JP2011029366A - Laminated structure, method for producing the same, and electronic element comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated structure that can lower the driving voltage of an electroluminescent element and can make power consumption small. <P>SOLUTION: The laminated structure comprises an electrode, a polymer binding layer arranged on the electrode, and an electrically conductive organic material layer arranged on the polymer binding layer, wherein the polymer binding layer comprises an aromatic polymeric compound which has a structure represented by formula (I) [wherein Ar represents a conjugated divalent group which may have a substituent, provided that when there are multiple Ar's, the Ar's may be the same as or different from each other; and n represents an integer of 1 or greater] and has a number average molecular weight of 1×10<SP>3</SP>to 1×10<SP>8</SP>inclusive in terms of polystyrene content, the polymer binding layer is bonded to the electrode via a chemical bond between the aromatic polymeric compound and the surface of the electrode, and an electrically conductive organic material that composes a layer included in the electrically conductive organic material layer and arranged adjacent to the polymer binding layer has a number average molecular weight of 3×10<SP>2</SP>to 1×10<SP>8</SP>inclusive in terms of polystyrene content. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminated structure used for an electroluminescent element, a photoelectric conversion element or the like.

  In order to improve the characteristics of an electroluminescent element including a laminated structure, it has been studied to insert a bonding layer of an aromatic organic compound chemically bonded to the electrode surface between the conductive organic material layer and the electrode. For example, a laminated structure in which a bonding layer having a triphenylamine skeleton or a thiophene skeleton having a group capable of chemical bonding with a reactive group present on the anode surface is inserted between the anode and the conductive organic material layer is known. (Patent Document 1, Non-Patent Document 1, Non-Patent Document 2).

  However, these aromatic organic compounds are all low molecular compounds or oligomer compounds having a polystyrene-equivalent number average molecular weight of less than 1000, and the molecular chain length was 5 nm or less. When using a compound with such a low degree of polymerization, the compound crystallizes when producing a chemically bonded layer on the electrode surface, making it difficult to produce a uniform bonded layer with good reproducibility. There is a problem that the drive voltage of the electroluminescent element is high and the power consumption is large.

JP 2005-310469 A

J. et al. Am. Chem. Soc. 2005, 127, 10058-10062 J. et al. Mater. Chem. , 2003, 13, 38-43

  The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a laminated structure that can reduce the driving voltage of an electroluminescent element and reduce power consumption.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have a specific number average molecular weight between the electrode in the laminated structure and the conductive organic material layer and the surface of the electrode. By inserting a polymer bonding layer composed of an aromatic polymer compound that can be chemically bonded, such a laminated structure can improve the characteristics of the electroluminescent device and the photoelectric conversion device. As a result, the present invention has been completed.

That is, the laminated structure of the present invention includes an electrode, a polymer binding layer disposed on the electrode, and a conductive organic material layer disposed on the polymer binding layer.
The polymer binding layer has the following formula (I):

(In the formula, Ar is a conjugated divalent group which may have a substituent, and when there are a plurality of them, they may be the same or different, and n is an integer of 1 or more. .)
And an aromatic polymer compound having a polystyrene-reduced number average molecular weight of 1 × 10 ³ or more and 1 × 10 ⁸ or less,
The polymer bonding layer is bonded to the electrode through a chemical bond between the aromatic polymer compound and the electrode surface,
The conductive organic material constituting the layer adjacent to the polymer bonding layer in the conductive organic material layer has a polystyrene equivalent number average molecular weight of 3 × 10 ² or more and 1 × 10 ⁸ or less.

  In the laminated structure of the present invention, the film thickness of the polymer bonding layer is 0.1 nm to 100 μm, and the film thickness of the layer adjacent to the polymer bonding layer in the conductive organic material layer is 0.1 nm. It is preferably ˜1 cm.

  Further, the orbital energy of the lowest unoccupied molecular orbital (LUMO) of the aromatic polymer compound is −4.0 eV or more and −0.5 eV or less and / or the highest occupied molecular orbital (HOMO) of the aromatic polymer compound. Preferably, the orbital energy is −6.0 eV or more and −4.0 eV or less, and the LUMO orbital energy of the aromatic polymer compound and the layer adjacent to the polymer bonding layer in the conductive organic material layer are configured. The difference between the LUMO orbital energy of the conductive organic material to be -2.5 eV to +2.5 eV and / or the HOMO orbital energy of the aromatic polymer compound and the polymer in the conductive organic material layer It is also preferable that the difference between the HOMO orbital energy of the conductive organic material constituting the layer adjacent to the bonding layer is −1.5 eV or more and +1.5 eV or less.

  In the laminated structure of the present invention, it is preferable that a terminal group of the aromatic polymer compound is chemically bonded to a reactive group present on the surface of the electrode. The electrode includes a base metal, a noble metal, and an oxidation thereof. It is preferable that it contains at least one electrically conductive compound selected from the group consisting of materials.

  As the polymer binding layer, the following formula (II):

(In the formula, Ar ¹ is a divalent group having an aromatic ring, G is an r + p valent group having an aromatic ring, X ¹ is a terminal group, and r is an integer of 1 to 10, n and p are each independently an integer of 1 or more, and when r is 2 or more, a plurality of existing E ^a may be the same or different, and exist when n is 2 or more. A plurality of Ar ¹ may be the same or different, and when p is 2 or more, a plurality of X ^{1 present} may be the same or different, and E ^a is a mercapto group, hydroxy Group, carboxyl group, sulfonic acid group, phosphonic acid group, trialkoxysilyl group, trihydroxysilyl group, chlorocarbonyl group, chlorophosphonic acid group, chlorosulfonic acid group, cyanato group, isocyanato group, amino group, substituted amino group and Substituted disul Is a monovalent group selected from the group consisting of I de group.)
It is preferable that the electrode is formed by immersing the electrode in a solution containing the conjugated polymer represented by the formula (1) at a concentration of 0.0001% by mass or more and / or applying the solution to the electrode.

  Moreover, as said polymer coupling layer, the following formula (III):

(In the formula, G is an r + p-valent group having an aromatic ring, X ^a is a halogen atom or —SO ₃ Q ^a (where Q ^a represents an alkyl group or an aryl group, and the alkyl group and the aryl are substituted) And r is an integer of 1 or more and 10 or less, p is an integer of 1 or more, and when p is 2 or more, a plurality of X present ^a may be the same or different, and E is a mercapto group, hydroxy group, carboxyl group, sulfonic acid group, phosphonic acid group, trialkoxysilyl group, trihydroxysilyl group, chlorocarbonyl group, chlorophosphonic acid A monovalent group selected from the group consisting of a group, a chlorosulfonic acid group, a cyanato group, an isocyanato group, an amino group, a substituted amino group and a substituted disulfide group, and a reactive group present on the electrode surface It is a linking group formed by a chemical bond.)
In the presence of an electrode to which a group represented by formula (IV) is bonded, the following formula (IV):

(In the formula, Ar ¹ is a divalent group having an aromatic ring, M is a halogen atom, a hydrogen atom, —B (OQ ¹ ) ₂ (where Q ¹ is independently a hydrogen atom, an alkyl group, or an aryl group). Represents a ring formed by bonding to each other, the alkyl and the aryl group may have a substituent, and —Si (Q ² ) ₃ (where Q ² is an alkyl group). Or an alkoxy group, wherein the alkyl group and the alkoxy group may have a substituent, -Sn (Q ³ ) ₃ (where Q ³ is an alkyl group which may have a substituent). A group represented by —SO ₃ Q ^a (wherein Q ^a is an alkyl group or an aryl group, and the alkyl group and the aryl group may have a substituent), or —Z ¹ (Z ² ) _m (where Z ¹ is a metal atom or metal And Z ² is a counter anion), and two Ms may be the same or different.)
It is also preferable that the aromatic compound represented by the formula (1) is formed by polycondensation using a polymerization catalyst or an equivalent reactant.

  Moreover, as said polymer coupling layer, following formula (V):

(In the formula, Ar ¹ is a divalent group having an aromatic ring, G is an r + p valent group having an aromatic ring, X ¹ is a terminal group, and r is an integer of 1 to 10, n and p are each independently an integer of 1 or more, and when r is 2 or more, a plurality of existing E may be the same or different. When n is 2 or more, a plurality of existing E Ar ¹ may be the same or different, and when p is 2 or more, a plurality of X ^{1 present} may be the same or different, and E is a mercapto group, a hydroxy group, Carboxyl group, sulfonic acid group, phosphonic acid group, trialkoxysilyl group, trihydroxysilyl group, chlorocarbonyl group, chlorophosphonic acid group, chlorosulfonic acid group, cyanato group, isocyanato group, amino group, substituted amino group and substituted disulfide A linking group formed by a chemical bond between a monovalent group selected from the group consisting of groups and a reactive group present on the surface of the electrode.)
It is also preferable that it has the structure represented by these.

  The bonding group E in the formula (V) is at least one selected from the group consisting of a covalent bond, a coordinate bond, a hydrogen bond and an ionic bond between the monovalent group and a reactive group present on the electrode surface. A linking group formed by a seed is preferable, and the monovalent group includes a mercapto group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a chlorocarbonyl group, a chlorophosphonic acid group, and a chlorosulfonic acid group. It is preferably a monovalent group selected from the group.

  As G in the formula (V), a monocyclic ring which may have a substituent, a condensed ring which may have a substituent, a ring assembly which may have a substituent, and a substituent. Preferably, it is at least one r + p-valent group selected from the group consisting of the bridged polycyclic ring which may have, and the r + p-valent group includes the following formulas (1) to (16):

More preferably, it contains at least one of the heterocyclic ring and aromatic ring represented by the formula (5), and particularly preferably contains one heterocyclic ring represented by the formula (5).

  In the laminated structure of the present invention, r in the formula (V) is an integer of 1 or more and 3 or less (provided that G in the formula (V) is a monocyclic aromatic ring structure and constitutes the ring structure. It is preferable that r is 1 when there are 2 carbon atoms and r is 1 or 2 when there are 3 carbon atoms.

As Ar ¹ in the formula (V), the following formula (VI):

Wherein R ⁵ is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the alkyl group, the aryl group, the arylalkyl group and the monovalent heterocyclic group are R ⁶ may have a substituent, and R ⁶ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group , Arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, carbamoyl group, imide residue, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Group, the alkyl group, the alkoxy group, the alkylthio group, the aryl group. The aryloxy group, the arylthio group, the arylalkyl group, the arylalkoxy group, the arylalkylthio group, the arylalkenyl group, the arylalkynyl group, the acyl group, the acyloxy group, the carbamoyl group, and the monovalent group. The heterocyclic group may have a substituent, and a plurality of R ⁵ and R ⁶ may be the same or different, and R ⁵ and an alkyl group which may have a substituent. When a plurality of R ⁶ are present, they may be bonded to each other to form a ring.)
Is contained in an amount of 0.1% by mass or more based on the total mass of all repeating units in the aromatic polymer compound constituting the polymer binding layer, and / or the following formula (VII ):

(Wherein, ^{R 6} has the same meaning as ^{R 6} in formula (VI).)
It is preferable that 0.1 mass% or more is contained with respect to the total mass of the number of all the repeating units in the aromatic polymer compound which comprises the polymer coupling layer.

  In the laminated structure of the present invention, the molar percentage of the repeating unit represented by the above formula (VI) and the above formula with respect to the total of all repeating units in the aromatic polymer compound constituting the polymer binding layer. The total with the mole percentage of the repeating unit represented by (VII) is preferably 10 mol% or more and 100 mol% or less.

  The method for producing a laminated structure of the present invention has the following formula (I):

(In the formula, Ar is a conjugated divalent group which may have a substituent, and when there are a plurality of them, they may be the same or different, and n is an integer of 1 or more. .)
The number average molecular weight in terms of polystyrene is 1 × 10 ³ or more and 1 × 10 ⁸ or less, and the aromatic polymer compound is chemically bonded to the electrode surface. Forming a polymer binding layer,
Forming a layer composed of a conductive organic material having a polystyrene-equivalent number average molecular weight of 3 × 10 ² or more and 1 × 10 ⁸ or less on the polymer binding layer;
It is a method including.

  The electronic device of the present invention includes the laminated structure of the present invention, and is used for, for example, an electroluminescent device or a photoelectric conversion device.

  The conjugated polymer of the present invention has the following formula (VIII):

(In the formula, Ar ¹ is a divalent group having an aromatic ring, X ¹ is a terminal group, n is an integer of 1 or more, Ar ¹⁵ is an i + p valent group having an aromatic ring, and i And p are each independently an integer of 1 or more, i + p is 2 or more and 20 or less, Y is an oxygen atom, sulfur atom, imino group, substituted imino group, ethenylene group, substituted ethenylene group or ethynylene group, j Is 0 or 1, and R ⁷ is a hydrogen atom, alkyl group, alkylthio group, aryl group, arylthio group, arylalkyl group, arylalkylthio group, arylalkenyl group, arylalkynyl group, silyl group, substituted silyl group, acyl group Or a monovalent heterocyclic group, the alkyl group, the alkylthio group, the aryl group, the arylthio group, the arylalkyl group, the arylalkyl The thio group, the arylalkenyl group, the arylalkynyl group, the acyl group, and the monovalent heterocyclic group may have a substituent, and two R ⁷ may be the same or different. It may be bonded to each other to form a ring.)
It can be suitably used for forming a polymer binding layer in the laminated structure of the present invention.

  The conjugated compound of the present invention has the following formula (IX):

(In the formula, Ar ¹⁵ is an i + p-valent group having an aromatic ring, i and p are each independently an integer of 1 or more, i + p is 2 or more and 20 or less, and X ^a is a halogen atom or —SO _3. Q ^a (wherein Q ^a represents an alkyl group which may have ^a substituent), Y represents an oxygen atom, sulfur atom, imino group, substituted imino group, ethenylene group, substituted ethenylene A group or an ethynylene group, j is 0 or 1, and R ⁷ is a hydrogen atom, alkyl group, alkylthio group, aryl group, arylthio group, arylalkyl group, arylalkylthio group, arylalkenyl group, arylalkynyl group, silyl group Group, substituted silyl group, acyl group or monovalent heterocyclic group, the alkyl group, the alkylthio group, the aryl group, the arylthio group, the aryl Alkyl group, the arylalkylthio group, the arylalkenyl group, the arylalkynyl group, the acyl group and the monovalent heterocyclic group may have a substituent, the two R ⁷ have the same May be different from each other and may be bonded to each other to form a ring).
It can be suitably used to form a polymer binding layer in the laminated structure of the present invention, and particularly used as a raw material for the conjugated polymer represented by the formula (II). In addition, the conjugated compound represented by the formula (IX) is bonded to the electrode surface, and the aromatic compound represented by the formula (IV) is converted into a polymerization catalyst or equivalent reaction using this as a starting point. It is also effective to perform polycondensation using an agent.

  By using the laminated structure of the present invention, an electroluminescent element with low driving voltage and low power consumption can be obtained. Further, by using the conjugated polymer or conjugated compound of the present invention, a polymer binding layer constituting such a laminated structure can be formed.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the laminated structure of the present invention will be described. The laminated structure of the present invention is composed of an electrode, an aromatic polymer compound having a specific molecular weight disposed on the electrode, and bonded by chemical bonding between the aromatic polymer compound and the electrode surface. A molecular bonding layer and a layer made of a conductive organic material having a specific molecular weight disposed on the polymer bonding layer are provided.

<Electrode>
Examples of the electrode used in the present invention include those containing an electrically conductive compound such as a metal, an alloy, a metal oxide, a metal sulfide, and a metal halide. Examples of the metal include base metals, noble metals, alkali metals, alkaline earth metals, and the like, and examples of the alloys include alloys containing one or more of these metals, and the metal oxides, metal sulfides, and metal halogens. Examples of the halide include oxides, carbonates, composite oxides, sulfides, and halides of these metals. These electrically conductive compounds may be used alone or in combination of two or more.
Of these, base metals, noble metals and oxides thereof are preferable, and aluminum, chromium, copper, gold, silver, platinum, indium tin oxide (ITO), indium zinc oxide, molybdenum oxide, and aluminum oxide are more preferable, and aluminum, silver, and oxidation are preferable. Indium tin (ITO) is more preferable. Further, the electrode may have a single layer structure composed of one or more of these materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions.

<Conductive organic material layer>
The conductive organic material layer used in the present invention includes a hole injection layer, a hole transport layer, an interlayer, a light emitting layer, an electron transport layer, a hole block layer, an electron injection layer, and an electron donating compound, which will be described later. Examples thereof include a layer and a layer containing an electron-accepting compound. Such a conductive organic material layer is composed of a conductive organic material.

