubility.

  Examples of the photoinsolubilizable group having a formula weight of 300 or less include a haloethenyl group and / or a boronic acid derivative group. Specific examples of photoinsolubilizable groups include haloethenyl groups such as chloroethenyl group, bromoethenyl group, and iodoethenyl group, boronic acid groups, and boronic ester groups (examples of ester groups include methyl ester, ethyl ester, propyl ester, and butyl And boronic acid derivative groups such as esters). Among these, a haloethenyl group is preferable. The formula amount of the photoinsolubilizable group is more preferably 200 or less, and still more preferably 120 or less.

  The photoinsolubilizable group having a formula weight of 300 or less may be bonded to any of both ends, one end, and an arylene group in the middle of the molecular chain of poly (arylene vinylene). It is preferable that it exists in one terminal or both terminal, More preferably, it is the aspect which has the said photo-insoluble group in both terminal. In particular, poly (arylene vinylene) having a specific group at the end (group capable of photoinsolubilization having a formula weight of 200 or less) is a resin composition (solid content excluding solvent) 100 that forms the conductive resin film according to the present invention. It is preferable that 10 mass% or more exists with respect to the mass%. More preferably, it is 50 mass% or more, More preferably, it is 80 mass% or more. Of course, all of them may be poly (arylene vinylene) having the specific photoinsolubilizable group at the terminal. When the content of poly (arylene vinylene) having a specific photoinsolubilizable group at the terminal is low, the decrease in solubility due to light irradiation may be insufficient.

  In addition, poly (arylene vinylene) having a photoinsoluble group at the terminal can be confirmed by proton NMR measurement or elemental analysis. Further, the conductive resin composition according to the present invention is a mixture of poly (arylene vinylene) having a photoinsoluble group at the terminal and poly (arylene vinylene) having no photoinsoluble group at the terminal. In this case, the content of poly (arylene vinylene) having a terminal capable of photoinsolubilization at the terminal can be similarly confirmed by proton NMR measurement or elemental analysis. For example, in the case of analyzing a compound having a bromoethenyl group as a terminal photoinsolubilizable group by proton NMR measurement, the poly (arylene) having the terminal group is determined from the integral ratio of the proton peak derived from the terminal bromoethenyl group. The abundance of vinylene) can be calculated.

  The conductive resin composition of the present invention contains poly (arylene vinylene) as a conductive resin, and the poly (arylene vinylene) includes trans- (arylene vinylene) and cis- (arylene vinylene). included. The ratio of poly (arylene vinylene) in the resin composition to the trans isomer relative to the cis isomer may be the same as that of the conductive resin film before light irradiation, and cis isomer / trans isomer = 65/35 or more (mass) Ratio). More preferably, it is 80/20 or more, More preferably, it is 90/10 or more.

  Moreover, it is preferable that the conductive resin composition concerning this invention contains 3 mass% or more of sulfur atoms. More preferably, it is 5 mass% or more, More preferably, it is 10 mass or more, Most preferably, it is 20 mass% or more. If the sulfur atom content is too high, the resin composition may be difficult to dissolve in an organic solvent during film formation. Therefore, it is preferable that it is 80 mass% or less, More preferably, it is 60 mass%, More preferably, it is 50 mass% or less. If the content of sulfur atoms is within the above range, the conductive resin film formed from the resin composition has a structure that is easily oxidized. Therefore, carriers are easily generated in the conductive resin film, and charge transfer occurs. The degree is thought to improve. The sulfur atom is preferably derived from a poly (arylene vinylene) compound.

  The content of sulfur atoms in the conductive resin composition can be measured with an ICP emission spectroscopic analyzer (for example, “SPS4000” manufactured by Seiko Denshi Kogyo Co., Ltd.). The measurement can be performed by analyzing a measurement solution prepared by dissolving the conductive resin composition in a solvent in which the conductive resin composition is soluble (for example, THF, toluene, chloroform, etc.) using an ICP emission spectroscopic analyzer. It is possible to measure the sulfur atom content in the conductive resin composition.

  In the conductive resin composition concerning this invention, other conductive resins other than the said poly (arylene vinylene) may be included. The content of the other conductive resin is preferably about 10 to 90% by mass in 100% by mass of the conductive resin composition according to the present invention. Examples of other conductive resins include polyaniline and polyfluorene.

  Next, the manufacturing method of the said poly (arylene vinylene) is demonstrated. The poly (arylene vinylene) according to the present invention is obtained by polycondensation of the first arylene compound and the second arylene compound. As a specific method for producing poly (arylene vinylene), a method in which a first arylene compound and a second arylene compound are subjected to a coupling reaction in the presence of a palladium catalyst (Suzuki-Miyaura coupling, Hiyama cross coupling), Examples include Gilch method, Honer-Emons reaction, Stille coupling reaction, Witting-Honer reaction, and terminal treatment.

  When a poly (arylene vinylene) is produced by a coupling reaction of a first arylene compound and a second arylene compound under a palladium catalyst (Suzuki-Miyaura coupling), first, the first arylene compound, The 2 arylene compound is dissolved in an organic solvent. Next, 1 to 5 equivalents of a base with respect to the first or second arylene compound and 0.1 to 10 mol% of a palladium catalyst with respect to the first or second arylene compound are added thereto. Thereafter, poly (arylene vinylene) can be obtained by heating and stirring at room temperature to 180 ° C. under light shielding conditions.

  Examples of the first arylene compound include arylene compounds in which at least two cis- or trans-form haloethenyl groups are bonded. Here, the arylene group preferably has 1 to 20 carbon atoms (more preferably 3 to 12 carbon atoms), and preferably a 5 to 6 membered ring. In addition, when elements, such as O, N, and S, are included, it is preferable that the number of such elements is 1 to 4 (more preferably 1 to 2), and specifically, the chemical formulas (1) to Examples include those in which a cis- or trans-bromoethenyl group is bonded to an arylene group having the structure represented by (19).

  The arylene group may have a substituent other than the haloethenyl group. Examples of the substituent include an alkyl group having 3 or more carbon atoms, an alkoxy group, a carbonyl group, an amino group, a nitro group, a cyano group, and a fluorine group. In addition, from the viewpoint of adjusting a coating solution for forming a coating film, the substituent is preferably capable of improving solubility in an organic solvent. Examples of the substituent include an alkyl group having 3 carbon atoms (more preferably 6 carbon atoms or more) (for example, propyl group, butyl group, pentyl group, hexyl group, octyl group, etc.), 3 carbon atoms or more (more preferably carbon atoms). (Six or more) alkoxy groups (hexyloxy group, 2-ethyl-hexyloxy group, octyloxy group).