  As such a conductive organic material, the following formula (X):

An aromatic polymer compound having a structure represented by: In the laminated structure of the present invention, the conductive organic material layer may have a single-layer structure including one or more of the conductive organic materials, or a multilayer composed of a plurality of layers having the same composition or different compositions. A structure may be used.

In the formula (X), Ar ¹ is a divalent group having an aromatic ring, X ¹ is a terminal group, two X ¹ may be the same or different, and n is 1 It is an integer above, preferably an integer from 1 to 1 × 10 ⁶ , more preferably an integer from 1 to 1 × 10 ⁵ . X ¹ is bonded to the carbon atom constituting the aromatic ring in Ar ¹ . Examples of such X ¹ include a halogen atom, a nitro group, —SO ₃ Q ^a (where Q ^a is an alkyl group which may have a substituent, or an aryl group which may have a substituent. Group), an alkyl group which may have a substituent, an aryl group which may have a substituent, and the like.

In the laminated structure of the present invention, the number average molecular weight in terms of polystyrene of the conductive organic material constituting the layer adjacent to the polymer binding layer in the conductive organic material layer is 3 × 10 ² or more and 1 × 10 ⁸ or less. It is. When this number average molecular weight is less than the lower limit, the crystallinity of the conductive organic material becomes high, and it becomes difficult to form a uniform layer with good reproducibility. On the other hand, when the upper limit is exceeded, the conductive organic material becomes difficult to dissolve in the organic solvent, and it becomes difficult to handle. In the present invention, from such a viewpoint, the number average molecular weight in terms of polystyrene of the conductive organic material is preferably 5 × 10 ² or more and 1 × 10 ⁸ or less, and preferably 1 × 10 ³ or more and 1 × 10 ⁷ or less. It is more preferable that

  In the present invention, the “layer adjacent to the polymer bonding layer in the conductive organic material layer” means the layer itself when the conductive organic material layer has a single layer structure, In the case of a multilayer structure, the conductive organic material layer means a layer disposed at a position closest to the polymer bonding layer.

  In addition, the film thickness of the layer adjacent to the polymer bonding layer in the conductive organic material layer can employ an optimum film thickness depending on the material to be used. For example, the drive voltage and the light emission efficiency are appropriate. It can be selected to be a value. The specific film thickness is preferably 0.1 nm to 1 cm, more preferably 1 nm to 100 μm, and particularly preferably 5 nm to 10 μm. When the film thickness of the conductive organic material layer is less than the lower limit, pinholes tend to be generated. On the other hand, when the film thickness exceeds the upper limit, the driving voltage of the element tends to increase. In addition, the film thickness of the layer adjacent to the polymer bonding layer in the conductive organic material layer is determined using a high-precision fine shape measuring instrument (for example, Kosaka Laboratory Co., Ltd., trade name: Surfcorder ET3000). Average value.

<Polymer bonding layer>
The polymer bonding layer used in the present invention is a layer disposed between the electrode and the conductive organic material layer, and has the following formula (I):

(In the formula, Ar is a conjugated divalent group which may have a substituent, and when there are a plurality of them, they may be the same or different, and n is an integer of 1 or more. It is preferably an integer of 1 to 1 × 10 ⁶ , more preferably an integer of 1 to 1 × 10 ⁵ , and even more preferably an integer of 1 to 1 × 10 ⁴ .
It is comprised by the aromatic polymer compound which has a structure represented by these. Further, in the laminated structure of the present invention, the polymer binding layer is formed through a chemical bond between the aromatic polymer compound (preferably its end group) and the electrode surface (preferably a reactive group present on it). Are joined to the electrodes.

In the present invention, the number average molecular weight in terms of polystyrene of the aromatic polymer compound is 1 × 10 ³ or more and 1 × 10 ⁸ or less. When the number average molecular weight is less than the lower limit, it is difficult to form a polymer bonding layer with good reproducibility, and when the upper limit is exceeded, the aromatic polymer compound is difficult to dissolve in an organic solvent and is difficult to handle. In the present invention, from such a viewpoint, the number average molecular weight in terms of polystyrene of the aromatic polymer compound is preferably 1 × 10 ³ or more and 1 × 10 ⁷ or less, more preferably 2 × 10 ³ or more and 1 × 10 ⁷ or less. 4 × 10 ³ or more and 1 × 10 ⁶ or less are particularly preferable.

  The number average molecular weight in terms of polystyrene of the aromatic polymer compound constituting the polymer binding layer used in the present invention is that the polymer binding layer is a conjugated polymer represented by the formula (II) 0 0.0001% by mass of the conjugated polymer when the electrode is formed by immersing the electrode in a solution containing a concentration of 0.0001% by mass or more and / or applying the solution to the electrode. The molecular weight in terms of polystyrene was measured using gel permeation chromatography (GPC) (trade name: HLC-8220GPC, manufactured by Tosoh Corporation) for the solution contained at the above concentration, and the number averaged value. In the presence of an electrode in which the group represented by the formula (III) is bonded to the surface of the polymer bonding layer in the solution, the polymer represented by the formula (IV) is polymerized as a polymerization catalyst or an equivalent reaction. In the case where it is formed by polycondensation using an agent, the polymer binding layer formed on the electrode is immersed in a suitable solvent, and the aromatic compound constituting the polymer binding layer in this solvent After confirming that the solution was dissolved, the elution time of this solution was measured using a GPC (manufactured by Shimadzu Corporation: LC-10 series) equipped with a fluorescence detector (manufactured by Agilent Technologies, trade name: Agilent 1100 Series). Is a value calculated from a calibration curve of a polymer having a known molecular weight in terms of polystyrene.

  The film thickness of the polymer binding layer is usually preferably from 0.1 nm to 100 μm, more preferably from 0.2 nm to 10 μm, from the viewpoint of manufacturability and structural functionality. More preferably, it is 0.2 nm-1 micrometer, and it is especially preferable that it is 0.2 nm-500 nm.

  The film thickness of the polymer bonding layer is from the position on the electrode surface determined using a high-precision fine shape measuring instrument (trade name: Surfcorder ET3000, manufactured by Kosaka Laboratory Ltd.) to the highest position of the polymer bonding layer. Is the thickness.

  In the laminated structure of the present invention, the minimum unoccupied molecular orbital (LUMO) of the aromatic polymer compound is used from the viewpoint of supplying charge from the electrode to the polymer bonding layer or from the polymer bonding layer to the conductive organic material layer. ) Orbital energy is preferably −4.0 eV or more and −0.5 eV or less, more preferably −3.7 eV or more and −0.5 eV or less, and −3.5 eV or more and −0.5 eV or less. It is particularly preferred. Further, the orbital energy of the highest unoccupied molecular orbital (HOMO) of the aromatic polymer compound is preferably −6.0 eV or more and −4.0 eV or less, and −5.7 eV or more and −4.0 eV or less. Is more preferable, and −5.5 eV or more and −4.0 eV or less is particularly preferable. In the present invention, the orbital energy of at least one of LUMO and HOMO of the aromatic polymer compound is preferably within the above range, and it is particularly preferable that the orbital energy of both LUMO and HOMO is within the above range.

  Further, in the laminated structure of the present invention, from the viewpoint of supply of electric charge from the polymer binding layer to the conductive organic material layer, the LUMO orbital energy of the aromatic polymer compound constituting the polymer binding layer and The difference in orbital energy of LUMO of the conductive organic material constituting the layer adjacent to the polymer bonding layer in the conductive organic material layer is preferably −2.5 eV or more and +2.5 eV or less, and −2. It is more preferably 3 eV or more and +2.3 eV or less, and further preferably -2.0 eV or more and +2.0 eV or less. Further, the difference between the HOMO orbital energy of the aromatic polymer compound and the HOMO orbital energy of the conductive organic material constituting the layer adjacent to the polymer bonding layer in the conductive organic material layer is -1.5 eV. It is preferably +1.5 eV or less, more preferably -1.3 eV or more and +1.3 eV or less, and further preferably -1.2 eV or more and +1.2 eV or less.

In the present invention, the values of the orbital energy of LUMO and HOMO of the aromatic polymer compound and the conductive organic material can be calculated by a theoretical chemical method using a similar polymer. The similar polymer in the present invention is a polymer compound in which Ar ¹ in the formulas (V) and (X) is represented by the same structural formula.

The theoretical chemical method is a combination of a B3LYP density functional and a 6-31G ^* basis function (hereinafter referred to as “B3LYP / 6-31G ^* method”). Using the above method, the stable molecular structure and molecular orbital energy of similar polymers were calculated (see Chem. Phys. Lett. 2007, 439, pages 35 to 39). The calculation can be performed using a quantum chemical calculation program such as Gaussian 03.

  For example, the following formula:

(In the formula, m ² represents the degree of polymerization.)
In the polymer compound represented by the formula, the similar polymer is represented by the following formula in which Ar ¹ in the formulas (V) and (X) is the same structural formula:

(In the formula, m ² represents the degree of polymerization.)
It is a compound represented by these.

With respect to this similar polymer, the stable molecular structure and molecular orbital energy of the similar polymer were calculated using the B3LYP / 6-31G ^* method, and the orbital energies of LUMO and HOMO were calculated to be −1.70 eV and −4, respectively. 97 eV. Table 1 shows LUMO orbital energy and HOMO orbital energy of other similar polymers. Incidentally, m ¹ in the structural formula of Table 1 represents the degree of polymerization.

<Aromatic polymer compound>
The aromatic polymer compound used in the present invention has a structure represented by the formula (I). Examples of the divalent group having an aromatic ring which is Ar in the formula (I) include the following formulas (C-1) to (C-22), (D-1) to (D-24), (E- Examples thereof include divalent groups represented by 1) to (E-26), (G-1) to (G-8), and (J-1) to (J-22).

  Above all, from the viewpoints of stability and ease of synthesis, the above formulas (C-1) to (C-20), (D-1) to (D-20), (E-1) to (E-2) , (E-7) to (E-13), (E-15) to (E-20), (E-22) to (E-26), (G-1) to (G-8), ( Divalent groups represented by J-1) to (J-3), (J-5) to (J-14), and (J-18) to (J-22) are preferred, and the above formula (C- 1) to (C-6), (C-10), (C-11), (C-15), (D-16) to (D-20), (E-17) to (E-20) , (G-1) to (G-8), and (J-1) to (J-3) are more preferably divalent groups represented by the formulas (C-1) to (C-3), (C-10), (C-11), (C-15), (D-16) to (D-19), (E-17) to (E-20) , (G-1) to (G-6) are more preferable, and the above formulas (C-1), (C-11), (C-15), (D-16), The divalent groups represented by (E-20), (G-1), and (G-2) are particularly preferable.

R ^c in the above formula represents a hydrogen atom or a substituent, and from the viewpoint of stability of the copolymer and ease of synthesis, preferably a hydrogen atom, an alkyl group which may have a substituent, a substituted group An alkoxy group which may have a group, an alkylthio group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a substituent An arylthio group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkoxy group which may have a substituent, an arylalkylthio group which may have a substituent, a substituent An arylalkenyl group which may have a group, an arylalkynyl group which may have a substituent, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, and a substituent. Good acyl group, An acyloxy group which may have a substituent, a carbamoyl group which may have a substituent, an imide residue, a monovalent heterocyclic group which may have a substituent, a carboxyl group, a substituted carboxyl group And a cyano group, more preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and a substituent. An aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkoxy group which may have a substituent, a substituted amino group, a substituted silyl group and a substituent An optionally substituted acyl group, a substituted carboxyl group and a cyano group, and more preferably a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, and a substituted group. Have An aryloxy group which may have a substituent, an aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkoxy group which may have a substituent, and a substituted carboxyl group, Particularly preferred are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group and an optionally substituted aryl group, particularly preferably a hydrogen atom, It is an alkyl group which may have a substituent. Further, a plurality of R ^c present in the above formula may be the same or different.

Here, the alkyl group which may have a substituent may be linear, branched or cyclic, and usually has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 15 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, Heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, lauryl, 1-adamantyl, 2-adamantyl, trifluoromethyl, pentafluoroethyl, perfluoro Butyl group, perfluorohexyl group, perfluorooctyl group, methoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, etc. From the viewpoint of device characteristics, ease of synthesis, etc. and heat resistance, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl Group, hexyl group, octyl group, 2-ethylhexyl group, decyl group and 3,7-dimethyloctyl group are preferred. When there are a plurality of R ^{c s} that are alkyl groups that may have a substituent, two alkyl groups may be bonded to each other to form a ring.

  The alkoxy group which may have a substituent may be linear, branched or cyclic, and usually has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Specific examples thereof include a methoxy group. Ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2- Ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyl Oxy group, 2-methoxyethyloxy group, 2-ethoxy Ethyloxy group and the like. From the balance of solubility in organic solvent, easiness of synthesis and heat resistance, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy The group 3,7-dimethyloctyloxy group is preferred.

  The alkylthio group which may have a substituent may be linear, branched or cyclic, and usually has 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Examples of the substituent include an alkoxy group.

  The aryl group which may have a substituent is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and a group having a condensed ring, an independent benzene ring or two or more condensed rings are directly or vinylene. A group bonded through a group or the like is also included. The aryl group generally has 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, and 2-anthracenyl. Group, 9-anthracenyl group, and pentafluorophenyl group, and these may further have a substituent such as an alkyl group, an alkoxy group, an alkyloxycarbonyl group, and a substituted amino group. From the viewpoint of solubility in these organic solvents, device characteristics, easiness of synthesis, etc., it is selected from the group consisting of alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms and alkyloxycarbonyl groups. Preferred is a phenyl group having one or more substituents. Specific examples thereof include 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-propylphenyl group, mesityl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-isobutyl. Phenyl group, 4-s-butylphenyl group, 4-t-butylphenyl group, 4-pentylphenyl group, 4-isoamylphenyl group, 4-hexylphenyl group, 2,6-dimethyl-4-t-butylphenyl group 4-heptylphenyl group, 4-octylphenyl group, 4-nonylphenyl group, 4-decylphenyl group, 4-dodecylphenyl group, 3-methyloxyphenyl group, 4-methyloxyphenyl group, 3,5-dimethyl Oxyphenyl group, 4-propyloxyphenyl group, 4-isopropyloxyphenyl group, 4-butyloxypheny Group, 4-isobutyloxyphenyl group, 4-s-butyloxyphenyl group, 4-t-butyloxyphenyl group, 4-hexyloxyphenyl group, 3,5-dihexyloxyphenyl group, 4-heptyloxyphenyl group, 4-octyloxyphenyl group, 4-nonyloxyphenyl group, 4- (methoxymethoxy) phenyl group, 3- (methoxymethoxy) phenyl group, 4- (2-ethoxy-ethoxy) phenyl group, 3- (2-ethoxy) -Ethoxy) phenyl group, 3,5-bis (2-ethoxy-ethoxy) phenyl group, 3-methoxycarbonylphenyl group, 4-methoxycarbonylphenyl group, 3,5-dimethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group 4-ethoxycarbonylphenyl group, 3-ethyloxycarbonyl- - methoxyphenyl group, 3-ethyl-oxy-4- ethoxyphenyl group, 3-ethyl-oxy-4- hexyloxyphenyl group, and a 4-diphenylaminophenyl group.

The aryloxy group which may have a substituent usually has 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group ( C ₁ -C ₁₂ indicate that it has 1 to 12 carbon atoms, and the same applies to the following.), C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyl An oxy group is mentioned, and from the viewpoint of solubility in an organic solvent and ease of synthesis, a C _{1 to} C ₁₂ alkoxyphenoxy group and a C _{1 to} C ₁₂ alkylphenoxy group are preferable.

Good arylthio group which may have a substituent has a carbon atom number of usually 6 to 60, and specific examples thereof include a phenylthio _group, C 1 _{-C 12} alkoxyphenyl-thio _group, C 1 _{-C 12} alkylphenylthio Group, 1-naphthylthio group, 2-naphthylthio group and pentafluorophenylthio group.

The arylalkyl group which may have a substituent usually has 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkyl group, C _1. -C ₁₂ alkoxyphenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkyl group, 1-naphthyl _-C 1 _{-C 12} alkyl group, 2-naphthyl _-C 1 -C ₁₂ alkyl groups are mentioned. From the viewpoints of solubility in organic solvents, device characteristics, and ease of synthesis, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ alkylphenyls. -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group which may have a substituent usually has 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenylmethoxy group, a phenylethoxy group, a phenylbutoxy group, Phenyl-C ₁ -C ₁₂ alkoxy groups such as phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, phenyloctyloxy group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl _-C 1 _{-C 12} alkoxy groups, 1-naphthyl _-C 1 _{-C 12} alkoxy group, a 2-naphthyl _-C 1 _{-C 12} alkoxy group.

  The arylalkylthio group which may have a substituent usually has 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Examples of the substituent include an alkyl group and an alkoxy group.

The arylalkenyl group which may have a substituent usually has 8 to 60 carbon atoms, and specific examples thereof include a phenyl-C _{2 to} C ₁₂ alkenyl group (“C _{2 to} C ₁₂ alkenyl” means that the carbon number of the alkenyl moiety is 2 to 12. hereinafter, the _same.), C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkenyl _group, C 1 _{-C 12} alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl _-C 2 _{-C 12} alkenyl group, a 2-naphthyl _-C 2 _{-C 12} alkenyl group.

Which may have a substituent arylalkynyl group has a carbon number of usually 8 to 60, and examples thereof include phenyl _-C 2 _{-C 12} alkynyl group ( _"C 2 _{-C 12} alkynyl" the number of carbon atoms of the alkynyl moiety means that it is 2 to 12. hereinafter, the _same.), C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkynyl _group, C 1 _{-C 12} alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl _-C 2 _{-C 12} alkynyl group, a 2-naphthyl _-C 2 _{-C 12} alkynyl group.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The monovalent heterocyclic group may have a substituent. Carbon number of a substituted amino group is 1-60 normally without including carbon number of this substituent, Preferably it is 2-48. Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, s-butylamino group T-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxy Phenylamino group, a di _(C 1 _{-C 12} alkoxyphenyl) amino group, di _(C 1 _{-C 12} alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group , pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, a phenyl _-C triazyl amino group 1 _{-C 12} alkylamino _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkylamino _group, C 1 -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) Amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C _1- C ₁₂ alkylamino groups and the like.

  Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Carbon number of a substituted silyl group is 1-60 normally, Preferably it is 3-48. The alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group may have a substituent.

  The acyl group which may have a substituent usually has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include an acetyl group, a propionyl group, a butyryl group, and an isobutyryl group. , Pivaloyl group, benzoyl group, trifluoroacetyl group, and pentafluorobenzoyl group. Examples of the substituent include an alkyl group and an alkoxy group.

  The acyloxy group which may have a substituent usually has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an iso group. Examples include butyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, and pentafluorobenzoyloxy group. Examples of the substituent include an alkyl group and an alkoxy group.

  The carbamoyl group which may have a substituent usually has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include a formamide group, an acetamide group, a propioamide group, and a butyroamide group. Benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group. Examples of the substituent include an alkyl group and an alkoxy group.

The monovalent heterocyclic group which may have a substituent means an atomic group remaining after removing one hydrogen atom from a heterocyclic compound, and usually has 4 to 60 carbon atoms, preferably 4 ~ 20. The carbon number of the monovalent heterocyclic group does not include the carbon number of the substituent substituted on the heterocyclic ring. Here, a heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring contain not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Say. Specifically, a thienyl _group, C 1 _{-C 12} alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl _group, C 1 _{-C 12} alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , _C 1 _{-C 12} alkyl thienyl group, a pyridyl _group, a C 1 _{-C 12} alkyl pyridyl group are preferable.

<Method for forming polymer bonding layer>
Examples of the polymer binding layer used in the present invention include the following formula (XI):

What has the structure represented by these is mentioned.

G ¹ in the formula (XI) is an s + u + 1 valent group, an atom, a cation, an anion, or a single bond, and is generated from an atom belonging to Group 14 of the periodic table or an atom belonging to Group 13 of the periodic table. A cation generated from an atom belonging to Group 15 of the periodic table, a tetravalent adamantyl group, or a single bond, preferably a carbon atom, a silicon atom, a boron anion, a nitrogen cation, a tetravalent adamantyl group, Alternatively, a single bond is more preferable, and a carbon atom, a silicon atom, or a single bond is particularly preferable. G ² is a q + 1 valent group or a single bond, and among them, a q + 1 valent group or a single bond having an aromatic ring which may have a substituent is preferable. G ³ is a t + p valent group, and among them, a t + p valent group having an aromatic ring which may have a substituent is preferable. R ¹⁷ is a group defined in the same manner as R ^c described above, and the preferred range is also the same.

Q in the formula (XI) is an integer of 1 or more, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 5 or less, and further preferably an integer of 1 or more and 3 or less. Particularly preferred is 1 or 2. s is an integer of 1 or more, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 5 or less, still more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2 It is. u is an integer of 0 or more, preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 2 or less, and still more preferably 0. t is an integer of 1 or more, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 5 or less, still more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2 It is. When G ¹ is an atom belonging to Group 14 of the periodic table, an anion generated from an atom belonging to Group 13 of the periodic table, a cation generated from an atom belonging to Group 15 of the periodic table, or a tetravalent adamantyl group, When s + u = 3 and G ¹ is a single bond, s = 1 and u = 0. When G ² is a single bond, q = 1. Note that E, Ar ¹ , X ¹ , p and n in the formula (XI) will be described together in <Method (A) for binding conjugated polymer> described later.

  Among the polymer binding layers having such a structure represented by the formula (XI), the following formula (V):

What has the structure represented by these is preferable. Here, r = q × s × t, and G is the following formula (XII):

It becomes a structure represented by. ^{G 1, G 2, G 3} , p in the formula (XII), q, ^G 1 of s and t in the formula ^{(XI), G 2, G} 3, p, q, synonymous with s and t is there. * Represents a binding site to E or Ar ¹ . In the formula (XII), R ¹⁷ bonded to G ² is omitted.

  The polymer bonding layer can be formed by any method as long as the polymer bonding layer can be formed on the electrode. For example, a method of chemically bonding a conjugated polymer described later to the electrode surface [Method (A) And a method [method (B)] in which an aromatic compound is polycondensed with a functional group present on the electrode surface.

<Method of binding conjugated polymer (A)>
First, the method (A) for bonding a conjugated polymer will be described by taking as an example the case where the polymer binding layer represented by the formula (V) is formed. This method (A) comprises the following formula (II):

Depending on the kind and molecular weight of the conjugated polymer represented by the formula, it can be carried out in the gas phase, liquid phase, or solid phase, and is preferably carried out in the liquid phase from the viewpoint of ease of handling. When performed in a gas phase, it can be formed by depositing on a clean electrode in a vacuum by a method such as vapor deposition. When performed in a solid phase, it can be formed by rubbing the conjugated polymer represented by the formula (II) on a clean electrode. When performing in the liquid phase, the electrode is immersed in a solution containing the conjugated polymer represented by the formula (II) at a concentration of 0.0001% by mass or more, or the solution is applied to the electrode. Alternatively, the polymer bonding layer can be formed on the electrode by immersing the electrode in the solution and then applying the solution on the electrode. The details of the formula (II) will be described later.

  In any method, it is preferable to clean the surface of the electrode. If dirt or dust adheres to the electrode surface, defects may occur in the polymer binding layer. Therefore, it is preferable to immediately enter the step of forming a polymer binding layer on the electrode after washing the electrode. The cleaning method can be selected according to the type of electrode, and a known method can be used for each electrode. In order to form a polymer bonding layer with few defects, it is preferable to treat with ozone, plasma, etc. in the final cleaning step, more preferably with active oxygen species such as ozone, oxygen plasma, etc. In view of the above, it is particularly preferable to treat with ozone.

  The concentration of the solution containing the conjugated polymer represented by the formula (II) is a viewpoint that the polymer binding layer composed of the aromatic polymer compound having the structure represented by the formula (I) is stably obtained. Is preferably 0.0001 to 50% by mass, more preferably 0.001 to 10% by mass, and particularly preferably 0.005 to 1% by mass. In addition, the immersion time when the polymer binding layer is formed by immersion is usually within 100 hours, although it varies depending on the kind of the conjugated polymer.

  Further, it is preferable to use a solution from which impurities are removed as much as possible. In particular, if dust or other molecules adsorbing on the electrode surface are mixed in the solution, defects may occur in the resulting polymer bonding layer. The polymer bonding layer thus formed has a structure represented by (V).

Ar ¹ in the formulas (II), (V) and (XI) has the same meaning as Ar in the formula (I). G is an r + p-valent group having an aromatic ring, X ¹ is a terminal group, r is an integer of 1 to 10, and n and p are each independently an integer of 1 or more. When r is 2 or more, a plurality of existing E ^a and E may be the same or different. When n is 2 or more, the plurality of Ar ¹ present may be the same or different. When p is 2 or more, the plurality of X ¹ present may be the same or different. X ¹ is bonded to the carbon atom constituting the aromatic ring in Ar ¹ .

The terminal group X ¹ in the formulas (II), (V) and (XI) includes a hydrogen atom, a halogen atom, a nitro group, —SO ₃ Q ^a (where Q ^a may have ^a substituent). A good alkyl group or an aryl group which may have a substituent), an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An alkylthio group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a substituent Arylalkyl group which may have, arylalkoxy group which may have substituent, arylalkylthio group which may have substituent, arylalkenyl group which may have substituent, substituted Arylalkyl optionally having a group Nyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, optionally substituted acyl group, optionally substituted acyloxy group, carbamoyl group, imide residue A monovalent heterocyclic group optionally having a substituent, a carboxyl group, a substituted carboxyl group, a hydroxy group, a sulfonic acid group, a cyano group, a phosphoric acid group and a mercapto group, preferably a hydrogen atom, An alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a substitution An arylalkyl group which may have a group, an arylalkoxy group which may have a substituent, a halogen atom or a sulfonic acid group, more preferably a hydrogen atom or a substituent. Aryl group which may have a substituent aryloxy group, an aryl alkyl group which may have a substituent. When a plurality of end groups X ¹ are present, they may be the same or different from each other.

E ^a in the formula (II) is preferably a mercapto group, a hydroxy group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a trialkoxysilyl group, a trihydroxysilyl group, a chlorocarbonyl group (—COCl), A monovalent group selected from the group consisting of a chlorophosphonic acid group (—POCl ₂ ), a chlorosulfonic acid group (—SO ₂ Cl), a cyanato group, an isocyanato group, an amino group, a substituted amino group, and a substituted disulfide group; More preferably, it is a monovalent group selected from the group consisting of a mercapto group, a hydroxy group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a chlorocarbonyl group, a chlorophosphonic acid group and a chlorosulfonic acid group, and more preferably a mercapto group. Group, carboxyl group, sulfonic acid group, phosphonic acid group, chlorocarbonyl group, chlorophos It is a monovalent group selected from the group consisting of phonic acid groups and chlorosulfonic acid groups, and particularly preferably a monovalent group selected from the group consisting of mercapto groups and carboxyl groups. In addition, the substituted disulfide group is often formed by the combination of two mercapto groups. Like the mercapto group, the substituted disulfide group causes at least one kind of interaction selected from the group consisting of a covalent bond, a coordination bond, a hydrogen bond and an ionic bond. It is what has.

Here, the substituted disulfide group is a group represented by -SS- ^RD , and ^RD is preferably an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group. More preferably, it is a group.

E in the formulas (V) and (XI) is a group formed by chemical bonding of E ^a in the formula (II) with a reactive group present on the surface of the electrode, preferably the formula (II) E ^a therein is a linking group formed by at least one interaction selected from the group consisting of a covalent bond, a coordinate bond, a hydrogen bond and an ionic bond by reacting with a reactive group present on the electrode surface. As the E ^a for forming the bonding group E such a monovalent group exemplified as E ^a in the formula (II).

Incidentally, the formula (V) and (XI) of the binding group E in the state, i.e., is not clear binding state between the reactive groups present in E ^a and the electrode surface, E in the formula (II) The case where ^a is a mercapto group (—SH) will be described as an example. When the mercapto group forms a covalent bond with the reactive group present on the electrode surface, it can be represented by a structure in which the hydrogen atom of the mercapto group is replaced with an atom on the electrode surface. When the mercapto group forms a coordinate bond with the reactive group present on the electrode surface, the unshared electron pair on the sulfur atom of the mercapto group can be represented by being donated and bonded to the atom on the electrode surface. When a mercapto group forms a hydrogen bond with a reactive group present on the electrode surface, the hydrogen atom or sulfur atom of the mercapto group can be represented by a hydrogen bond with an atom on the electrode surface. When a mercapto group is ionically bonded to a reactive group present on the electrode surface, the mercapto ion generated by elimination of the hydrogen atom of the mercapto group as a ptron and the cationic species on the electrode surface are expressed in an electrostatic interaction state. be able to.

The reactive groups present on the electrode surface, represents an atomic and atomic groups of formula (II) in E ^a and capable of reacting with the electrode surface of the. For example, when the electrode is aluminum, the aluminum atoms present on the surface and the aluminum ions generated therefrom are reactive groups, and when the electrode is silver, the silver atoms present on the surface and the silver generated therefrom are present. Ions are reactive groups. When the surface of such a metal electrode is oxidized, an atomic group such as an oxygen atom, an oxygen ion, or a hydroxy group, a metal atom, and a metal ion present on the surface are reactive groups. For example, when the electrode is made of an oxide such as ITO, an atomic group such as an oxygen atom, an oxygen ion, or a hydroxy group, a metal atom, and a metal ion present on the surface are reactive groups. Such reactive groups are those present on the electrode surface, it is possible to improve the reactivity due cleaning treatment and activation treatment the electrode and E ^a in the formula (II).

G in the formulas (II) and (V) is an r + p-valent group having an aromatic ring. Accordingly, at least one of G ¹ , G ² , and G ^{3 in} the formula (XI) (where r = q × s × t) is a group having an aromatic ring. Further, G in the formulas (II) and (V) is preferably a monocyclic ring, a condensed ring, a ring assembly, or a bridged polycyclic r + p-valent group. The r + p-valent group is represented by the following formulas (1) to (16):

It is preferably a monocyclic ring, a condensed ring, a ring assembly or a bridged polycyclic ring containing at least one of the heterocyclic ring and the aromatic ring represented by formula (5), and one heterocyclic ring represented by the formula (5) It is more preferably a monocyclic ring, a condensed ring, a ring assembly, or a bridged polycyclic ring. The monocycle, the fused ring, the ring assembly, and the bridged polycycle may have a substituent. In the formulas (1) to (16), the binding site and the substituent are omitted. In the present invention, the “group having an aromatic ring” includes an aromatic carbon hydrogen group and a heterocyclic aromatic hydrocarbon group. When G in the formula (V) is a monocyclic, condensed ring, ring assembly, or bridged polycyclic r + p valent group, the formula (XI) (where r = q × s × t). G ¹ and G ² therein are both single bonds, G ³ is G, and q = 1, s = 1, t = r, u = 0.

  Examples of the group having an aromatic ring include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, and a furan. A monocyclic aromatic ring such as a ring, a pyrrole ring, a thiophene ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a thiadiazole ring, or an azadiazole ring; A condensed aromatic ring in which two or more are condensed; two or more rings independently selected from the monocyclic aromatic ring and / or the condensed polycyclic aromatic ring are a single bond, methylene group An aromatic ring assembly linked by a divalent atom or group such as ethylene group, ethenylene group, ethynylene group, oxygen atom, sulfur atom, imino group, carbonyl group, sulfonyl group; the condensed polycyclic aromatic ring or the aromatic ring Collection Two aromatic rings a methylene group adjacent to, an ethylene group, a carbonyl group, and a bridged polycyclic aromatic ring having 1 or more bridged crosslinked with divalent group such as a sulfonyl group. Further, the number of monocyclic aromatic rings condensed in the condensed aromatic ring is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2. The number of monocyclic aromatic rings and / or condensed aromatic rings connected in the aromatic ring assembly is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2. The number of monocyclic aromatic rings and / or condensed aromatic rings that are bridged in the bridged polycyclic aromatic ring is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2.

  Specific examples of such a group having an aromatic ring are shown below in terms of its basic structure (that is, in an unsubstituted state). In the following chemical formula, the binding site is omitted. Examples of the monocyclic aromatic ring include:

Is mentioned.

  As the condensed aromatic ring, for example,

Is mentioned.

  As an aromatic ring assembly, for example,

Is mentioned.

  Examples of the bridged polycyclic aromatic ring include:

Is mentioned.

  Among these groups having an aromatic ring, the formulas 20, 21, 23, 24, 25, 26, 29, 30, 33, 34, 50, 51, 53, 54, 56, 58, 66, 67, 72, 75, 76, 80, 81, 82, 90, 91, 92, 93, 94, 96, 97, 98, 99, 100, 101, 106, 107, 108, 109, 110, 111, 112, 120, 124, The group having an aromatic ring represented by 129, 130 is preferable, and the formulas 20, 21, 23, 24, 25, 26, 50, 53, 80, 82, 90, 91, 92, 93, 94, 96, 97 , 106, 107, 108, 109, 110, 111, 120, 124 are more preferable, and groups having an aromatic ring represented by the formulas 20, 21, 23, 24, 25, 26, 80, 90, 94, 96 are preferable. 97, 10 , 111, 120, and 124 are more preferable, and groups having an aromatic ring represented by the formulas 20, 21, 25, 26, 90, 97, 120, and 124 are particularly preferable. Groups having an aromatic ring represented by the formulas 20, 25, 90, 97 and 120 are particularly preferred.