  Specific examples of the first arylene compound include 1,4-bis (trans-2-bromoethenyl) benzene, 1,4-bis (cis-2-bromoethenyl) benzene, 2,7-bis (trans-bromoethenyl)- 9,9-dihexylfluorene, bis (cis-bromoethenyl) -9,9-dihexylfluorene, bis (trans-bromoethenyl) fluorene, bis (cis-bromoethenyl) fluorene, 2,5-bis (cis-2-bromoethenyl) thiophene 2,5-bis (cis-2-bromoethenyl) -3-hexylthiophene, 2,5-bis (cis-2-bromoethenyl) -3,4-ethylenedioxythiophene, 5,5'-bis (cis- 2-Bromoethenyl) -2,2′-bithiophene, 4,4′-dihexyl-5,5′-bis (cis-2-bromoethenyl) -2,2 - bithiophene, 3,3'-bis (alkoxy) -5,5'-bis (cis-2-bromoethenyl) -2,2'-bithiophene and the like.

  The first arylene compound may have either a trans-haloethenyl group or a cis-haloethenyl group. That is, when an arylene compound having a cis-haloethenyl group is used as the first arylene compound, cis-poly (arylene vinylene) is obtained, and when an arylene compound having a trans-haloethenyl group is used, trans-poly (arylene vinylene) is obtained. When the first arylene compound has a cis-haloethenyl group, isomerization from the cis isomer to the trans isomer occurs when the reaction solution after the coupling reaction with the second arylene compound is irradiated with ultraviolet light. Therefore, a trans-poly (arylene vinylene) solution is obtained.

  Examples of the second arylene compound include an arylene compound in which at least two boronic acids (or ester groups thereof) are bonded. It is preferable to use 1 equivalent of the second arylene compound with respect to the first arylene compound.

  Examples of the arylene group that the second arylene compound has include the same arylene group as that of the first arylene compound. That is, the second arylene compound has the same arylene group as the first arylene compound except that boronic acid is bonded instead of the haloethenyl group. Specific examples of the second arylene compound include 1,4-dioctyloxy-2,5-benzenediboronic acid, 1- (2-ethylhexyloxy) -4-methoxy-2,5-benzenediboronic acid, , 4-Bis [(S) -2-methylbutoxy] -2,5-benzenediboronic acid, 2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaboro Ranyl) thiophene, 2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -3-hexylthiophene, 2,5-bis (4,4,4) 5,5-tetramethyl-1,3,2-dioxaborolanyl) -3-hexyloxythiophene, 2,5-bis (4,4,5,5-tetramethyl-1,3,2-di Oxaborolanyl) -3,4-ethylenedioxythiophene, 3,3′-bis ( Lucoxy) -5,5′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2,2′-bithiophene, 4,4′-dihexyl-5 5'-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2,2'-bithiophene, 5,5'-bis (4,4,5,5 -Tetramethyl-1,3,2-dioxaborolanyl) -2,2'-bithiophene and the like can be exemplified.

  From the viewpoint of increasing the molecular weight of poly (arylene vinylene), it is preferable to use a boronic acid ester obtained by esterifying a boronic acid. Boronic acid tends to generate a condensate (boroxin) during the polycondensation reaction, and it may be difficult to keep the composition in the reaction system constant. However, the above condensation can be achieved by esterifying the boronic acid in advance. The production of products can be suppressed, and the composition in the system can be easily kept constant. Moreover, the solubility of the second arylene compound in the reaction system can be improved by esterifying the boronic acid. Preferred boronic acid esters include boronic acid pinacol ester, boronic acid ethylene glycol ester, boronic acid propylene glycol ester, boronic acid dimethyl ester, boronic acid diethyl ester, boronic acid dipropyl ester, boronic acid dibutyl ester and the like.

  In addition, when a compound in which two haloethenyl groups or two boronic acids (or ester groups thereof) are used as the first and second arylene compounds, a polymer having a linear spread is obtained. In order to obtain a polymer having a structure extending in a plane, two or more compounds having three or more reactive functional groups such as haloethenyl groups and boronic acids are used as the first and / or second arylene compounds. The first and second arylene compounds having a haloethenyl group or boronic acid may be used in combination.

  In the above reaction, the mixing ratio of the first arylene compound and the second arylene compound is preferably 70 (first arylene compound) / 30 (second arylene compound) to 30/70. More preferably, it is 55/45 to 45/55, and ideally 50/50.

  As a base that can be used in the above reaction, sodium hydroxide, potassium hydroxide, barium hydroxide, potassium carbonate, sodium carbonate, potassium phosphate, silver oxide, or an aqueous solution thereof can be used. The amount of these bases used is preferably 0.1 to 10 equivalents relative to the total amount of the first and second arylene compounds. More preferably, it is 0.5-5 equivalent, More preferably, it is 1-2 equivalent.

  Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, dichloro {1,1'-bis (diphenylphosphino) ferrocene} palladium and the like. The amount of the palladium catalyst used is preferably 0.01 to 50 mol% with respect to the total amount of the first and second arylene compounds. More preferably, it is 0.1-5 mol%, More preferably, it is 0.5-2 mol%.

  In addition to the palladium catalyst, a phase transfer catalyst such as tetraammonium bromide, trioctylmethylammonium chloride, trioctylmethylammonium bromide, or trioctylmethylammonium hydroxide may be used. Among these, when using the ammonium salt which has a long-chain alkyl group, since the usage-amount can be reduced, it is preferable. The amount of the phase transfer catalyst used is preferably 0.01 to 10 equivalents relative to the total amount of the first and second arylene compounds as the reaction substrate. More preferably, it is 0.01-1 equivalent, and it is recommended that it be 0.01-0.1 equivalent from the viewpoint of increasing the molecular weight of poly (arylene vinylene).

  Examples of the organic solvent include tetrahydrofuran (THF), toluene, xylene, ethylbenzene, mesitylene, N, N-dimethylformamide (DMF), dioxane, and the like. The stirring time is preferably 12 to 60 hours (more preferably 12 to 24 hours). The reaction temperature is preferably room temperature to 180 ° C, more preferably 80 to 140 ° C. From the viewpoint of increasing the molecular weight of poly (arylene vinylene), a temperature of 100 to 120 ° C. is recommended.

  The Gilch method, Honer-Emons reaction, and Stille coupling reaction are described in detail on pages 297-304 of Synthetic Metals 150 (2005). For example, in the Gilch method, the conductive resin according to the present invention is described. Are produced, the first arylene compound and the second arylene compound each having two halogenated methyl groups (the arylene groups of the first and second arylene compounds may be the same or different from each other). .) Can be used. First, the first arylene compound is dissolved in an organic solvent (for example, THF). Here, the second arylene compound is added and reacted under a nitrogen stream, and 100 to 1000 mol% of a metal alkoxide (for example, t-butoxy potassium) is rapidly added to the first or second arylene compound. Thereafter, when refluxed for 1 to 48 hours, trans-poly (arylene vinylene) is obtained as a viscous crude product. If this is refine | purified using a centrifuge etc., trans-poly (arylene vinylene) will be obtained.