  In the present invention, the group having an aromatic ring preferably consists of only a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom, and more preferably consists only of a hydrogen atom, a carbon atom and a nitrogen atom.

  In the group having an aromatic ring, a hydrogen atom bonded to a carbon atom constituting the aromatic ring is a hydroxy group, a fluorine atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydrocarbon disubstituted amino group, an alkylthio group, a carbonized group. It may be substituted with a hydrogen carbonyl group, a hydrocarbon oxycarbonyl group, a hydrocarbon disubstituted aminocarbonyl group, or a hydrocarbon sulfonyl group. Among these, as the substituent, a fluorine atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydrocarbon disubstituted amino group, an alkylthio group, a hydrocarbon carbonyl group, and a hydrocarbon oxycarbonyl group are more preferable. More preferably a group, a cyano group, an alkyl group, an alkoxy group, or a hydrocarbon disubstituted amino group. Moreover, the hydrogen atom couple | bonded with the nitrogen atom which comprises an aromatic ring may be substituted by the hydrocarbon group. Further, when there are two or more substituents on the carbon atom and / or nitrogen atom, two substituents selected from them may be bonded to each other to form a ring. Good.

  The hydrocarbon carbonyl group, hydrocarbon oxycarbonyl group, and hydrocarbon sulfonyl group are groups in which one hydrocarbon group is bonded to each of a carbonyl group, an oxycarbonyl group, and a sulfonyl group. A hydrocarbon disubstituted amino group and a hydrocarbon disubstituted aminocarbonyl group are groups in which two hydrocarbon groups are bonded to each of an amino group and an aminocarbonyl group.

  When the group having an aromatic ring is a bifunctional or higher functional organic group, examples of the substituent on the carbon atom of the group having an aromatic ring include an alkyl group, an alkoxy group, a hydrocarbon disubstituted amino group, an alkylthio group. Group, hydrocarbon carbonyl group and hydrocarbon oxycarbonyl group are preferred, alkyl group, alkoxy group and hydrocarbon disubstituted amino group are more preferred, and alkyl group and alkoxy group are still more preferred. Moreover, as a substituent on a nitrogen atom, an alkyl group is preferable.

N in the formulas (II), (V) and (XI) is an integer of 1 or more, preferably an integer of 1 or more and 1 × 10 ⁶ or less, more preferably an integer of 1 or more and 1 × 10 ⁵ or less. More preferably, it is an integer of 1 or more and 1 × 10 ⁴ or less. In the formulas (II) and (V), r is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3. Or 2 is particularly preferred. However, when G in the formulas (II) and (V) is a monocyclic aromatic ring structure and the number of carbon atoms constituting the ring structure is two (for example, the formulas 11, 12, and 15) , R is 1, and r is 1 or 2 when the number of carbon atoms is 3 (for example, the formulas 5, 8 to 10 and 13).

  P in the formulas (II), (V) and (XI) is an integer of 1 or more, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 5 or less. An integer of 3 or less is particularly preferable, and 1 or 2 is particularly preferable. However, when G in the formulas (II) and (V) is a monocyclic aromatic ring structure and the number of carbon atoms constituting the ring structure is two (for example, the formulas 11, 12, and 15) , P is 1, and p is 1 or 2 when the number of carbon atoms is 3 (for example, the formulas 5, 8 to 10 and 13).

  In the formulas (II) and (V), r + p which is the valence of G is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, more preferably 2 to 5. It is more preferable that it is an integer of 2, and 2 or 3 is particularly preferable.

In the present invention, Ar ¹ in the formulas (II), (V) and (XI) is represented by the following formula (VI):

Is contained in an amount of 0.1% by mass or more based on the total mass of all repeating units in the aromatic polymer compound constituting the polymer binding layer, and / or the following formula ( VII):

It is preferable that 0.1 mass% or more is contained with respect to the total mass of the number of all the repeating units in the aromatic polymer compound which comprises the said polymer coupling layer. The content of the repeating unit represented by the formula (VI) is more preferably 1% by mass or more, and particularly preferably 5% by mass or more. The content of the repeating unit represented by the formula (VII) is more preferably 1% by mass or more, and particularly preferably 5% by mass or more.

  Further, in the laminated structure of the present invention, the molar percentage of the repeating unit represented by the formula (VI) with respect to the total of all repeating units in the aromatic polymer compound constituting the polymer binding layer; The total of the repeating units represented by the formula (VII) and the mole percentage is preferably 10 mol% or more and 100 mol% or less, more preferably 15 mol% or more and 100 mol% or less, and more preferably 20 mol% % To 100 mol% is more preferable.

R ⁵ in the formula (VI) is a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an arylalkyl group that may have a substituent. Or it is the monovalent | monohydric heterocyclic group which may have a substituent, and when two or more exist, it may be same or different.
From the viewpoints of copolymer stability and ease of synthesis, R ⁵ is a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, An arylalkyl group which may have a substituent and a monovalent heterocyclic group which may have a substituent are preferable, and an alkyl group which may have a substituent and a substituted group are more preferable. An aryl group which may have a group and an arylalkyl group which may have a substituent, and more preferably an alkyl group which may have a substituent and a substituent. An aryl group. When there are a plurality of R ^{5 s} , which may be an alkyl group which may have a substituent, or an aryl group which may have a substituent, they may be bonded to each other to form a ring.

R ⁶ in the formulas (VI) and (VII) may be a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. A good alkylthio group, an aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, and an optionally substituted group An arylalkyl group, an arylalkoxy group which may have a substituent, an arylalkylthio group which may have a substituent, an arylalkenyl group which may have a substituent, and a substituent. Aryl alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, optionally substituted acyl group, acyloxy group, carbamoyl group, imide residue, substituted group Even if There monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or cyano group, or be the same or different when there are multiple. R ⁶ has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkoxy group which may have a substituent, a substituted amino group, a substituted silyl group and a substituent. An acyl group, a substituted carboxyl group and a cyano group are preferred, more preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. A good aryl group, an aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkoxy group which may have a substituent, a substituted carboxyl group, Good A hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryl group which may have a substituent, particularly preferably a hydrogen atom, It is an alkyl group. When there are a plurality of R ⁶ which are alkyl groups which may have a substituent, they may be bonded to each other to form a ring.

  Moreover, as an aromatic high molecular compound used for the laminated structure of this invention, following formula (VIII):

A conjugated polymer represented by

Wherein Ar ¹ in the formula (VIII) has the same meaning as Ar in the formula (I) and ^{(II), X} 1, n and p as defined in ^X 1, n and p are each the formula (II) It is. I is an integer of 1 or more, preferably an integer of 1 or more, 10 or less, more preferably an integer of 1 or more and 5 or less, particularly preferably an integer of 1 or more and 3 or less. Or 2 is particularly preferred. i + p is an integer of 2 or more and 20 or less, preferably an integer of 2 or more and 10 or less, more preferably an integer of 2 or more and 5 or less, and particularly preferably 2 or 3. When i is 2 or more, a plurality of Y and R ⁷ may be the same or different. When p is 2 or more, a plurality of X ¹ may be the same or different.

Ar ¹⁵ in the formula (VIII) is an i + p-valent group having an aromatic ring, and is preferably a monocyclic, condensed ring, ring assembly, or bridged polycyclic r + p-valent group. The r + p-valent group is a monocyclic ring, a condensed ring, a ring assembly, or a bridged polycyclic ring including at least one of the heterocyclic ring and the aromatic ring represented by the formulas (1) to (16). It is preferable. The monocycle, the fused ring, the ring assembly, and the bridged polycycle may have a substituent. Specific examples of the basic structure (unsubstituted state) of the group having an aromatic ring include those represented by the above formulas 20 to 133 (bonding sites are omitted).

  Among these groups having an aromatic ring, those represented by the formulas 20, 21, 23-26, 50, 51, 80, 82, 90-94, 96, 97, 106-111, 120, 124 are preferable. , The formulas 20, 21, 23, 24, 26, 51, 80, 90, 94, 96, 97, 107, 111, 120, 124 are more preferable, and the formulas 20, 21, 23, 51 are preferable. , 90, 120, and 124 are more preferable, and those represented by the formulas 20, 90, and 120 are particularly preferable.

J in the formula (VIII) is 0 or 1, and 0 is preferable. Y is an oxygen atom, sulfur atom, imino group, substituted imino group, ethenylene group, substituted ethenylene group or ethynylene group. The substituted imino group is a group represented by —N (Q ⁴ ) — (where Q ⁴ represents a substituent), and examples of Q ⁴ include an alkyl group which may have a substituent. Specific examples thereof are the same as those exemplified above. The substituted ethenylene group is —C (Q ⁵ ) ═C (Q ⁶ ) — (where Q ⁵ and Q ⁶ are each independently a hydrogen atom or a substituent, but at least one of Q ⁵ and Q ⁶ Is a substituent.) Examples of the substituents Q ⁵ and Q ⁶ include an alkyl group. Specific examples of the alkyl group are the same as those exemplified above. As such Y, an oxygen atom, a sulfur atom, an imino group, a substituted imino group, and an ethynylene group are preferable, an oxygen atom, a sulfur atom, an imino group, and a substituted imino group are more preferable, and an oxygen atom and an imino group are still more preferable.

R ⁷ in the formula (VIII) is a hydrogen atom, an alkyl group which may have a substituent, an alkylthio group which may have a substituent, an aryl group which may have a substituent, or a substituent. An arylthio group which may have a group, an arylalkyl group which may have a substituent, an arylalkylthio group which may have a substituent, an arylalkenyl group which may have a substituent, An arylalkynyl group which may have a substituent, a silyl group, a substituted silyl group, an acyl group which may have a substituent, and a monovalent heterocyclic group which may have a substituent, A plurality of R ⁷ may be the same or different and may be bonded to each other to form a ring. Among such R ⁷ , a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an arylalkyl group which may have a substituent, a silyl group A substituted silyl group and an optionally substituted acyl group are preferred, a hydrogen atom, an optionally substituted alkyl group, a substituted silyl group, and an optionally substituted acyl group. More preferred. Specific examples of these groups are the same as those exemplified above.

When producing the laminated structure of the present invention, among the conjugated polymers represented by the formula (VIII), R ⁷ has a hydrogen atom, an alkylthio group which may have a substituent, or a substituent. An arylthio group which may have an arylthio group or an optionally substituted arylalkylthio group can be used as it is for the formation of the polymer binding layer, but R ⁷ is a group other than these. For stuff, R ⁷ can be combined with PROTECTIVE GROUPS in ORGANIC SYNTHESIS THIRD EDITION, THEODORA W. GREENE, PETER G. M.M. WUTS, WILEY-INTERSCIENCE, pages 454-493, J. Am. Chem. Soc. , 1949, pages 1253-1257, the reaction using sodium metal, J. Am. Am. Chem. Soc. , 2005, 8036-8043, and the like using a reaction using iodine, etc., a hydrogen atom, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, or a substituent. By converting it to an arylalkylthio group which may be used, it can be used for forming the polymer binding layer.

In the process of producing the conjugated polymer represented by the formula (VIII), R ⁷ may be converted to a hydrogen atom, and in this case, a hydrogen atom and an alkylthio group optionally having substituent (s) , Conversion to an arylthio group optionally having substituents or an arylalkylthio group optionally having substituents can be omitted.

Therefore, among the conjugated polymers represented by the formula (VIII), those in which R ⁷ is a hydrogen atom and an alkylthio group which may have a substituent, the R ⁷ is a hydrogen atom, As for the group other than the alkylthio group which may have a substituent, a group obtained by converting R ⁷ into a hydrogen atom or an alkylthio group which may have a substituent is represented by the formula (II). G is the following formula (XIII):

In a structure represented, E ^a is R ⁷ -S (provided that, R ⁷ is a hydrogen atom, which may have a substituent alkylthio group which may have a substituent arylthio group or a substituted group It is an arylalkylthio group that may have an anion) and corresponds to a conjugated polymer with r = 2 × i. In the formula (XIII), Y, Ar ¹⁵ , i, and j are respectively synonymous with Y, Ar ¹⁵ , i, and j in the formula (VIII), and * is ^a binding site to E ^a or Ar ^1. Represents.

  Preferred specific examples of the conjugated polymer represented by the formula (II) are shown below.

Here, ^{E a} has the same meaning as ^{E a} in the above formula (II), ^{Ar 16} is - ^(Ar ₁₎ n is -X ^1, Ar ¹ is Ar in the formula (I) and (II) in the above formula, X ¹ and n are respectively the same as the X ¹ and n in the formula (II).

  Among these, conjugated polymers represented by the formulas (L-2) to (L-4), (L-6), (L-9), (L-10), and (L-11) are more preferable. The conjugated polymers represented by the formulas (L-4), (L-9), and (L-10) are particularly preferable.

(Method for producing conjugated polymer)
The method for producing a conjugated polymer used in the present invention will be described using the conjugated polymer represented by the formula (II) as an example. The conjugated polymer represented by the formula (II) is represented by the following formula (XIV):

A conjugated compound represented by the following formula (IV):

Can be produced by polycondensation using a polymerization catalyst or an equivalent reactant.

G in formula (XIV), r and p G in formula (II), have the same meanings as r and p, the Ar ¹ in formula (IV) with Ar ¹ in the formula (II) It is synonymous. Further, M in the formula (IV) has the same meaning as M in the formula (IV) described in <Method of polycondensing an aromatic compound (B)> described later. Furthermore, the polymerization catalyst, the equivalent reactant and the polycondensation conditions are the same as in the method (B) for polycondensing an aromatic compound described later.

E ^b in the formula (XIV) is a group that can be converted to E ^a in the formula (II) and / or E ^{a in} the formula (II). Examples of such E ^b include those exemplified as —S—R ⁷ in the above formula (VIII) when E ^a is a mercapto group or a substituted disulfide group. Further, when E ^a is a carboxyl group, an atomic group —C (O) O—R including an ester bond with an alkyl group R which may have a substituent may be mentioned.

X ^a in the formula (XIV) is a halogen atom or —SO ₃ Q ^a (where Q ^a is an alkyl group which may have a substituent, or an aryl group which may have a substituent). Represents a group represented by: Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferable. Examples of the group represented by -SO ₃ Q ^a, methanesulfonate group, benzenesulfonate group, p- toluenesulfonate group, trifluoromethane sulfonate group.

Of these, a chlorine atom as X ^a, bromine atom, iodine atom, p- toluenesulfonate group, preferably a trifluoromethanesulfonate group, a bromine atom, an iodine atom, more preferably a trifluoromethane sulfonate group, a bromine atom, an iodine atom Particularly preferred.

  When the conjugated polymer of the present invention represented by the formula (VIII) is produced as the conjugated polymer represented by the formula (II), the aromatic compound represented by the formula (IV) is polycondensed. In the following formula (IX):

It is preferable to add a conjugated compound represented by The addition amount of the formula (IX) may be adjusted according to the molecular weight of the target polymer. Usually, the addition amount of the formula (IX) is 0.00001 mol% or more and 50 mol% or less, preferably 0.8. It is 0001 mol% or more and 30 mol% or less, more preferably 0.0001 mol% or more and 20 mol% or less. Incidentally, ^{R 7, Y, Ar 15,} i and j in the formula (IX) has the same meaning as ^{R 7, Y, Ar 15,} i and j in the formula (VIII), also the above formula (IX ) ^{X a} in is synonymous with ^{X a} in the formula (XIV).

  Thus, the conjugated polymer represented by the formula (II) formed by the polycondensation reaction is composed of a linear aromatic polymer compound when p is 1, Further, when p is 2 or more, it is composed of an aromatic polymer compound in which a linear polymer chain is branched into p in G, and in any of these, an electrode and It has a group that can be chemically bonded.

<Method of polycondensing aromatic compound (B)>
The polymer bonding layer used in the present invention can also be formed by a method (B) in which an aromatic compound is polycondensed on an electrode as follows. Here, a case where the polymer binding layer represented by the formula (V) is formed will be described as an example. This method (B) has the following formula (III):

In the presence of an electrode to which a group represented by formula (IV) is bonded:

The polymer bonded layer is formed on the electrode by polycondensing the aromatic compound represented by the formula (1) using a polymerization catalyst or an equivalent reactant. The polymer bonding layer thus formed has a structure represented by the formula (V).

Ar ¹ in the formula (IV) has the same meaning as Ar ¹ in the formula (II). M in the formula (IV) is a hydrogen atom, a halogen atom, -B (OQ ¹ ) ₂ , -Si (Q ² ) ₃ , -Sn (Q ³ ) ₃ , a group represented by -SO ₃ Q ^a , or ^-Z 1 ^(Z ₂₎ represents a _m, M present two may be different even in the same.

Q ¹ in the -B (OQ ¹ ) ₂ is independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and bonded to each other. To form a ring. Q ¹ is preferably an alkyl group which may have a substituent, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, or a nonyl group, and a methyl group More preferably an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group. In the case of forming a ring, as the bifunctional hydrocarbon group consisting of two Q ¹ , 1,2-ethylene group, 1,1,2,2-tetramethyl-1,2-ethylene group, 1 , 3-propylene group, 2,2-dimethyl-1,3-propylene group and 1,2-phenylene group are preferred.

Q ² in the -Si (Q ²⁾ ₃ are each independently optionally substituted alkyl group, or an optionally substituted alkoxy group, the Q ^2, methyl , Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, nonyl group, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, pentyloxy group, hexyl An oxy group is preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, and a butoxy group are more preferable.

Q ³ in the -Sn (Q ^{₃₎ 3} are each independently optionally substituted alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group Hexyl group and nonyl group are preferable, and methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group are more preferable.

Q ^a in the -SO ₃ Q ^a is an optionally substituted alkyl group, or have a substituent is also an aryl group. As the group represented by —SO ₃ Q ^a , ^a methanesulfonate group, a benzenesulfonate group, a p-toluenesulfonate group, and a trifluoromethanesulfonate group are preferable.

Wherein ^{-Z 1 (Z} ₂₎ Z 1 in _m is a metal atom or metal ion, ^{Z 2} is a counter anion, m is an integer of 0 or more. Examples of Z ¹ include Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Pb, Sc, Ti, V, Cr, Mn, Fe, and Co. , Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, La, Ce, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg And atoms or ions. Preferably, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Pb, Sc, Ti, Cu, Zn, Y, Zr, Ag, Hg, More preferably, Li, Na, K, Rb, Cs, Be, Mg, Ca, In, Tl, Pb, Cu, Zn, Zr, Ag, Hg, and still more preferably Li, Na, K, Mg, Ca, Cu and Zn.

As Z ² , a conjugate base of Bronsted acid is usually used. For example, fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, tetrafluoro ion. Borate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, oxide ion, Examples include methoxide ions and ethoxide ions. Preferably chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, A benzoate ion, more preferably a chloride ion, bromide ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, More preferred are chloride ion, bromide ion, methanesulfonate ion, trifluoromethanesulfonate ion, acetate ion and trifluoroacetate ion.

When M is _{^{-Z 1 (Z 2) m,}} m is determined as the aromatic compound represented by the formula (IV) is electrically neutral. That is, when the aromatic compound represented by the formula (IV) is represented by ^Z 1 ^(Z ₂₎ m ^-Ar 1 -M ^as +1 valent Z ^{1 (Z} _{2) m} portion, Ar ¹ It is preferable that the —M moiety is regarded as −1 valence, and the Z ¹ (Z ² ) _m moiety and the Ar ¹ -M moiety are ion-bonded.

M in the formula (IV) is preferably a halogen atom, a boron atom, a silicon atom, a tin atom, an atomic group containing a metal atom, or a group represented by —SO ₃ Q ^a , a halogen atom, a boron atom An atomic group including an atom, a tin atom, a magnesium atom, and a zinc atom, and a group represented by —SO ₃ Q ^a are more preferable, and an atomic group including a halogen atom and a boron atom is particularly preferable.

  When two kinds of M in the formula (IV) are the same, specific combinations in the polycondensation reaction include a combination of only dihalogenated compounds; a combination of only bis (alkyl sulfonate) compounds; a dihalogenated compound and bis (aryl And combinations of at least one selected from the group consisting of (alkyl sulfonate) compounds and at least one selected from the group consisting of diboric acid compounds and diboric acid ester compounds.

  In addition, when the two types of M are different, from the viewpoint that a polymer bonding layer can be formed with good reproducibility, the aromatic compound includes a halogen-boric acid compound, a halogen-boric acid ester compound, an alkylsulfonate-boric acid. Compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, arylalkyl sulfonate-boric acid compounds, arylalkyl sulfonate-boric acid ester compounds are preferred, halogen-boric acid compounds, More preferred are halogen-boric acid ester compounds.

E, G, r and p in the formula (III) have the same meanings as E, G, r and p in the formula (V), and X ^a in the formula (III) is a halogen atom or —SO _3. Q ^a (where Q ^a represents an alkyl group which may have a substituent or an aryl group which may have a substituent).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferable. Examples of the group represented by -SO ₃ Q ^a, methanesulfonate group, benzenesulfonate group, p- toluenesulfonate group, trifluoromethane sulfonate group.

Of these, a chlorine atom as X ^a, bromine atom, iodine atom, p- toluenesulfonate group, preferably a trifluoromethanesulfonate group, a bromine atom, an iodine atom, more preferably a trifluoromethane sulfonate group, a bromine atom, an iodine atom Particularly preferred.

  The group represented by the formula (III) is represented by the following formula (XV):

(E ^a in the formula (XV) is synonymous with E ^a in the formula (II), and G, X ^a , r and p in the formula (XV) are G, X in the formula (III). It is synonymous with ^a , r, and p.)
The electrode can be formed on the electrode surface by immersing the electrode in a solution containing a conjugated compound represented by the formula (1) or by applying the solution to the electrode.

  The group represented by the formula (III) is represented by the following formula (IX):

(The same meaning as ^{R 7, Y, Ar 15,} i, R 7 in the j and p is the formula ^{(VIII), Y, Ar 15} , i, j and p in the formula (IX), the formula (IX ) ^{X a} in is synonymous with ^{X a} in the formula (III).)
It can also form on the electrode surface using the conjugated compound of this invention represented by these.

When manufacturing the laminated structure of the present invention, among the conjugated compounds represented by the formula (IX), R ⁷ has a hydrogen atom, an alkylthio group which may have a substituent, or a substituent. Those having an arylthio group which may have a substituent or an arylalkylthio group which may have a substituent can be used as they are for the formation of the polymer binding layer, but R ⁷ is a group other than these. For R ⁷ , PROTECTIVE GROUPS in ORGANIC SYNTHESIS THIRD EDITION, THEODORA W. GREENE, PETER G. M.M. Including the method described in WUTS, WILEY-INTERSCIENCE, pages 454-493, Chem. Commun. The reaction using t-BuSNa described in ESI (Electronic supplementary information) S3 on pages 1355 to 1357, J. Chem. Am. Chem. Soc. , 2005, 8036-8043, and the like using a reaction using iodine, etc., a hydrogen atom, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, or a substituent. By converting it to an arylalkylthio group which may be used, it can be used for forming the polymer binding layer.

Therefore, among the conjugated polymers represented by the formula (IX), those in which R ⁷ is a hydrogen atom and an alkylthio group which may have a substituent, the one as it is, R ⁷ is a hydrogen atom, As for the group other than the alkylthio group which may have a substituent, a group obtained by converting R ⁷ into a hydrogen atom or an alkylthio group which may have a substituent is represented by the formula (XV). G is the following formula (XIII):

In a structure represented, E ^a is R ⁷ -S (provided that, R ⁷ is a hydrogen atom, which may have a substituent alkylthio group which may have a substituent arylthio group or a substituted group Is an arylalkylthio group optionally having r.) And corresponds to a conjugated compound with r = 2 × i. In the formula (XIII), Y, Ar ¹⁵ , i, and j are respectively synonymous with Y, Ar ¹⁵ , i, and j in the formula (VIII), and * represents a binding site.

  Specific examples of the group represented by the formula (III) in the present invention include the following groups, which have a structure in which one or more hydrogen atoms bonded to an element constituting an aromatic ring are replaced with E. May be. In addition, E in a following formula is synonymous with E in the said Formula (V).

  Among these groups, groups represented by the following formulas (M-1) to (M-14) are preferable, and the following formulas (M-2) to (M-4), (M-6), (M- 9), groups represented by (M-10) and (M-11) are more preferred, and groups represented by the following formulas (M-4), (M-9) and (M-10) are particularly preferred. .

  The conditions for the polycondensation reaction in the method for producing the conjugated polymer and the method (B) are described in Chem. Rev. 102, 1359 (2002) and Bull. Chem. Soc. Jpn. 72, 621 (1999) and their references, various reaction conditions for aromatic coupling using a palladium complex or a nickel complex as a polymerization catalyst can be employed. In addition, Chem. Lett. 153 (1988), and reaction conditions using an equivalent reactant such as a Ni (0) compound can also be employed. The Ni (0) compound will be described as an example of the equivalent reactant. When M in the formula (IV) is a halogen atom, an Ar—Ar coupling reaction proceeds by reaction with the Ni (0) compound. , Ni (II) compound is produced as a by-product. When the Ni (II) compound is not reduced and does not act as a catalyst, the Ni (0) compound acts as an equivalent reactant. Among these aromatic coupling reactions, the Suzuki coupling reaction is preferable as a condition for the polycondensation reaction.

  Moreover, as a solvent used in the manufacturing method of the said conjugated polymer and the said method (B), according to the compound and reaction to be used, what used the thing which fully deoxygenated in order to suppress a side reaction generally is used. During the polycondensation reaction, the reaction is preferably allowed to proceed under an inert atmosphere using such an organic solvent. In the organic solvent, it is preferable to perform a dehydration process in the same manner as the deoxygenation process. However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction. Furthermore, in the said method (B), it is preferable to select the organic solvent in which the electrode used is insoluble and an electrode is not impaired.

  Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; chain and cyclic aliphatic hydrocarbons such as heptane and cyclohexane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and dichloromethane; Nitriles such as acetonitrile and benzonitryl; alcohols such as methanol, ethanol, n-propyl alcohol and iso-propyl alcohol; ethers such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether; N, N-dimethylformamide, N- Amides such as methylpyrrolidone; nitro compounds such as nitromethane and nitrobenzene; and water. As the reaction solvent, aromatic hydrocarbons, halogenated hydrocarbons, nitriles, ethers, nitro compounds or water are preferable. These reaction solvents may be used alone or as a mixture of two or more.

  The concentration of the aromatic compound represented by the formula (IV) in the solution varies depending on the type of the aromatic compound, but is preferably prepared within a concentration range in which the aromatic compound can be stably dissolved. . Specifically, from the viewpoint of stably forming the conjugated polymer and the polymer binding layer used in the present invention, the concentration of the aromatic compound is a concentration capable of stably dissolving the aromatic compound. And it is preferable that it is 0.001-1000 g / L, it is more preferable that it is 0.01-100 g / L, and it is especially preferable that it is 0.01-30 g / L.

  In the polycondensation reaction, it is preferable to add a base, an appropriate catalyst, or an equivalent reactant in order to react the aromatic compound represented by the formula (IV). Such a base, a catalyst, and an equivalent reactant can be selected according to a polymerization method to be employed. As such a base, catalyst, and equivalent reactant, those that are sufficiently dissolved in the solvent used in the reaction are preferable. In addition, as a method of mixing the base, catalyst and equivalent reactant, the solution, solid, etc. of the base, catalyst and equivalent reactant are gradually added while stirring the reaction solution under an inert atmosphere such as argon or nitrogen. Alternatively, a method in which the reaction solution is gradually added to a solution or suspension of the base, the catalyst, and the equivalent reactant can be used.

  Specific examples of the base in the present invention include a hydroxide salt, carbonate, phosphorus, wherein the counter cation is at least one selected from the group consisting of lithium ion, sodium ion, potassium ion, cesium ion and tetraalkylammonium ion. Acid salts and fluoride salts are mentioned. Of these, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate are preferable.

  The amount of the base used is preferably 0.01 to 1000 mol times, more preferably 0.1 to 100 mol times the amount of the aromatic compound represented by the formula (IV). More preferably, the amount is 1 to 30 mole times.

  The reaction temperature of the polycondensation is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 150 ° C., more preferably −20 ° C. to 100 ° C. The reaction time is usually 0.1 minute to 1,000 hours, preferably 1 minute to 500 hours, and more preferably 5 minutes to 200 hours.

As a more preferable method as the method (B), the method described in JP2009-19186A can be mentioned. That is, an electrode to which a group represented by the formula (III) is bonded is brought into contact with a toluene solution of Pd (Pt-Bu ₃ ) ₂ to carry a palladium complex on the electrode surface. In this method, polycondensation proceeds by bringing the mixture into contact with a mixture of an aromatic compound, a base, and a solvent.

  The polymer binding layer having the structure represented by the formula (V) formed by the polycondensation reaction in this way was composed of a linear aromatic polymer compound when p is 1. And when p is 2 or more, it is composed of an aromatic polymer compound in which the linear polymer chain is branched into p in G. And chemically bonded to the electrode.

(Method for producing conjugated compound)
The method for producing a conjugated compound used in the present invention will be described using the conjugated compound of the present invention represented by the formula (IX) as an example. The conjugated compound represented by the formula (IX) is, for example, first of the following formula (XVI):

(Formula ^{(Ar 15, X a,} i and p in XVI) is as defined ^{Ar 15, X a,} i and p in the formula (IX).)
And a compound represented by the following formula (XVII):

(The X ^b in the formula (XVII) a group convertible to R ⁷ -S group, X ^c is a group capable of forming a Y or a single bond by reacting with X ^a.)
Is reacted with a cyanuric acid derivative represented by the following formula (XVIII):

^(Ar 15 in formula ^{(XVIII), X a, Y} , i and p ^{Ar 15,} X a in the above formula (IX), Y, have the same meaning as i, and p, ^{X b} in the formula (XVIII) Is synonymous with ^Xb in the formula (XVII).)
To obtain a compound represented by:

Here, examples of X ^b in the formulas (XVII) and (XVIII) include a hydrogen atom, a halogen atom, a hydroxy group, an amino group, and the like. X ^c in the formula (XVII) includes a halogen atom, a hydroxy group, and the like. Group, amino group, monosubstituted amino group, ethenylene group, substituted ethenylene group, ethynylene group and the like.

Thereafter, the conjugated compound represented by the formula (IX) can be obtained by converting ^Xb of the compound represented by the formula (XVIII) into R ⁷ -S. For example, X ^b in the formula (XVIII) is converted to a mercapto group (-SH) by reacting the compound with thiourea acid represented by the formula (XVIII), the formula R ⁷ is a hydrogen atom ( A conjugated compound represented by IX) is obtained. The substitution mercaptan R ⁷ -SH this mercapto group (R ⁷ is R ⁷ as defined in formula (IX) (excluding hydrogen atoms).) A group R ⁷ is other than hydrogen atom by reacting A certain conjugated compound represented by the formula (IX) is obtained.

  Preferred specific examples of the conjugated compound represented by the formula (IX) are shown below.

  Among these, the formulas (K-3), (K-6) to (K-9), (K-13), (K-15), (K-18), (K-20), (K -22) is more preferable, and the conjugated compound represented by the formula (K-3), (K-7), (K-8), (K-18), or (K-20). Are more preferable, and conjugated compounds represented by the formulas (K-8), (K-18), and (K-20) are particularly preferable.

<Laminated structure>
Next, the laminated structure of the present invention will be described. The laminated structure of the present invention comprises the electrode, the polymer bonding layer disposed on the electrode, and the conductive organic material layer disposed on the polymer bonding layer. Since such a laminated structure has a conductive organic material layer, it can be used for an electroluminescent element, a photoelectric conversion element, or the like.

  Examples of the method for forming the conductive organic material layer include a method of forming a film from a solution containing a conductive organic material.

  Since the aromatic polymer compound used in the present invention has a bonding group bonded to an electrode, when the laminated structure of the present invention is used in an electroluminescent device, an element that emits light with high luminance is obtained. Moreover, when the laminated structure of this invention is used for a photoelectric conversion element, an element with high conversion efficiency is obtained. Furthermore, the polymer bonding layer constituting the laminated structure of the present invention has a bonding group of an aromatic polymer compound chemically bonded to the electrode, so that even if a film forming operation such as a spin coating method is performed, it can be easily performed from above the electrode. It has stability that is not excluded.

<Electroluminescent device>
The electroluminescent device using the laminated structure of the present invention includes an electrode (cathode or anode), the polymer binding layer disposed on the electrode, and the conductive organic disposed on the polymer binding layer. And a material layer. Such an electroluminescent element can usually further include a substrate and a second electrode as optional components, the substrate on the electrode side of the laminated structure, the second electrode on the conductive organic material layer side, and Other optional components can be provided as needed.