  When the conductive resin of the present invention is produced by the Honor-Emmons method, a first arylene compound having two phosphoryl groups and a second arylene compound having two formyl groups may be used as raw materials.

  First, a 1st arylene compound is dissolved in an organic solvent (for example, DMF etc.), and 100-1000 mol% metal alkoxide (for example, sodium methoxide) is dripped and added here with respect to a 1st arylene compound. Next, after stirring for 1 to 48 hours, if a predetermined amount of methanol is added, a product (trans-poly (arylene vinylene)) is produced as a precipitate. This precipitate is purified using a Soxhlet extraction apparatus or the like. Then, trans-poly (arylene vinylene) is obtained.

  When the conductive resin according to the present invention is produced by the Stille coupling method, a dihalogenated arylene compound and an alkylstannylethene may be used. First, the dihalogenated arylene compound is dissolved in an organic solvent (for example, toluene). To this, 0.01 to 10 mol% of a palladium catalyst (for example, tetrakistriphenylphosphine palladium) and alkylstannylethene are added with respect to the arylene compound, and then refluxed at 80 to 130 ° C. for 1 to 48 hours. Next, after the reaction solution is cooled to room temperature, if a predetermined amount of methanol is added, crude trans-poly (arylene vinylene) is obtained as a precipitate. If this is purified, trans-poly (arylene vinylene) is obtained. .

  Among the above-mentioned methods, when it is desired to obtain cis-poly (arylene vinylene) with high stereoselectivity, a compound having a cis-haloethenyl group is used as the first arylene compound, and Suzuki-Miyaura cross coupling or Kashiyama The polycondensation reaction is performed by a cross coupling method such as cross coupling (“Jornal of Organometallic Chemistry” (USA), 2003, Vol. 676, pp. 49-54). Is preferred. On the other hand, from an economic point of view, the Gilch method or Honor-Emmons reaction, which can be synthesized with an inexpensive alkali metal (such as K), is employed compared to a coupling reaction using a heavy metal such as Pd as a catalyst. Is preferred.

  Next, a method for forming the conductive resin film of the present invention will be described. The method for forming a conductive resin film of the present invention includes a step of forming a coating film with a conductive resin film forming solution containing the resin composition, and a step of irradiating the coating film with light having a wavelength of 200 to 600 nm. , Including features.

  The conductive resin film-forming solution (coating solution) is obtained by dissolving the conductive resin composition of the present invention containing poly (arylene vinylene) obtained by the above-described manufacturing method in one or more mixed solvents. Can be prepared. The concentration of the coating solution can be appropriately changed according to the desired film thickness. In order to suppress the occurrence of pinholes, it is recommended that the film thickness be 0.5 nm or more, more preferably 1 nm or more. Although the upper limit of a film thickness is not specifically limited, It is preferable to set it as 10 micrometers or less, and 1 micrometer or less is preferable. When a film having a thickness of 10 μm or less is produced by a solution coating method, the solution concentration is preferably about 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.

Apply dopants such as halogens such as I ₂ and Br ₂ , alkali metals such as Na and K, sulfonic acids such as p-toluenesulfonic acid, and other compounds depending on the purpose of improving the conductivity of the coating. You may mix in a solution.

  The solvent is not particularly limited as long as the conductive resin of the present invention can be dissolved. For example, aromatic solvents such as benzene, toluene and xylene, halogen systems such as chloroform, methylene chloride and chlorobenzene, tetrahydrofuran and the like And ether type organic solvents. There is no limitation also about the base material which forms a coating film, What is necessary is just to determine suitably according to the use which uses the electroconductive resin film of this invention, such as glass, a silica, and a resin film.

  As a method for forming a coating film, a solution coating method such as a spin coating method, a cast method, a roll coating method, a spray coating method, a bar coating method, a dip coating method, a screen printing method, a flexographic printing method, an inkjet printing method, etc. A well-known method can be illustrated. In these, since a spin coat method is easy, it is preferable. For example, when a coating film is formed by a spin coating method, it is preferable to dry the solvent while rotating the substrate at 100 to 8000 rpm for about 60 seconds at around room temperature. After spin coating, vacuum drying or heat treatment at 20 to 300 ° C. may be performed as necessary.

  When the coating film formed as described above is irradiated with light having a wavelength of 200 to 600 nm, a thin film insoluble in an organic solvent can be obtained. The irradiation time is not limited, but is preferably 1 to 4000 seconds, for example. As the light source, a xenon lamp, a deuterium lamp, or the like is used.

  Moreover, it is preferable to heat a coating film before light irradiation, simultaneously with light irradiation, and at any one or more steps after light irradiation, or in all steps. By heating the coating film, the insolubilization time can be shortened and the insolubilization rate can be improved, and further, the charge mobility of the conductive resin film can be expected. The heating of the coating film is more preferably performed simultaneously with light irradiation and / or after light irradiation, and more preferably is performed simultaneously with light irradiation. The heating temperature at this time is preferably set to be equal to or higher than the Tg of the conductive resin of the present invention used for forming the coating film, particularly the cis body.

  The light-irradiated thin film (conductive resin film) may be used for various applications as it is, but the present invention shows that the charge mobility can be improved by about one order by performing a rinse step after the light irradiation. They found out. Usually, in applications such as organic EL and organic FET, the thin film after film formation is used for the next step without any treatment. The reason why the charge mobility is improved by rinsing after film formation is not clear, but from the change in spectrum before and after the rinsing step shown in FIG. 1 and the like (from the ultraviolet-visible absorption spectrum of the resin film of Synthesis Example 5 described later) Fig.), The inventors have swelled the resin film with the rinsing solvent, which increases the mobility of the conductive resin molecular chain in the resin film and changes the molecular orientation structure. I guess that will improve. Moreover, it is considered that the impurities in the film can be removed by rinsing.

  The solvent that can be used in the rinsing step is not particularly limited, but preferably alcohols such as methanol, ethanol, and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; chloroform, And halogen-based organic solvents such as methylene chloride and 1,2-dichloroethane.

  The resin film after the rinsing process is preferably dried in the drying process. The drying temperature and drying time are not particularly limited, and may be appropriately determined according to the film thickness, solvent, conductive resin or resin composition used, and for example, the temperature is preferably 20 to 300 ° C., more Preferably it is 80-180 degreeC, It is preferable that drying time is 1-120 minutes, More preferably, it is 5-60 minutes. In addition, you may perform drying under reduced pressure and it is also a preferable aspect to carry out in inert gas atmosphere, such as argon and nitrogen.