  The conductive organic material layer in the electroluminescent element is at least one of the following hole injection layer, hole transport layer, interlayer, light emitting layer, electron transport layer, hole block layer, and electron injection layer It consists of This conductive organic material layer may have a single layer structure composed of one or more of the conductive organic materials constituting these layers, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. There may be.

  As one aspect of the electroluminescent device using the laminated structure of the present invention, an anode is provided on a substrate, a polymer bonding layer is disposed thereon, a conductive organic material layer is disposed thereon, and There may be mentioned those having a cathode disposed thereon. As another embodiment, a cathode is provided on a substrate, a polymer bonding layer is disposed thereon, a conductive organic material layer is disposed thereon, and an anode is disposed thereon. Can be mentioned. Furthermore, as other embodiments, electroluminescent devices such as a bottom emission type that samples light from the substrate side, a top emission type that samples light from the opposite side of the substrate, or a double-sided light-emitting type can be cited. Moreover, as another aspect, what further provided the layer which has other functions, such as arbitrary protective films, buffer films | membranes, a reflection layer, is mentioned. The configuration of the electroluminescent element will be described in detail later. The electroluminescent element is further covered with a sealing film or a sealing substrate to form a light emitting device in which the electroluminescent element is shielded from the outside air.

  The polymer bonding layer used in the present invention can be used as a layer between the cathode and the light emitting layer or a layer between the anode and the light emitting layer in the electroluminescent device, and as a charge injection layer or a charge transport layer. Used.

  Usually, the electroluminescent element has a cathode and an anode, a conductive organic material layer, and further includes other components. For example, one or more of a hole injection layer, an interlayer, and a hole transport layer can be provided between the anode and the light emitting layer. When the hole injection layer is present, one or more of an interlayer and a hole transport layer can be provided between the light emitting layer and the hole injection layer. Meanwhile, one or more of an electron injection layer, an electron transport layer, and a hole blocking layer may be provided between the cathode and the organic light emitting layer. When the electron injection layer is present, one or more of an electron transport layer and a hole blocking layer can be provided between the organic light emitting layer and the electron injection layer.

  The polymer bonding layer used in the present invention can be used for such a hole injection layer, a hole transport layer, an interlayer, an electron injection layer, an electron transport layer, a hole block layer and the like. When the polymer bonding layer is used as a hole injection layer, a hole transport layer, or an interlayer, the electrode serves as an anode and the second electrode serves as a cathode. When the polymer bonding layer is used as an electron injection layer, an electron transport layer, or a hole blocking layer, the electrode serves as a cathode and the second electrode serves as an anode.

  Here, the anode supplies holes to a hole injection layer, a hole transport layer, an interlayer, a light emitting layer, etc., and the cathode serves as an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer. Etc. to supply electrons.

  A light-emitting layer is a function that receives holes from a layer adjacent to the anode side and receives electrons from a layer adjacent to the cathode side when an electric field is applied, and the received charges (electrons and holes) by the force of the electric field. A layer having a function of transferring, a field of recombination of electrons and holes, and a function of connecting this to light emission.

  The electron injection layer and the electron transport layer refer to a layer having any one of a function of receiving electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. In addition, the hole blocking layer mainly has a function of blocking holes injected from the anode, and if necessary, a layer having either a function of receiving electrons from the cathode or a function of transporting electrons. Say.

  The hole injection layer and the hole transport layer are any one of a function of receiving holes from the anode, a function of transporting holes, a function of supplying holes to the light emitting layer, and a function of blocking electrons injected from the cathode. A layer having The interlayer has at least one of a function of receiving holes from the anode, a function of transporting holes, a function of supplying holes to the light emitting layer, and a function of blocking electrons injected from the cathode, Usually, the light-emitting layer is disposed adjacent to the light-emitting layer and serves to isolate the light-emitting layer and the anode, or the light-emitting layer and the hole injection layer or the hole transport layer.

  The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. The electron injection layer and the hole injection layer are collectively referred to as a charge injection layer.

  That is, the electroluminescent element of the present invention can have the following layer configuration (a), or from the layer configuration (a), a hole injection layer, a hole transport layer, an interlayer, a hole blocking layer, an electron It may have a layer structure in which one or more of the transport layer and the electron injection layer are omitted. In the layer structure (a), the polymer binding layer used in the present invention is selected from the group consisting of a hole injection layer, a hole transport layer, an interlayer, an electron injection layer, an electron transport layer, and a hole blocking layer. It can be used as the above layer.

(A) Anode-hole injection layer- (hole transport layer and / or interlayer) -light emitting layer- (hole block layer and / or electron transport layer) -electron injection layer-cathode Indicates that the layers are stacked adjacent to each other.

  “(Hole transport layer and / or interlayer)” means a layer consisting of only a hole transport layer, a layer consisting only of an interlayer, a layer configuration of a hole transport layer-interlayer, an interlayer-hole transport layer A layer configuration or any other layer configuration including one or more hole transport layers and interlayers is shown.

  “(Hole blocking layer and / or electron transporting layer)” means a layer consisting of only a hole blocking layer, a layer consisting only of an electron transporting layer, a layer configuration of a hole blocking layer-electron transporting layer, an electron transporting layer—positive The layer configuration of the hole blocking layer, or any other layer configuration including at least one hole blocking layer and one electron transporting layer is shown. The same applies to the description of the layer structure below.

  Furthermore, the electroluminescent element using the laminated structure of the present invention can have two light emitting layers in one laminated structure. In this case, the electroluminescent device can have the following layer configuration (b), or from the layer configuration (b), a hole injection layer, a hole transport layer, an interlayer, a hole blocking layer, an electron transport layer. It is also possible to have a layer structure in which one or more layers of the electron injection layer and the electrode are omitted. In the layer structure (b), the polymer bonding layer used in the present invention is present between the anode and the light emitting layer closest to the anode, and is used as a layer bonded to the electrode or most between the cathode and the cathode. It is used as a layer that exists between the adjacent light emitting layers and is bonded to the cathode.

(B) Anode-hole injection layer- (hole transport layer and / or interlayer) -light emitting layer- (hole block layer and / or electron transport layer) -electron injection layer-electrode-hole injection layer- ( Hole transport layer and / or interlayer) -light emitting layer- (hole block layer and / or electron transport layer) -electron injection layer-cathode Here, "-" indicates that each layer is laminated adjacently. Indicates.

  Furthermore, the electroluminescent element using the laminated structure of the present invention can have three or more light emitting layers in one laminated structure. In this case, the electroluminescent element can have the following layer configuration (c), or from the layer configuration (c), a hole injection layer, a hole transport layer, an interlayer, a hole block layer, an electron transport layer. It is also possible to have a layer structure in which one or more layers of the electron injection layer and the electrode are omitted. In the layer structure (c), the polymer bonding layer used in the present invention exists between the anode and the light emitting layer closest to the anode, and is used as a layer bonded to the anode, or is the most to the cathode and the cathode. It is used as a layer that exists between the adjacent light emitting layers and is bonded to the cathode.

(C) Anode-hole injection layer- (hole transport layer and / or interlayer) -light emitting layer- (hole block layer and / or electron transport layer) -electron injection layer-repeating unit A-repeating unit A. ..- Cathode Here, "repeating unit A" is electrode-hole injection layer-(hole transport layer and / or interlayer)-light emitting layer-(hole block layer and / or electron transport layer)-electron The unit of the layer structure of the injection layer is shown.

Preferable specific examples of the layer structure of the electroluminescent element of the present invention include the following.
In the following layer configuration, the polymer binding layer used in the present invention is one or more selected from the group consisting of a hole injection layer, a hole transport layer, an interlayer, an electron injection layer, an electron transport layer, and a hole block layer. Can be used as a layer.
(D) Anode-hole transport layer-light-emitting layer-cathode (e) Anode-light-emitting layer-electron transport layer-cathode (f) Anode-hole transport layer-light-emitting layer-electron transport layer-cathode “-” Indicates that each layer is laminated adjacently.

In addition, for each of these structures, a structure in which an interlayer is provided adjacent to the light emitting layer between the light emitting layer and the anode is also exemplified. That is, the following structures (d ′) to (g ′) are exemplified.
(D ′) Anode-interlayer-light-emitting layer-cathode (e ′) Anode-hole transport layer-interlayer-light-emitting layer-cathode (f ′) Anode-interlayer-light-emitting layer-electron transport layer-cathode (g ') Anode-hole transport layer-interlayer-light-emitting layer-electron transport layer-cathode Here, the symbol "-" indicates that each layer is laminated adjacently.

In the present invention, an electroluminescent device provided with a charge injection layer (electron injection layer, hole injection layer) includes an electroluminescent device provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided electroluminescent element is mentioned. Specifically, for example, the following structures (h) to (s) are exemplified.
(H) Anode-charge injection layer-light emitting layer-cathode (i) Anode-light emitting layer-charge injection layer-cathode (j) Anode-charge injection layer-light emitting layer-charge injection layer-cathode (k) anode-charge injection Layer-hole transport layer-light emitting layer-cathode (l) anode-hole transport layer-light emitting layer-charge injection layer-cathode (m) anode-charge injection layer-hole transport layer-light emitting layer-charge injection layer- Cathode (n) anode-charge injection layer-light emitting layer-electron transport layer-cathode (o) anode-light emitting layer-electron transport layer-charge injection layer-cathode (p) anode-charge injection layer-light emitting layer-electron transport layer -Charge injection layer-Cathode (q) anode-Charge injection layer-Hole transport layer-Light emitting layer-Electron transport layer-Cathode (r) anode-Hole transport layer-Light emitting layer-Electron transport layer-Charge injection layer-Cathode (S) Anode-charge injection layer-hole transport layer-light-emitting layer-electron transport layer-charge injection layer-cathode Here, "-" indicates that each layer is laminated adjacently. Indicates that

  Further, similar to (d ′) to (g ′), for each one of these structures, a structure in which an interlayer is provided adjacent to the light emitting layer between the light emitting layer and the anode is also exemplified. In this case, the interlayer may also serve as a hole injection layer and / or a hole transport layer.

  In the electroluminescent device, the polymer binding layer used in the present invention is preferably an electron injection layer or a hole injection layer.

  In the electroluminescent device using the laminated structure of the present invention, an insulating layer is provided adjacent to the electrode in order to improve adhesion to the electrode and to improve injection of electric charges (ie, holes or electrons) from the electrode. Alternatively, a thin buffer layer may be inserted at the interface of the charge transport layer (that is, the hole transport layer or the electron transport layer) or the light emitting layer in order to improve the adhesion at the interface or prevent mixing. The order and number of layers to be stacked, and the thickness of each layer can be used in consideration of light emission efficiency and element lifetime.

  Next, the material and forming method of each layer constituting the electroluminescent element of the present invention will be described more specifically.

<Board>
The substrate constituting the electroluminescent device using the laminated structure of the present invention may be any substrate as long as it does not change when an electrode is formed and an organic layer is formed, for example, glass, plastic, polymer film, metal film. Silicon, a laminate of these, or the like is used. A commercially available substrate is available as the substrate, or can be manufactured by a known method.

  When the electroluminescent element using the laminated structure of the present invention constitutes a pixel of a display device, a pixel driving circuit may be provided on the substrate, or a planarization film may be provided on the driving circuit. May be provided. When a planarization film is provided, it is preferable that the centerline average roughness (Ra) of the planarization film satisfies Ra <10 nm. Ra can be measured with reference to JIS-B0651 to JIS-B0656, JIS-B0671-1, and the like based on JIS-B0601-2001 of Japanese Industrial Standards JIS.

<Anode>
The anode constituting the electroluminescent element using the laminated structure of the present invention is a polymer bonding layer or a conductive organic material of the anode from the viewpoint of the ability to supply holes to the conductive organic material layer or the polymer bonding layer. It is preferable that the work function of the layer side surface is 4.0 eV or more.

  As the material for the anode, a metal, an alloy, a metal oxide, an electrically conductive compound such as a metal sulfide, or a mixture thereof can be used. Specifically, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and molybdenum oxide, or metals such as gold, silver, chromium, and nickel Furthermore, a mixture of these conductive metal oxides and metals can be used. The anode may have a single layer structure composed of one or more of these materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. In the case of a multilayer structure, it is more preferable to use a material having a work function of 4.0 eV or more for the outermost surface layer of the polymer bonding layer or the conductive organic material layer.

  As a method for producing the anode, a known method can be used, and examples thereof include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

  The film thickness of the anode is usually 10 nm to 10 μm, preferably 50 nm to 500 nm. Further, from the viewpoint of preventing poor electrical connection such as a short circuit, the center line average roughness (Ra) of the light emitting layer side surface of the anode desirably satisfies Ra <10 nm, and more preferably Ra <5 nm.

  Further, after the anode is prepared by the above method, electron acceptance such as UV ozone, silane coupling agent, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, etc. In some cases, the surface treatment may be performed with a solution containing an ionic compound. The electrical connection with the organic layer in contact with the anode is improved by the surface treatment.

  When the anode is used as a light reflecting electrode in the electroluminescent device of the present invention, the anode includes a light reflecting layer made of a highly light reflecting metal and a high work function material layer including a material having a work function of 4.0 eV or more. A combined multilayer structure is preferred.

As a specific configuration example of such an anode,
(I) Ag-MoO ₃
(Ii) (Ag—Pd—Cu alloy) — (ITO and / or IZO)
(Iii) (Al—Nd alloy) — (ITO and / or IZO)
(Iv) (Mo-Cr alloy)-(ITO and / or IZO)
(V) (Ag—Pd—Cu alloy) — (ITO and / or IZO) —MoO ₃
Etc. In order to obtain a sufficient light reflectivity, the film thickness of the highly light-reflective metal layer such as Al, Ag, Al alloy, Ag alloy, or Cr alloy is preferably 50 nm or more, and more preferably 80 nm or more. The film thickness of the high work function material layer such as ITO, IZO, MoO ₃ is usually in the range of 5 nm to 500 nm.

<Cathode>
In the electroluminescent device using the laminated structure of the present invention, the cathode has a function of supplying electrons to these layers adjacent to the conductive organic material layer or the polymer bonding layer. The cathode may have a single layer structure made of a single material or a plurality of materials, or a multilayer structure made of a plurality of layers. In the case of a multilayer structure, a two-layer structure of a first cathode layer and a cover cathode layer or a three-layer structure of a first cathode layer, a second cathode layer, and a cover cathode layer is preferable. Here, the first cathode layer refers to the layer on the most conductive organic material layer or polymer bonding layer side in the cathode, and the cover cathode layer has a three-layer structure in the case of a two-layer structure. In this case, it means a layer covering the first cathode layer and the second cathode layer. From the viewpoint of electron supply capability, the work function of the material of the first cathode layer is preferably 3.5 eV or less. Further, metal oxides, fluorides, carbonates, composite oxides, and the like having a work function of 3.5 eV or less are also preferably used as the first cathode layer material. As a material for the cover cathode layer, a metal, a metal oxide, or the like having a low resistivity and high corrosion resistance to moisture is preferably used.

  Specific examples of the first cathode layer material include alkali metals and alkaline earth metals, alloys containing one or more of the metals, oxides of the metals, halides, carbonates, composite oxides, and mixtures thereof. Can be mentioned. Examples of alkali metals or oxides thereof, halides, carbonates, composite oxides include lithium, sodium, potassium, rubidium, cesium, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium fluoride, Sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, potassium molybdate, potassium titanate, potassium tungstate, cesium molybdate, etc. . Examples of alkaline earth metals or their oxides, halides, carbonates, composite oxides include magnesium, calcium, strontium, barium, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium fluoride, calcium fluoride Strontium fluoride, barium fluoride, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, barium molybdate, barium tungstate, and the like. Examples of alloys containing at least one alkali metal or alkaline earth metal include Li—Al alloys, Mg—Ag alloys, Al—Ba alloys, Mg—Ba alloys, Ba—Ag alloys, Ca—Bi—Pb—Sn. Alloys, etc. Further, a composition of a material listed as the first cathode layer material and a material listed as a material constituting the electron injection layer can also be used for the first cathode layer. Examples of the material of the second cathode layer include the same materials as the material of the first cathode layer.

  Specific examples of the cover cathode layer material include low resistance metals such as gold, silver, copper, aluminum, chromium, tin, lead, nickel, titanium, and alloys containing these metals, tin oxide, zinc oxide, indium oxide, and indium oxide. Examples thereof include conductive metal oxides such as tin (ITO), indium zinc oxide (IZO), and molybdenum oxide, and a mixture of these conductive metal oxides and metals.