  The conductive resin composition of the present invention is not limited to a thin film, and can also be used to produce molded bodies having various shapes (for example, cubes, rectangular parallelepipeds, cones, columns, spheres, etc.). The conductive resin composition of the present invention can also be used as a patterning material. Furthermore, the conductive resin composition of the present invention may contain other resins that are not insolubilized by light. In such a case, a coating film is formed from the coating solution prepared using the conductive resin composition of the present invention containing a mixture of the above-mentioned poly (arylene vinylene) compound and other resin that is not photo-insolubilized. What is necessary is just to elute other resin with a solvent, after irradiating light from on the mask, insolubilizing the conductive resin which concerns on this invention. If the conductive resin composition according to the present invention is used, the conductive resin film can be directly patterned without using a resist.

  Moreover, since the conductive resin film of the present invention has high charge mobility, it is suitable for materials (devices) such as organic EL (organic electroluminescence), organic FET (organic field effect transistor), batteries, and capacitors. Used. In addition, by changing the substituent on the aromatic ring or heterocyclic ring of arylene vinylene contained in the conductive resin film of the present invention, it has characteristics according to various uses such as organic EL, organic FET, battery, and capacitor. You can also.

  For example, an organic EL element has a structure in which an organic thin film layer is sandwiched between electrodes (anode, cathode), and the organic thin film layer is formed from the anode side, a hole transport layer, a light emitting layer, an electron transport layer. have. The conductive resin film of the present invention is suitable as a hole transport layer of an organic EL element having such a structure, and the organic EL element provided with the conductive resin film of the present invention as a hole transport layer has a high performance. Therefore, it is expected to be an EL element with high brightness. In addition to the hole transport layer, the conductive resin film of the present invention can also be used as an organic film layer provided on a general organic semiconductor such as a light emitting layer or an electron transport layer.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples as a matter of course, and appropriate modifications are made within a range that can meet the purpose described above and below. Of course, it is also possible to implement them, and they are all included in the technical scope of the present invention. Various physical properties were measured according to the following methods.

<Measurement of absorbance>
1. Measurement of absorbance (before and after light irradiation) Poly (arylene vinylene) (about 2 mg) obtained in each synthesis example was dissolved in chloroform (1 ml, for ultraviolet absorption spectrum), and a syringe filter (ADVANTEC; DISMIC-13 JP) , PTFE 0.50 μm, Hydrophobic). After 50 μl of this solution was dropped on a quartz plate (1 cm × 0.9 cm × 0.5 mm), using a spin coater (“1H-DX2” manufactured by Mikasa Co., Ltd.), it was set to 1200 rpm over 2 seconds and 1200 rpm for 10 seconds. Subsequently, the film was formed by rotating at 2000 rpm for 60 seconds. This was dried at room temperature (25 ° C.) for 30 minutes under reduced pressure to produce a poly (arylene vinylene) thin film on a quartz substrate.

  The obtained substrate was placed in a quartz cell for ultraviolet-visible absorption spectrum measurement, and then purged with nitrogen. Using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, V-550), an ultraviolet region in the region of 300 to 800 nm was used. The visible absorption spectrum was measured (before light irradiation, spectrum A).

Next, a quartz substrate having a poly (arylene vinylene) thin film was placed on a stainless steel holder with a quartz glass window, and the atmosphere was replaced with nitrogen. Using a xenon lamp (manufactured by Asahi Spectral Co., Ltd., LAX101), ultraviolet light (main wavelength 365 nm, illuminance 21.0 mW / cm ² ) on a quartz plate having a poly (arylene vinylene) thin film at room temperature in a nitrogen stream Was irradiated for 1 hour. Then, the board | substrate was taken out from the stainless steel holder, and the ultraviolet visible absorption spectrum was measured by the above-mentioned method. (Spectrum B after light irradiation).

2. Measurement of absorbance (after rinsing) (Synthesis Example 3-2, Synthesis Examples 5 to 10)
Using tweezers, the substrate whose absorbance was measured before and after light irradiation was immersed in chloroform (1 ml, for ultraviolet absorption spectrum) and shaken for 5 seconds. Next, the substrate was taken out, soaked in fresh chloroform (1 ml, for ultraviolet absorption spectrum) for 1 second, dried at room temperature (25 ° C.) under reduced pressure, and then the ultraviolet-visible absorption spectrum was measured by the method described above. (Spectrum C after rinsing).

3. Measurement of absorbance (after rinsing) (Synthesis Example 9)
Absorbance (after rinsing) was measured in the same manner as 1 and 2 above, except that ultraviolet light irradiation (main wavelength 365 nm, illuminance 21.0 mW / cm ² , 1 hour) was performed at a temperature of 150 ° C. went.

<Measurement of charge mobility>
A substrate in which a 3000 ＳｉＯ SiO ₂ film is formed as a dielectric film on a p-type Si wafer (manufactured by Furuuchi Chemical Co., Ltd., single-sided polishing, resistance 0.02 Ω · cm or less) as a gate electrode It was cut into a size and subjected to ultrasonic cleaning for 10 minutes in 2-propanol, followed by boiling cleaning. Poly (arylene vinylene) obtained in each synthesis example was dissolved in chloroform, and a conductive resin film having a thickness of 30 nm was formed by spin coating (100 to 8000 rpm, 60 seconds), followed by light irradiation as necessary. A rinse treatment was performed. Thereafter, an Au electrode (30 nm) was formed by vacuum deposition as a source / drain electrode. At this time, the electrodes were formed using a mask so that the distance between the electrodes was 20 μm and the electrode length was 5 mm. The charge mobility (TFT) was measured using two source meters (model number 2400, manufactured by Keithley Instruments Inc.) under the conditions of a gate electrode of 0 to 100 V and a source-drain electrode of 0 to 100 V. The evaluation element was manufactured and measured in an Ar gas atmosphere in a glove box (water content: 1 ppm or less, oxygen: 1 ppm or less) connected to a vacuum vapor deposition machine.

In Synthesis Example 9, in addition to the above-described measurement of charge mobility, charge mobility using an ODTS-treated substrate was also measured. Here, the “ODTS-treated substrate” means that the substrate having the SiO ₂ film after boiling cleaning is immersed in an octadecyltrichlorosilane (manufactured by Acros) for 12 hours in an inert gas, taken out, and excessive on the surface. A surface-modified substrate obtained by washing octadecyltrichlorosilane adhering to dehydrated hexane, and in Synthesis Example 9, a poly (arylene vinylene) thin film and a source-drain were formed on this ODTS-treated substrate by the method described above. An electrode was formed. In addition, the conductive resin thin film formed at this time was irradiated with light under heating at 150 ° C.

<Measurement of band gap>
A thin film of poly (arylene vinylene) obtained in each synthesis example is formed by spin coating on a slide glass substrate that has been ultrasonically cleaned in distilled water and isopropanol for about 10 minutes and finally boiled and cleaned in isopropanol. did. The absorption spectrum of the obtained thin film was measured in the wavelength range of 300 to 1100 nm with a spectrophotometer (“Agilent8453” manufactured by Agilent Technologies). Assuming that the energy of the wavelength λ (nm) at the longest absorption edge of the absorption peak is the lowest excitation energy, that is, the band gap (Bg), Bg was calculated from the wavelength λ and the following equation.
Bg (eV) = h × ν = 1240 / λ
(In the formula, h is a Planck constant, and ν represents the frequency of light.)

In addition, when measuring about the conductive resin film after light irradiation, a slide glass substrate having a poly (arylene vinylene) thin film is installed in a stainless steel holder substituted with nitrogen by the same method as the measurement of absorbance described above, Using a xenon lamp (manufactured by Asahi Spectral Co., Ltd., LAX101), a glass slide glass substrate having a PPV thin film is irradiated with ultraviolet light (main wavelength: 365 nm, illuminance: 21.0 mW / cm ² ) for 1 hour under nitrogen flow did. Then, the board | substrate was taken out from the stainless steel holder, and the band gap was measured according to the said method using the spectrophotometer.

<Measurement of HOMO and LUMO levels of conductive resin film>
A thin film of poly (arylene vinylene) obtained in each synthesis example was formed on a glass substrate washed in the same manner as the calculation of the band gap. The photoelectron emission threshold value of this thin film was measured with an atmospheric photoelectron spectrometer (“AC-2” or “AC-3” manufactured by Riken Keiki Co., Ltd.). This photoelectron emission threshold, that is, the ionization potential, was regarded as the HOMO level (the energy level at the uppermost end of the valence band).

  On the other hand, the LUMO level was calculated from the HOMO level and the band gap value.

  Further, the LUMO level and the HOMO level were calculated for the conductive resin film after the light irradiation by the same method.

<Measurement of sulfur atom content>
Using an ICP emission analyzer (“SPS4000” manufactured by Seiko Denshi Kogyo Co., Ltd.), the content of sulfur atoms contained in the poly (arylene vinylene) obtained in the synthesis example was measured. The measurement solution was prepared by dissolving in toluene so that the concentration of poly (arylene vinylene) was 1% by mass.

[Synthesis Example 1]
(Z, Z) -1,4-bis (2-bromoethenyl) benzene (173 mg, 0.60 mmol, first arylene compound), 1,4-dioctyloxy-2,5-benzenediboronic acid (255 mg,. 60 mmol, second arylene compound), tetrakis (triphenylphosphine) palladium (6.9 mg, 0.0060 mmol), and tetrabutylammonium bromide (193 mg, 0.6 mmol) were placed in a 20 ml Schlenk tube and purged with nitrogen. Toluene (3 ml) and 3M aqueous potassium hydroxide solution (0.6 ml, 1.8 mmol) were added thereto, and the mixture was stirred at 80 ° C. for 24 hours under light-shielding conditions. The reaction solution was cooled to room temperature, washed with water (6 ml) three times, and poured into stirring methanol (150 ml). The deposited precipitate was collected by filtration, washed with methanol, and dried to obtain a yellow solid (yield: 290 mg, yield: 99% or more).

The obtained solid was dissolved in deuterated chloroform (CDCl ₃ , reference substance: tetramethylsilane) and subjected to ¹ H-NMR measurement (300 MHz, manufactured by Varian, Mercury 300). As a result, cis-poly (phenylene vinylene) ( (Hereinafter abbreviated as cis-PPV)) was confirmed to account for 99% or more (ratio of cis structure / trans structure: 99/1 or more). Further, about 1 mg of the obtained cis-PPV was dissolved in THF, and gel permeation chromatography (GPC, manufactured by JASCO, columns: KF-801, KF-803L, KF-805L, manufactured by Shodex, standard substance: polystyrene) result of the analysis, the number-average molecular weight ^_(M n b) 7700, with a polydispersity index 2.69 (polystyrene standard).

In addition, since the ¹ H-NMR chart of cis-PPV obtained at this time was complicated and it was difficult to analyze the terminal structure, the Br content was measured by elemental analysis, and this value was calculated from the cis-PPV. The amount of bromoethenyl group present at the end was taken as the amount. Elemental analysis is performed by elemental analyzer (sample pretreatment unit: automatic sample combustor AQF-100 type, manufactured by Dia Instruments Co., Ltd., ion chromatograph: ICS-1500 (electric conductivity detection, suppressor (SRS) type), column: DIONEX Ion Pac AS12A, manufactured by DIONEX). As a result, it was confirmed that the obtained cis-PPV contained 1.04% (calculated value) of Br.

  Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 1.

[Synthesis Example 2]
(Z, Z) -1,4-bis (2-bromoethenyl) benzene (172 mg, 0.60 mmol, first arylene compound), 1,4-bis (4,4,5,5-tetramethyl-1,3 , 2-Dioxaborolanyl) -2.5-dioctyloxybenzene (351.9 mg, 0.60 mmol, second arylene compound), tetrakis (triphenylphosphine) palladium (10.4 mg, 0.009 mmol), chloride Trioctylmethylammonium (24.3 mg, 0.06 mmol) was placed in a 20 ml Schlenk tube with an internal volume and purged with nitrogen. Toluene (3.0 ml) and 2M aqueous sodium carbonate solution (0.9 ml, 1.80 mmol) were added thereto, and the mixture was refluxed on a 115 ° C. oil bath for 24 hours under light-shielding conditions. The reaction solution is cooled to room temperature, diluted with dichloromethane (8 ml), washed three times with water (3 ml), and the dichloromethane solution is poured into a stirring solvent mixture of methanol (150 ml) / dichloromethane (30 ml). It is. The deposited precipitate was collected by filtration, washed with methanol, and dried to obtain a yellow solid (yield: 254 mg, yield: 92%).

The obtained solid was dissolved in CDCl ₃ by the same method as in Synthesis Example 1 and subjected to ¹ H-NMR measurement. As a result, cis-poly (99% or more of vinylene sites in the polymer chain was controlled to have a cis structure (99% or more). Phenylene vinylene (hereinafter abbreviated as cis-PPV) (ratio of cis structure / trans structure: 99/1 or more). Further, the resulting cis-PPV about 1mg dissolved in THF, GPC (standard substance: polystyrene) result of analysis, the number-average molecular weight ^_(M n b) 11200, polydispersity 2.66 (polystyrene standards) Met.

  Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 1.