Examples of the cathode having a multilayer structure include Mg / Al, Ca / Al, Ba / Al, NaF / Al, KF / Al, RbF / Al, CsF / Al, Na ₂ CO ₃ / Al, K ₂ CO ₃ / Al, Cs ₂ CO ₃ / Al, etc., a first cathode layer and a cover cathode layer, two-layer structure, LiF / Ca / Al, NaF / Ca / Al, KF / Ca / Al, RbF / Ca / Al, CsF / Ca / Al, Ba / Al / Ag, KF / Al / Ag, KF / Ca / Ag, K ₂ CO ₃ / Ca / Ag, etc., three-layer structure of first cathode layer, second cathode layer and cover cathode layer (Where the symbol “/” indicates that each layer is adjacent). The material of the second cathode layer preferably has a reducing action on the material of the first cathode layer. Here, the presence / absence / degree of the reducing action between materials can be estimated from, for example, bond dissociation energy (ΔrH °) between compounds. That is, in the case of a combination in which the bond dissociation energy is positive in the reduction reaction of the material constituting the second cathode layer to the material constituting the first cathode layer, the material of the second cathode layer is the first cathode layer. It can be said that this material has a reducing action. The bond dissociation energy can be referred to, for example, in “Electrochemical Handbook 5th Edition” (Maruzen, published in 2000), “Thermodynamic Database MALT” (Science and Technology, published in 1992), and the like.

  Various known methods can be used as a method for producing the cathode, and examples thereof include vacuum deposition, sputtering, and ion plating. When using metals, metal oxides, fluorides, and carbonates, vacuum evaporation is often used, and high-boiling metal oxides, metal composite oxides, and conductive metal oxides such as indium tin oxide (ITO) are used. In this case, sputtering and ion plating are frequently used. In the case of forming a composition with a different material, a co-evaporation method, a sputtering method, an ion plating method, or the like is used. In particular, a co-evaporation method is suitable for forming a film of a low molecular organic substance and a metal or metal oxide, fluoride, or carbonate.

  The optimum film thickness of the cathode varies depending on the material used and the layer structure, and may be selected so that the driving voltage, the light emission efficiency, and the element lifetime are appropriate. Usually, the thickness of the first cathode layer is in the range of 0.5 nm to 20 nm, and the thickness of the cover cathode layer is in the range of 10 nm to 1 μm. For example, when Ba or Ca is used for the first cathode layer and Al is used for the cover cathode layer, the film thickness of Ba or Ca is preferably 2 nm to 10 nm, and the film thickness of Al is preferably 10 nm to 500 nm. When using NaF or KF and Al for the cover cathode layer, the film thickness of NaF or KF is preferably 1 nm to 8 nm, and the film thickness of Al is preferably 10 nm to 500 nm.

<Hole injection layer>
In the electroluminescent device of the present invention, the material for forming the hole injection layer other than the conjugated polymer compound used in the present invention includes carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkanes. Derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, starburst amines, phthalocyanine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary Amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, organosilane derivatives And polymers containing them. In addition, conductive metal oxides such as vanadium oxide, tantalum oxide, tungsten oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, conductive polymers and oligomers such as polyaniline, aniline copolymers, thiophene oligomers, and polythiophenes, poly ( 3, 4-ethylenedioxythiophene) / polystyrene sulfonic acid, polypyrrole and other organic conductive materials, polymers containing these, and amorphous carbon. Furthermore, tetracyanoquinodimethane derivatives (for example, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), 1,4-naphthoquinone derivatives, diphenoquinone derivatives, polynitro compounds, etc. An acceptor organic compound, a silane coupling agent such as octadecyltrimethoxysilane, and the like can also be suitably used.

  The material may be used as a single component or as a composition comprising a plurality of components. In addition, the hole injection layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. In addition, materials listed as materials that can be used in the hole transport layer or the interlayer can also be used in the hole injection layer.

  Various known methods can be used as a method for forming the hole injection layer. In the case of inorganic compound materials, vacuum evaporation, sputtering, ion plating, etc. can be mentioned. In the case of low molecular organic materials, vacuum evaporation, transfer methods such as laser transfer and thermal transfer, and film formation from solution And a method (a mixed solution with a polymer binder may be used). In the case of a polymer organic material, a method of forming a film from a solution is exemplified.

  When the hole injection material is a low molecular compound such as a pyrazoline derivative, an arylamine derivative, a stilbene derivative, or a triphenyldiamine derivative, the hole injection layer can be formed using a vacuum deposition method.

  In addition, the hole injection layer can be formed using a mixed solution in which a polymer compound binder and the low molecular hole injection material are dispersed. As the polymer compound binder to be mixed, those that do not extremely inhibit charge transport are preferable, and those that do not strongly absorb visible light are preferably used. Specifically, poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, polycarbonate, Examples include polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  As a solvent used for film formation from a solution, any solvent that dissolves a hole injection material may be used. Examples of the solvent include water, chlorine-containing solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, butyl acetate and ethyl. Examples include ester solvents such as cellosolve acetate.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary Coating methods such as coating methods, spray coating methods, nozzle coating methods, etc., gravure printing methods, screen printing methods, flexographic printing methods, offset printing methods, reversal printing methods, inkjet printing methods, and other coating methods may be used. it can. From the viewpoint of easy pattern formation, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, a printing method such as an inkjet printing method, and a nozzle coating method are preferable.

When forming an organic compound layer such as a hole transport layer, an interlayer, or a light-emitting layer following the hole injection layer, especially when both layers are formed by a coating method, the previously applied layer is later. In some cases, the laminated structure cannot be prepared by dissolving in a solvent contained in the solution of the layer to be applied.
In this case, a method of making the lower layer solvent insoluble can be used. As a method for making the solvent insoluble, a cross-linking group is added to the polymer compound, and the cross-linking is performed by insolubilizing, a low molecular compound having a cross-linking group having an aromatic ring represented by aromatic bisazide is mixed as a cross-linking agent, Method of cross-linking and insolubilization, Method of mixing low molecular weight compounds having a cross-linking group that does not have an aromatic ring represented by an acrylate group as a cross-linking agent, cross-linking and insolubilization, and exposing the lower layer to UV light to cross-link And a method of insolubilizing in an organic solvent used for the production of the upper layer, a method of heating and crosslinking the lower layer, and a method of insolubilizing in the organic solvent used for the production of the upper layer. When heating the lower layer, the heating temperature is usually 100 ° C. to 300 ° C., and the time is usually 1 minute to 1 hour.

  In addition, as another method of laminating without dissolving the lower layer other than cross-linking, there is a method of using solutions of different polarities in the production of adjacent layers, for example, using a water-soluble polymer compound in the lower layer, There is a method of using an oil-soluble polymer compound so that the lower layer does not dissolve even when applied.

<Hole transport layer and interlayer>
In the electroluminescent device of the present invention, as a material constituting the hole transport layer and the interlayer other than the aromatic polymer compound used in the present invention, for example, a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, Imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds Styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, organosilane derivatives, and their structures Polymer containing thereof. In addition, conductive polymers and oligomers such as aniline-based copolymers, thiophene oligomers, and polythiophenes, and organic conductive materials such as polypyrrole can also be used.

  The material may be a single component or a composition comprising a plurality of components. Further, the hole transport layer and the interlayer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. . In addition, materials listed as materials that can be used in the hole injection layer can also be used in the hole transport layer.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3-37992, JP-A-3-152184, Compounds disclosed in Kaihei 5-263073, JP-A-6-1972, WO2005 / 52027, JP-A-2006-295203, and the like can be used as materials for the hole transport layer and the interlayer. Among them, a polymer containing a divalent aromatic amine residue as a repeating unit is preferably used.

  Examples of the divalent aromatic amine residue include a group represented by the formula (XIX).

In the formula, Ar ⁸ , Ar ⁹ , Ar ¹⁰ and Ar ¹¹ each independently represent an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent, Ar ¹² , Ar ¹³ and Ar ¹⁴ represent an aryl group which may have a substituent or a monovalent heterocyclic group which may have a substituent, and n ¹² and m ⁷ are each independently 0 or 1 is represented.

Examples of the substituent that the arylene group, aryl group, divalent heterocyclic group, and monovalent heterocyclic group may have include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, and an aryloxy group. Group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, carbamoyl group, acid imide group, imine residue, substitution Amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkyloxycarbonyl group, aryloxycarbonyl Group, arylalkyloxycarbonyl group Heteroaryl aryloxycarbonyl group and a carboxyl group and the like. The substituent is vinyl group, acetylene group, butenyl group, acrylic group, acrylate group, acrylamide group, methacryl group, methacrylate group, methacrylamide group, vinyl ether group, vinylamino group, silanol group, small ring (cyclopropyl group) , A group having a cyclobutyl group, an epoxy group, an oxetane group, a diketene group, an episulfide group, etc.), a lactone group, a lactam group, or a group containing a structure of a siloxane derivative. When n ¹² is 0, examples of the arylene group in which Ar ⁸ and Ar ¹⁰ may be bonded directly or via a divalent group such as —O— or —S— include a phenylene group. Examples of the valent heterocyclic group include a pyridinediyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the monovalent heterocyclic group include a pyridyl group.

  The polymer containing a divalent aromatic amine as a repeating unit may further have another repeating unit. Examples of other repeating units include arylene groups such as a phenylene group and a fluorenediyl group. Of these polymers, those containing a crosslinking group are more preferred.

  Examples of the method for forming the hole transport layer and the interlayer include the same method as that for forming the hole injection layer. Examples of the film forming method from the solution include the spin coating method, casting method, bar coating method, slit coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, and inkjet printing method. In the case of using a sublimable compound material, a vacuum deposition method, a transfer method, and the like can be given. Examples of the solvent used for film formation from a solution include the solvents listed in the film formation method for the hole injection layer.

  When an organic compound layer such as a light emitting layer is formed by a coating method following the hole transport layer and the interlayer, if the lower layer dissolves in the solvent contained in the solution of the layer to be applied later, hole injection is performed. Any material that dissolves the material may be used. The lower layer can be made insoluble in the same manner as exemplified in the method for forming the hole injection layer.

<Light emitting layer>
In the electroluminescent device of the present invention, when the conductive organic material layer has a light emitting layer, the light emitting layer includes a polyfluorene derivative, a polyparaphenylene vinylene derivative, a polyphenylene derivative, a polyparaphenylene derivative, a polythiophene derivative, a polydialkylfluorene, Luminescent material compounds such as polyfluorene benzothiadiazole and polyalkylthiophene can be suitably used.

  These light-emitting layers are composed of polymer dye compounds such as perylene dyes, coumarin dyes, rhodamine dyes, rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, nile red, coumarin 6, quinacridone, and the like. The low molecular dye compound may be contained. In addition, naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine series, xanthene series, coumarin series and cyanine series pigments, metal complexes of 8-hydroxyquinoline and derivatives thereof, aromatic amines, tetraphenylcyclopentadiene And a derivative thereof, or a metal complex that emits phosphorescence, such as tetraphenylbutadiene and a derivative thereof, tris (2-phenylpyridine) iridium, and the like.

  Moreover, the light emitting layer which the electroluminescent element of this invention has may be comprised from the composition of luminescent organic compounds, such as a nonconjugated polymer compound, the said organic pigment | dye, and the said metal complex. Non-conjugated polymer compounds include polyethylene, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, Examples thereof include phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and silicon resin. The non-conjugated polymer compound includes a carbazole derivative, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative, amino-substituted chalcone in the side chain. One selected from the group consisting of derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, and organosilane derivatives It may have a structure represented by the above derivatives or compounds.

  When the light emitting layer contains a low molecular weight compound, examples of the low molecular weight compound include rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, nile red, coumarin 6, carbazole, quinacridone, and other low molecular dye compounds, naphthalene derivatives. , Anthracene and derivatives thereof, perylene and derivatives thereof, polymethine, xanthene, coumarin, cyanine, indigo and other pigments, metal complexes of 8-hydroxyquinoline and derivatives thereof, metal complexes of phthalocyanine and derivatives thereof, aromatic Group amine, tetraphenylcyclopentadiene and derivatives thereof, or tetraphenylbutadiene and derivatives thereof.

  When the light emitting layer includes a metal complex that emits phosphorescence, examples of the metal complex include tris (2-phenylpyridine) iridium, thienylpyridine ligand-containing iridium complex, phenylquinoline ligand-containing iridium complex, and triazacyclononane. Examples include skeleton-containing terbium complexes.

  Specific examples of the light emitting material compound used for the light emitting layer include WO97 / 09394, WO98 / 27136, WO99 / 54385, WO00 / 22027, WO01 / 19834, GB2340304A, GB2348316, US573636, US5741921, US5777070, EP07007020, 111233, JP-A-10-324870, JP-A-2000-80167, JP-A-2001-123156, JP-A-2004-168999, JP-A-2007-162009, “Development and constituent materials of organic EL elements” (CM Publishing, 2006) ) And the like, their derivatives and copolymers, polyarylene, their derivatives and copolymers, polyarylene vinylene, their derivatives and copolymers, aromatic amino And (co) polymers of a derivative thereof.

  Specific examples of low molecular weight compounds include, for example, JP-A-57-51781, “Organic thin film work function data collection [2nd edition]” (CMC Publishing, 2006), “Development of organic EL elements and Examples thereof include compounds described in “Constituent Materials” (CMC Publishing, 2006).

  The material may be a single component or a composition comprising a plurality of components. In addition, the light emitting layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  Examples of the method for forming the light emitting layer include the same method as that for forming the hole injection layer. Examples of the film formation method from the solution include spin coating, casting, bar coating, slit coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, and inkjet printing. Examples of the method include a coating method and a printing method. When a sublimable compound material is used, a vacuum deposition method, a transfer method, and the like can be given. Examples of the solvent used for film formation from a solution include the solvents listed in the film formation method for the hole injection layer.

  When an organic compound layer such as an electron transport layer is formed by a coating method following the light emitting layer, if the lower layer dissolves in the solvent contained in the solution of the layer to be applied later, the hole injection layer is formed. The lower layer can be made insoluble in the same manner as exemplified in the method.

<Electron transport layer and hole blocking layer>
In the electroluminescent device using the laminated structure of the present invention, as materials constituting the electron transport layer and the hole blocking layer, known materials can be used, and triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, Fluorenone derivative, benzoquinone and its derivative, naphthoquinone and its derivative, anthraquinone and its derivative, tetracyanoanthraquinodimethane and its derivative, fluorenone derivative, diphenyldicyanoethylene and its derivative, diphenoquinone derivative, anthraquinodimethane derivative, anthrone derivative, Thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives , Metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes represented by metal complexes having benzoxazole or benzothiazole as ligands, organosilane derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline And derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, and the like. Among these, triazole derivatives, oxadiazole derivatives, benzoquinone and derivatives thereof, anthraquinone and derivatives thereof, or metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof Is preferred.

  The material may be a single component or a composition comprising a plurality of components. In addition, the electron transport layer and the hole blocking layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good. In addition, materials listed as materials that can be used in the electron injection layer can also be used in the electron transport layer and the hole blocking layer.

  Examples of the method for forming the electron transport layer and the hole blocking layer include the same methods as those for forming the hole injection layer. Examples of the film formation method from the solution include spin coating, casting, bar coating, slit coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, and inkjet printing. Examples of the method include a coating method and a printing method. When a sublimable compound material is used, a vacuum deposition method, a transfer method, and the like can be given. Examples of the solvent used for film formation from a solution include the solvents listed in the film formation method for the hole injection layer.

  When an organic compound layer such as an electron injection layer is formed by a coating method following the electron transport layer and the hole blocking layer, if the lower layer is dissolved in the solvent contained in the solution of the layer to be applied later, The lower layer can be made insoluble in the same manner as exemplified in the method for forming the hole injection layer.

<Electron injection layer>
In the electroluminescent device using the laminated structure of the present invention, a known material can be used as the electron injecting layer. Triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, benzoquinone and its derivatives, naphthoquinone And derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, anthraquinodimethane derivatives, anthrone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, Fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, gold of 8-quinolinol derivatives Complex, metal phthalocyanine, various metal complexes having benzoxazole or benzothiazole as represented by metal complexes having a ligand, organic silane derivatives, and the like.

  The material may be a single component or a composition comprising a plurality of components. In addition, the electron injection layer may have a single layer structure made of one or more of the materials, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions. In addition, materials listed as materials that can be used in the electron transport layer and the hole blocking layer can also be used in the electron injection layer.

  Examples of the method for forming the electron injection layer include the same method as that for forming the hole injection layer. Examples of the film formation method from the solution include spin coating, casting, bar coating, slit coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, and inkjet printing. Examples of the method include a coating method and a printing method. When a sublimable compound material is used, a vacuum deposition method, a transfer method, and the like can be given. Examples of the solvent used for film formation from a solution include the solvents listed in the film formation method for the hole injection layer.