[Synthesis Examples 3-1 and 3-2]
(Z, Z) -1,4-bis (2-bromoethenyl) benzene (115.2 mg, 0.40 mmol, first arylene compound), 1,4-bis (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolanyl) -2,5-dioctyloxybenzene (234.6 mg, 0.40 mmol, second arylene compound), tetrakis (triphenylphosphine) palladium (6.9 mg, 0.006 mmol) Trioctylmethylammonium chloride (16.2 mg, 0.04 mmol) was placed in a 20 ml Schlenk tube with an internal volume and purged with nitrogen. Toluene (2.0 ml) and a 2M aqueous sodium carbonate solution (0.6 ml, 1.20 mmol) were added thereto, and the mixture was refluxed for 24 hours on an oil bath at 115 ° C. under light-shielding conditions. The reaction solution was cooled to room temperature, diluted with dichloromethane (5 ml), washed three times with water (3 ml), and the dichloromethane solution was poured into a stirring solvent mixture of methanol (60 ml) / dichloromethane (60 ml). . The deposited precipitate was collected by filtration, washed with methanol, and dried to obtain a yellow solid (yield: 184 mg, yield: 99% or more).

The obtained solid was dissolved in CDCl ₃ in the same manner as in Synthesis Example 1, and ¹ H-NMR measurement was performed. As a result, cis-PPV in which the vinylene site in the polymer chain was controlled to a cis structure of 99% or more was obtained. It was confirmed (the ratio of cis structure / trans structure: 99/1 or more). Further, the resulting cis-PPV about 1mg dissolved in THF, GPC (standard substance: polystyrene) result of analysis, the number-average molecular weight ^_(M n b) 15700, polydispersity 2.49 (polystyrene standards) Met.

This cis-PPV is dissolved in chloroform, filtered through a syringe filter, and then high molecular weight using GPC (JAI, LC-918U, columns: JAIGEL-1H-A, JAIGEL-2H-A, solvent: chloroform). A portion was recycled and the solvent was distilled off under reduced pressure to obtain cis-PPV as a tan solid. Next, about 1 mg of the obtained cis-PPV was dissolved in THF and subjected to GPC (standard substance: polystyrene) analysis. As a result, the number average molecular weight (M _n ^b ) 34600, polydispersity 1.47 (polystyrene standard) Met. Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 1. In Table 1, Synthesis Example 3-2 means that the cis-PPV conductive resin film obtained in Synthesis Example 3-1 is subjected to a rinsing process (solvent: chloroform).

[Synthesis Example 4]
(Z, Z) -1,4-bis (2-bromoethenyl) benzene (288.0 mg, 1.0 mmol, first arylene compound), 1,4-dioctyloxy-2,5-benzenediboronic acid (433. 0 mg, 1.0 mmol, second arylene compound), tetrakis (triphenylphosphine) palladium (17.5 mg, 0.015 mmol), tetrabutylammonium bromide (322.5 mg, 1.0 mmol) were placed in a 20 ml Schlenk tube, Replaced with nitrogen. Toluene (5 ml) and 3M aqueous potassium hydroxide solution (1.0 ml, 3.0 mmol) were added thereto, and the mixture was stirred at 80 ° C. for 24 hours under light shielding conditions. The reaction solution was cooled to room temperature, methylene chloride (7 ml) was added, washed 3 times with water (3 ml), and poured into stirring methanol (200 ml). The deposited precipitate was collected by filtration, washed with methanol and dried to obtain an ocherous solid (yield: 414.1 mg, yield: 90%).

The obtained solid was dissolved in CDCl ₃ by the same method as in Synthesis Example 1 and subjected to ¹ H-NMR measurement. As a result, cis-poly (99% or more of vinylene sites in the polymer chain was controlled to have a cis structure (99% or more). Phenylene vinylene (hereinafter abbreviated as cis-PPV) (ratio of cis structure / trans structure: 99/1 or more). Further, the resulting cis-PPV about 1mg dissolved in THF, GPC (standard substance: polystyrene) result of analysis, the number-average molecular weight ^_(M n b) 5850, polydispersity 3.61 (polystyrene standards) Met.

  Table 1 shows the number average molecular weight before light irradiation, the charge mobility before and after light irradiation, the energy level after light irradiation, and the band gap values measured according to the method described above.

  The values of HOMO, LUMO level, and band gap (BG) in Table 1 above are values after light irradiation (Synthesis Example 3-2 is after light irradiation and a rinsing step).

  From Table 1 above, it can be seen that the charge mobility improves as poly (arylene vinylene) increases in molecular weight. In addition, it can be seen from Synthesis Examples 3-1 and 3-2 that the charge mobility can be further improved by employing a rinsing step after light irradiation.

[Synthesis Example 5]
A cis-PPV was prepared in the same procedure as in Synthesis Example 3-1. The ratio of cis structure / trans structure by ¹ H-NMR measurement is 99/1 or more, number average molecular weight (M _n ^b ) 15700 by GPC (standard substance: polystyrene) analysis, polydispersity 2.49 (polystyrene standard) Met.

Further, the high molecular weight portion of the obtained cis-PPV was recycled and collected in the same manner as in Synthesis Example 3-1, and the solvent was distilled off under reduced pressure to obtain a tan solid cis-PPV. Then, the resulting cis-PPV about 1mg dissolved in THF, GPC (standard substance: polystyrene) was analyzed, the number average molecular weight ^_(M n b) 34600, polydispersity 1.47 (polystyrene standards) Met. Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 2. Moreover, the ultraviolet-visible absorption spectrum before and after light irradiation of the thin film obtained using cis-PPV obtained at this time and after rinsing is shown in FIG.

[Synthesis Example 6]
(Z, Z) -2,5-bis (2-bromoethenyl) thiophene (29.4 mg, 0.10 mmol, first arylene compound), 1,4-bis (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolanyl) -2,5-dioctyloxybenzene (58.6 mg, 0.10 mmol, second arylene compound), tetrakis (triphenylphosphine) palladium (1.7 mg, 0.0015 mmol) Trioctylmethylammonium chloride (4.0 mg, 0.01 mmol) was placed in a 20 ml Schlenk tube with an internal volume and purged with argon. Toluene (0.50 ml) and 2M aqueous sodium carbonate solution (0.15 ml, 0.30 mmol) were added thereto, and the mixture was refluxed on a 115 ° C. oil bath for 24 hours under light-shielding conditions. After cooling to room temperature, the reaction solution was diluted with dichloromethane (3 ml), washed three times with water (3 ml), and this dichloromethane solution was poured into a stirred mixed solvent of methanol (25 ml) / dichloromethane (5 ml). . The deposited precipitate was collected by filtration, washed with methanol, and dried to obtain a red-orange viscous solid (yield: 42.3 mg, yield: 91%, S atom content: 6.8% by mass). .

The obtained solid was dissolved in CDCl ₃ (reference substance: tetramethylsilane) in the same manner as in Synthesis Example 1, and ¹ H-NMR measurement (400 MHz, manufactured by Burker, Avance 400) was performed. It was confirmed that cis-poly (phenylene vinylene thienylene vinylene) (cis-PPVTV) in which the vinylene site in the cis structure was controlled by 99% or more (cis-trans / trans structure ratio: 99/1 or more). Further, the resulting cis-PPVTV about 1mg dissolved in THF, GPC (standard substance: polystyrene) result of analysis, the number-average molecular weight ^_(M n b) 7300, polydispersity 2.31 (polystyrene standards) Met. Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 2.

[Synthesis Example 7]
(Z, Z) -2,5-bis (2-bromoethenyl) thiophene (34.1 mg, 0.116 mmol, first arylene compound), 2,5-bis (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolanyl) -3-hexylthiophene (48.8 mg, 0.116 mmol, second arylene compound), tetrakis (triphenylphosphine) palladium (1.7 mg, 0.0015 mmol), trichloride Octylmethylammonium (4.0 mg, 0.01 mmol) was placed in a 20 ml Schlenk tube with an internal volume and purged with argon. Toluene (0.50 ml) and 2M aqueous sodium carbonate solution (0.15 ml, 0.30 mmol) were added thereto, and the mixture was refluxed on a 115 ° C. oil bath for 24 hours under light-shielding conditions. After cooling the reaction solution to room temperature, dichloromethane (3 ml) was added thereto, washed with water (3 ml) three times, and this dichloromethane solution was poured into a stirring mixed solvent of methanol (25 ml) / dichloromethane (5 ml). It is. The deposited precipitate was collected by filtration, washed with methanol, and dried to obtain a reddish purple viscous solid (yield: 28.2 mg, yield: 81%, S atom content: 21.2% by mass). .

When the obtained solid was dissolved in CDCl ₃ (reference substance: tetramethylsilane) and subjected to ¹ H-NMR measurement in the same manner as in Synthesis Example 6, the vinylene moiety in the polymer chain was 99% or more in cis structure. Cis-poly (thienylene vinylene) (cis-PTV) was confirmed (cis / trans ratio: 99/1 or more). Further, the resulting cis-PTV about 1mg dissolved in THF, GPC (standard substance: polystyrene) result of analysis, the number-average molecular weight ^_(M n b) 2600, polydispersity 2.08 (polystyrene standards) Met. Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 2. Moreover, the ultraviolet-visible absorption spectrum before and after light irradiation of the thin film obtained using cis-PTV obtained at this time and after rinsing is shown in FIG.

[Synthesis Example 8]
A cis-PPV was prepared in the same procedure as in Synthesis Example 4. The ratio of cis structure / trans structure by ¹ H-NMR measurement is 99/1 or more, number average molecular weight (M _n ^b ) 5850 by GPC (standard substance: polystyrene) analysis, polydispersity 3.61 (polystyrene standard) Met. Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 2.

  Moreover, the ultraviolet visible absorption spectrum before and behind light irradiation of the thin film formed into a film using the polymer obtained by the synthesis examples 5 and 7 and after rinse is shown to FIGS.

  From the results of Table 2, it can be seen that when the thiophene skeleton is present in the resin film, the charge mobility can be remarkably improved (Synthesis Examples 6 and 7). It can also be seen that the charge mobility can be further improved by adopting a rinsing step even in the case of having a thiophene skeleton (Synthesis Example 7).

  From FIG. 1, in the spectrum B after the light irradiation, the peak top shifts to the longer wavelength side and the absorbance increases compared to the spectrum A before the light irradiation. From the change from spectrum A to B, it can be confirmed that trans-poly (arylene vinylene) is present in the resin film of Synthesis Example 5 after light irradiation. Further, in the spectrum C after rinsing, the peak top shifts to the longer wavelength side as compared with the spectrum B, and new absorption (shoulder) occurs near the wavelength of 510 nm. From this result, it is considered that by performing the rinsing step, a change occurs in the alignment structure in the resin film, which has some influence on the charge mobility. Also in Synthesis Example 7, the same spectrum change can be confirmed in the spectrum after rinsing (FIG. 2, shift of peak top to long wavelength side, shoulder). In addition, the charge mobility of each resin film after rinsing is increased, and it can be seen that the charge mobility of the conductive resin film can be improved by rinsing after light irradiation.

[Synthesis Example 9]
(Z, Z) -5,5′-bis (2-bromoethenyl) -2,2′-bithiophene (37.6 mg, 0.10 mmol, first arylene compound), 4,4′-dihexyl-5,5 ′ -Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2,2'-bithiophene (58.7 mg, 0.10 mmol, second arylene compound), tetrakis ( Triphenylphosphine) palladium (1.7 mg, 0.0015 mmol) and trioctylmethylammonium chloride (4.0 mg, 0.01 mmol) were placed in a Schlenk tube with an internal volume of 20 ml and purged with argon. Toluene (0.5 ml) and 2M aqueous sodium carbonate solution (0.15 ml, 0.30 mmol) were added thereto, and the mixture was heated to reflux on an oil bath at 115 ° C. for 24 hours under light-shielding conditions. After cooling the reaction solution to room temperature, dichloromethane (3 ml) was added, washed with water (3 ml) three times, and the resulting dichloromethane solution was stirred in a mixed solvent of methanol (25 ml) / dichloromethane (5 ml). It was dripped. The deposited precipitate was collected by filtration, washed with methanol, and dried to obtain a reddish purple solid (56.7 mg, S atom content: 22.8% by mass).

The obtained solid was dissolved in deuterated chloroform (CDCl ₃ , reference material: tetramethylsilane) and subjected to ¹ H-NMR measurement (400 MHz, Bruker, AVANCE 400). As a result, 99 of the polyvinylene moiety in the polymer chain was measured. % Or more was confirmed to be cis-poly (bithienylene vinylene) (hereinafter abbreviated as cis-PBTV) having a cis structure (ratio of cis structure / trans structure: 99/1 or more). Further, about 1 mg of the obtained cis-PBTV was dissolved in THF, and gel permeation chromatography (GPC, manufactured by JASCO, columns: KF-801, KF-803L, KF-805L, manufactured by Shodex, standard substance: polystyrene) result of the analysis, a number average molecular weight ^_(M n b) 11300, polydispersity 6.26 (polystyrene standard).

  Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 3.

[Synthesis Example 10]
(Z, Z) -5,5′-bis (2-bromoethenyl) -2,2′-bithiophene (75.2 mg, 0.20 mmol, first arylene compound), 4,4′-dihexyl-5,5 ′ -Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2,2'-bithiophene (117.4 mg, 0.20 mmol, second arylene compound), tetrakis ( Triphenylphosphine) palladium (3.4 mg, 0.003 mmol) and trioctylmethylammonium chloride (8.0 mg, 0.02 mmol) were placed in a Schlenk tube with an internal volume of 20 ml and purged with nitrogen. Toluene (1.0 ml) and a 2M sodium carbonate aqueous solution (0.3 ml, 0.60 mmol) were added thereto, and the mixture was heated to reflux on an oil bath at 115 ° C. for 24 hours under a light-shielding condition. After cooling the reaction solution to room temperature, dichloromethane (6 ml) was added, washed with water (3 ml) three times, and the resulting dichloromethane solution was stirred in a mixed solvent of methanol (50 ml) / dichloromethane (10 ml). It was dripped. The deposited precipitate was collected by filtration, washed with methanol, and dried to obtain a reddish purple solid (yield: 116 mg, S atom content: 23.3 mass%).

The obtained solid was dissolved in deuterated chloroform (CDCl ₃ , reference material: tetramethylsilane) and subjected to ¹ H-NMR measurement (400 MHz, Bruker, AVANCE 400). As a result, 99 of the polyvinylene moiety in the polymer chain was measured. % Or more was confirmed to be cis-poly (bithienylene vinylene) (hereinafter abbreviated as cis-PBTV) having a cis structure (ratio of cis structure / trans structure: 99/1 or more). Further, about 1 mg of the obtained cis-PBTV was dissolved in THF, and gel permeation chromatography (GPC, manufactured by JASCO, columns: KF-801, KF-803L, KF-805L, manufactured by Shodex, standard substance: polystyrene) result of the analysis, a number average molecular weight ^_(M n b) 12100, polydispersity 1.67 (polystyrene standard).

The total amount of the obtained cis-PBTV was dissolved in chloroform, filtered through a syringe filter, and then recycled preparative GPC (manufactured by JAI, LC918U, columns: JAIGEL-1H-A, JAIGEL-2H-A, solvent: chloroform). ), Three polymers having different molecular weights were obtained. Each fraction collected was air-dried under light shielding, and the solvent was distilled off under reduced pressure to obtain a reddish purple solid (cis-PBTV). The yield of the polymer, the number average molecular weight (M n ^_b) and polydispersity are as follows.
High molecular weight component (Yield: 9 mg, M _n ^b : 38300, polydispersity: 1.45)
Medium molecular weight component (Yield: 28 mg, M _n ^b : 19900, polydispersity: 1.35)
Low molecular weight component (Yield: 30 mg, M _n ^b : 7700, polydispersity: 1.23)
Various characteristics were evaluated according to the above measurement methods. The results are shown in Table 3.

* 1: This is an example in which light irradiation was performed under heating at 150 ° C. using an ODTS-treated substrate.

  From Table 3, it can be seen that when the bithiophene skeleton (bithienylene skeleton) is present in the thin film, the charge mobility is improved as compared with the case where the phenylene vinylene skeleton or the thiophene vinylene skeleton is present. The reason why the charge mobility is thus improved is not clear, but it is presumed that the presence of the bithiophene skeleton improves the packing of the conductive resin molecular chains.

  In addition, in FIG. 3, the same changes as in FIG. 1 (long wavelength shift of peak top after light irradiation, increase in absorbance), that is, generation of trans-poly (arylene vinylene) by light irradiation can be confirmed (spectrum A → spectrum). B). Also in the spectrum C after rinsing, the same changes as in FIG. 1 such as the shift of the peak top to the long wavelength side and the appearance of new absorption (shoulder) near 640 nm can be confirmed, and the thin film after light irradiation has been confirmed. It can be seen that the charge mobility of the conductive resin film can be improved by rinsing.

  In FIG. 3, the spectra of B ′ after heat / light irradiation and C ′ after rinsing show an example of light irradiation under heating. Compared with the spectrum B after light irradiation, the absorbance of the spectrum B ′ after light irradiation under heating is large, so that the transition from the cis body to the trans body can be promoted by light irradiation under heating. I understand.

  Since the conductive resin film of the present invention has high charge mobility, it is suitable for materials such as organic EL (organic electroluminescence), organic FET (organic field effect transistor), batteries, capacitors, and photoelectric conversion elements (solar cells). Used for. In addition, since the conductive resin film of the present invention can control the solubility of the film in an organic solvent by light irradiation, the solubility in an organic solvent can be reduced by reducing the solubility of the film in the organic solvent by light irradiation. Further, a similar material can be further stacked, and a device including a mixed layer in a part of the stacked structure can be manufactured. Thereby, the performance improvement of organic semiconductors, such as organic EL, an organic solar cell, and organic TFT, can be anticipated. Furthermore, by performing partial light irradiation, patterning can be performed by distinguishing between a light irradiation part and a light non-irradiation part.

  In addition, since the conductive resin film of the present invention can be improved from an electrically insulating state to a charge mobility higher than that of the semiconductor region by light irradiation, the conductive resin can be provided by distinguishing the light irradiated portion and the light non-irradiated portion. The electrical properties in the film can also be controlled.

Claims (10)

A resin composition for forming a conductive resin film, wherein the charge mobility of the conductive resin film is less than 1.0 × 10 ⁻⁶ cm ² V ⁻¹ s ⁻¹ to 1.0 × 10 ^{− when} irradiated with light. A resin composition characterized by improving to ⁵ cm ² V ^-1 s ^-1 or more.   The resin composition according to claim 1, wherein the resin composition contains poly (arylene vinylene).   The resin composition according to claim 1 or 2, wherein the poly (arylene vinylene) has a thiophene skeleton.   The said resin composition contains 3 mass% or more of sulfur atoms, The resin composition in any one of Claims 1-3 characterized by the above-mentioned.   The resin composition according to claim 1, wherein the poly (arylene vinylene) has a number average molecular weight of 7500 or more. It is an electroconductive resin film obtained from the resin composition in any one of Claims 1-5, Comprising: The charge mobility of the said resin film before light irradiation is 1.0 * 10 <^-6> cm < ^{2 >} V <^-1> s. A conductive resin film having a charge mobility of less than ⁻¹ and a charge mobility after light irradiation of 1.0 × 10 ⁻⁵ cm ² V ⁻¹ s ⁻¹ or more.   The conductive resin film according to claim 6, wherein the conductive resin film has a trans-poly (arylene vinylene) structure. A method for forming a conductive resin film according to claim 6 or 7,
Forming a coating film with a conductive resin film-forming solution containing the resin composition; and
A step of irradiating the coating film with light having a wavelength of 200 to 600 nm,
A method for forming a conductive resin film, comprising:   The method for forming a conductive resin film according to claim 8, further comprising a rinsing step after the light irradiation step. A device comprising the conductive resin film according to claim 1.