<Insulating layer>
The insulating layer having a film thickness of 5 nm or less that the electroluminescent device of the present invention can optionally have improves adhesion to the electrode, improves injection of electric charges (that is, holes or electrons) from the electrode, prevents mixing with an adjacent layer, etc. It has a function. Examples of the material for the insulating layer include metal fluorides, metal oxides, organic insulating materials (polymethyl methacrylate, etc.), and the like. As an electroluminescent element provided with an insulating layer having a thickness of 5 nm or less, an element having an insulating layer having a thickness of 5 nm or less adjacent to the cathode and an insulating layer having a thickness of 5 nm or less adjacent to the anode are provided. Can be mentioned.

  The method for producing an electroluminescent element using the laminated structure of the present invention can be produced, for example, by sequentially laminating each layer on a substrate. Specifically, an anode is provided on a substrate, a layer such as a hole injection layer, a hole transport layer, or an interlayer is provided thereon as necessary, a light emitting layer is provided thereon, and electron transport is provided thereon. A layer such as a layer or an electron injection layer is provided as necessary, and further, a cathode is laminated thereon, or a cathode is provided on a substrate, and an electron injection layer, an electron transport layer, A layer such as an interlayer is provided as necessary, a layer such as a hole transport layer and a hole injection layer is provided thereon as necessary, and an anode is further laminated thereon.

  A display device can be manufactured using the electroluminescent element of the present invention. The display device includes an electroluminescent element as a pixel unit. The arrangement mode of the pixel unit can be an arrangement normally employed in a display device such as a television, for example, an arrangement in which a large number of pixels are arranged on a common substrate. In the device of the present invention, the pixels arranged on the substrate can be formed in a pixel region defined by the bank, if necessary.

  The device may further include a sealing member on the side opposite to the substrate with the light emitting layer or the like interposed therebetween, as necessary. In addition, if necessary, the image display device can include optional components for configuring the display device, such as a filter such as a color filter or a fluorescence conversion filter, a circuit and a wiring necessary for driving a pixel, and the like.

In the laminated structure of the present invention, examples of suitable combinations of the electrode, the bonding group E, the r + p-valent group G having an aromatic ring, and Ar ¹ include the following. When the electrode of the laminated structure of the present invention functions as an anode, the electrode is preferably gold, silver, indium tin oxide (ITO), or indium zinc oxide, and as E, E ^a is a mercapto group, a carboxyl group, or a phosphonic acid group. , A bond group formed when it is a trialkoxysilyl group, G is a group constituting the conjugated polymer represented by the formula (L-4), (L-9), or (L-10). Ar ¹ preferably has a HOMO orbital energy of −5.5 eV to −4.0 eV. When the electrode of the laminated structure of the present invention functions as a cathode, the electrode is preferably aluminum or silver, and E and G are preferably the same as the above examples when the electrode of the laminated structure functions as an anode. Ar ¹ preferably has a LUMO orbital energy of −3.5 eV or more and −0.5 eV or less.

  Next, a photoelectric conversion element that can be manufactured using the laminated structure of the present invention will be described. The photoelectric conversion element using the laminated structure of the present invention has a polymer bonding layer between an electrode and a conductive organic material layer.

  The conductive organic material layer of the photoelectric conversion element of the present invention contains an electron donating compound and an electron accepting compound. Examples of the electron donating compound include conjugated polymer compounds, and specific examples include a polymer compound containing a thiophenediyl group and a polymer compound containing a fluorenediyl group. Moreover, fullerene, a fullerene derivative, etc. are mentioned as an electron-accepting compound.

  The photoelectric conversion element using the laminated structure of the present invention is usually formed on a support substrate. As a support substrate, the characteristic as an organic photoelectric conversion element should just be not inhibited, and a 2nd electrode, a glass substrate, a flexible film substrate, and a plastic substrate can also be used. When a polymer bonding layer is provided between the anode and the conductive organic material layer, the electrode is an anode, the second electrode is a cathode, and the polymer bonding layer is used as a hole transport layer or the like. When a polymer bonding layer is provided between the cathode and the conductive organic material layer, the electrode is a cathode, the second electrode is an anode, and the polymer bonding layer is used as an electron transport layer or the like.

  The photoelectric conversion element of the present invention can be produced by a known method, for example, Synth. Met. , 102, 982 (1999) and the method described in Science, 270, 1789 (1995).

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are determined by gel permeation chromatography (GPC) (trade name: HLC-8220GPC, manufactured by Tosoh Corporation), and the number average molecular weight in terms of polystyrene and It calculated | required as a weight average molecular weight. The sample to be measured is dissolved in tetrahydrofuran so that the concentration is about 0.5% by mass, and 50 μL is injected into GPC. Furthermore, tetrahydrofuran was used as the mobile phase of GPC and allowed to flow at a flow rate of 0.5 mL / min. The structural analysis of the polymer and the compound was performed by ¹ H-NMR analysis using a Varian 300 MHz NMR spectrometer. The measurement was performed by dissolving the sample in a soluble heavy solvent so as to have a concentration of 20 mg / mL. The area of the electrode when measuring the current-voltage of the laminated structure and the polymer film was 4 mm ² .

Example 1 Synthesis of Compound H
Magnesium (10.4 g) and THF (120 mL) were added to the reaction vessel, and a mixed solution of p-dibromobenzene (93.0 g) and THF (160 mL) was dropped into the reaction vessel (mixed solution 1). In a separate reaction vessel, 72.0 g of cyanuric chloride and 720 mL of toluene were added and cooled to 0 ° C., and mixed solution 1 was added dropwise thereto and stirred for 1 hour, and then an aqueous ammonium chloride solution was added, followed by liquid separation with chloroform. The layer was concentrated. The obtained crude product was purified by recrystallization to obtain 77.2 g of Compound J. The results of NMR analysis of this compound J are shown below.
¹ H NMR (400 MHz, CDCl ₃ , rt)
δ 7.68 (2H), 8.38 (2H)
From this result, the compound J is represented by the following formula:

It was confirmed that

Next, 15.0 g of the compound J, 188 mL of acetone and 7.5 g of thiourea were added to the reaction vessel, and the mixture was heated to reflux for 1 hour, cooled to 0 ° C., sodium carbonate was added dropwise and stirred. The reaction mixture was filtered, and the filtrate was acidified with hydrochloric acid, and the precipitate was collected by filtration to obtain a crude product. This was purified by column chromatography to obtain 6.8 g of Compound H. The results of NMR analysis of this compound H are shown below.
¹ H NMR (400 MHz, DMSO-d ₆ , rt)
δ 3.17 (1H), 7.78 (2H), 8.05 (2H), 13.87 (1H)
From this result, the compound H is represented by the following formula:

It was confirmed that

Example 2 Synthesis of Compound C
To the reaction vessel, 138 mL of isopropanol and 2.3 g of sodium metal were added and heated to reflux, and then 9.8 g of t-butyl mercaptan was added and cooled to room temperature. 15.0 g of the compound H was added to this and refluxed for 2 hours, then water and an aqueous sodium hydroxide solution were added, and the mixture was separated with t-butyl methyl ether to concentrate the organic layer. The crude product was washed with petroleum ether to obtain 8.1 g of Compound C. The results of NMR analysis of this compound C are shown below.
¹ H NMR (400 MHz, CDCl ₃ , rt)
δ 1.67 (18H), 7.62 (2H), 8.28 (2H)
From this result, the compound C is represented by the following formula:

It was confirmed that

Example 3 Synthesis of Composition A
In a 25 mL two-necked flask:

250 mg (0.43 mmol) of the compound B represented by the following formula:

Was charged with 14.0 mg (0.034 mmol) of Compound C, and the inside of the flask was replaced with argon gas. Thereto, 9 mL of toluene was charged and stirred at 45 ° C. for 5 minutes. Next, 0.58 mg (0.0006 mmol) of tris (dibenzylideneacetone) dipalladium and 1.80 mg (0.0051 mmol) of tris (2-methoxyphenyl) phosphine were added and stirred at 45 ° C. for 10 minutes, and 33% by mass of cesium carbonate After adding 2.0 mL of aqueous solution, it stirred at 45 degreeC for 5 minute (s). Next, the mixture was stirred at 110 ° C. for 2 hours, 0.58 mg (0.0006 mmol) of tris (dibenzylideneacetone) dipalladium and 1.80 mg (0.0051 mmol) of tris (2-methoxyphenyl) phosphine were added, and further 2 hours. After stirring, 0.58 mg (0.0006 mmol) of tris (dibenzylideneacetone) dipalladium and 1.80 mg (0.0051 mmol) of tris (2-methoxyphenyl) phosphine were added, and the mixture was further stirred for 2 hours.

  Next, 92.8 mg (0.43 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 2 mL of toluene were added, and tris (dibenzylideneacetone) dioxide was added. 0.58 mg (0.0006 mmol) of palladium, 1.80 mg (0.0051 mmol) of tris (2-methoxyphenyl) phosphine and 1.1 mL of 33% by mass cesium carbonate aqueous solution were added, and the mixture was stirred at 110 ° C. for 2 hours. Tris (dibenzylideneacetone) dipalladium 6.0 mg (0.0065 mmol) and tris (2-methoxyphenyl) phosphine 18.0 mg (0.051 mmol) were added and stirred for 8 hours. Then, after cooling to room temperature, the organic layer and aqueous layer of the reaction solution were separated, the organic layer was dropped into 120 mL of methanol to precipitate a precipitate, and the precipitate was filtered and dried to obtain a yellow solid. This yellow solid was dissolved in 20 mL of toluene, and subjected to column chromatography on silica gel and activated alumina, and concentrated to dryness. The obtained solid was dissolved in toluene, a solution was added dropwise to methanol to precipitate a precipitate, and the precipitate was filtered and dried to obtain 150 mg of Composition A.

  From the results of NMR analysis, the composition A has the following formula:

(In the formula, m ³ represents the degree of polymerization.)
And a polymer 1 represented by the following formula:

(In the formula, m ⁴ represents the degree of polymerization.)
And a polymer 2 represented by a molar ratio of 38:62. The polystyrene equivalent number average molecular weight Mn of the composition A was 7.9 × 10 ³ , and the polystyrene equivalent weight average molecular weight Mw was 1.7 × 10 ⁴ . Since the -S- (t-Bu) moiety was converted to -SH during the polymerization, the deprotection step was omitted.

Example 4 Synthesis of Composition D
In a 25 mL two-necked flask:

250 mg (0.47 mmol) of the compound E represented by the formula:

Was charged with 15.4 mg (0.037 mmol), and the inside of the flask was replaced with argon gas. Thereto, 9 mL of toluene was charged and stirred at 45 ° C. for 5 minutes. Next, 0.64 mg (0.0007 mmol) of tris (dibenzylideneacetone) dipalladium and 1.98 mg (0.0056 mmol) of tris (2-methoxyphenyl) phosphine were added and stirred at 45 ° C. for 10 minutes, and 33 mass% cesium carbonate. After adding 2.2 mL of aqueous solution, it stirred at 45 degreeC for 5 minute (s). Next, the mixture was stirred at 110 ° C. for 2 hours, and 0.64 mg (0.0007 mmol) of tris (dibenzylideneacetone) dipalladium and 1.98 mg (0.0056 mmol) of tris (2-methoxyphenyl) phosphine were added, and further 2 hours. The mixture was stirred, tris (dibenzylideneacetone) dipalladium 0.64 mg (0.0007 mmol) and tris (2-methoxyphenyl) phosphine 1.98 mg (0.0056 mmol) were added, and the mixture was further stirred for 2 hours.

  Subsequently, 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene (102.1 mg, 0.47 mmol) and toluene (2 mL) were added, and tris (dibenzylideneacetone) diethyl was added. After adding 0.64 mg (0.0007 mmol) of palladium, 1.98 mg (0.0056 mmol) of tris (2-methoxyphenyl) phosphine and 1.1 mL of 33% by mass cesium carbonate aqueous solution and stirring at 110 ° C. for 2 hours, further Tris (dibenzylideneacetone) dipalladium 6.0 mg (0.0065 mmol) and tris (2-methoxyphenyl) phosphine 18.0 mg (0.051 mmol) were added and stirred for 7 hours. Then, after cooling to room temperature, the organic layer and aqueous layer of the reaction solution were separated, the organic layer was dropped into 120 mL of methanol to precipitate a precipitate, and the precipitate was filtered and dried to obtain a yellow solid. This yellow solid was dissolved in 11 mL of toluene, subjected to column chromatography on silica gel and activated alumina, and concentrated to dryness. The obtained solid was dissolved in toluene, a solution was added dropwise to methanol to precipitate a precipitate, and the precipitate was filtered and dried to obtain 103 mg of composition D.

  From the results of NMR analysis, the composition D has the following formula:

(In the formula, m ⁵ represents the degree of polymerization.)
And a polymer 3 represented by the following formula:

(In the formula, m ⁶ represents the degree of polymerization.)
And a polymer 4 represented by a molar ratio of 27:73. The polystyrene equivalent number average molecular weight Mn of the composition D was 5.2 × 10 ³ , and the polystyrene equivalent weight average molecular weight Mw was 9.8 × 10 ³ . Since the -S- (t-Bu) moiety was converted to -SH during the polymerization, the deprotection step was omitted.

<Synthesis Example 1> -Synthesis of Polymer F-
In a 25 mL two-necked flask:

500 mg (0.85 mmol) and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene 3.9 mg (0.018 mmol), The inside of the flask was replaced with argon gas. Thereto was charged 18 mL of toluene, and the mixture was stirred at 45 ° C. for 5 minutes. Next, 1.17 mg (0.0013 mmol) of tris (dibenzylideneacetone) dipalladium and 3.6 mg (0.0102 mmol) of tris (2-methoxyphenyl) phosphine were added and stirred at 45 ° C. for 10 minutes, and 33 mass% cesium carbonate. After adding 3.9 mL of aqueous solution, it stirred at 45 degreeC for 5 minute (s). Next, the mixture was stirred at 110 ° C. for 3 hours, and then 108.8 mg (0.51 mmol) of 4-t-butylbromobenzene and 4 mL of toluene were added, and 1.17 mg (0.0013 mmol) of tris (dibenzylideneacetone) dipalladium and 3.6 mg (0.0102 mmol) of tris (2-methoxyphenyl) phosphine and 2.2 mL of 33% by mass aqueous cesium carbonate solution were added, and the mixture was stirred at 110 ° C. for 1.5 hours. Then, after cooling to room temperature, the organic layer and aqueous layer of the reaction solution were separated, the organic layer was dropped into 240 mL of methanol to precipitate a precipitate, and the precipitate was filtered and dried to obtain a yellow solid. This yellow solid was dissolved in 33 mL of toluene, subjected to column chromatography on silica gel and activated alumina, and concentrated to dryness. The obtained solid was dissolved in toluene, and a solution was added dropwise to methanol to precipitate a precipitate. The precipitate was filtered and dried to obtain 267 mg of polymer F.

The polystyrene equivalent number average molecular weight Mn of the polymer F was 6.6 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight Mw was 1.6 × 10 ⁵ .

<Synthesis Example 2> -Synthesis of Polymer G-
In the reaction vessel the following formula:

Was charged with 1.10 g (1.9 mmol) of Compound B, and the inside of the flask was replaced with argon gas. Thereto, 8.4 mg (0.04 mmol) of 4-t-butylbromobenzene and 39.5 mL of toluene were charged and subjected to Ar bubbling, followed by stirring at 45 ° C. for 5 minutes.
Subsequently, 2.6 mg (0.003 mmol) of tris (dibenzylideneacetone) dipalladium, 7.9 mg (0.02 mmol) of tris (2-methoxyphenyl) phosphine and 4.0 mL of toluene were added, and the mixture was stirred at 45 ° C. for 10 minutes. Thereafter, 8.5 mL of a 33 mass% cesium carbonate aqueous solution was added, and the mixture was stirred at 114 ° C for 30 minutes. Furthermore, 0.24 g (1.1 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 8.5 mL of toluene were added, and tris (dibenzylideneacetone) was added. ) 1.5 mg (0.002 mmol) of dipalladium, 4.6 mg (0.01 mmol) of tris (2-methoxyphenyl) phosphine, 2.0 mL of toluene and 5.0 mL of 33% by mass cesium carbonate aqueous solution were added at 114 ° C. Stir for 2 hours. Then, after cooling to room temperature, the organic layer and aqueous layer of the reaction solution were separated, and the precipitate obtained by dropping the organic layer into methanol was collected by filtration to obtain a yellow solid. This yellow solid was dissolved in toluene and subjected to column chromatography on silica gel and activated alumina, and the eluate was concentrated. The obtained concentrated liquid was added dropwise to methanol, and the deposited precipitate was collected by filtration and dried to obtain 0.64 g of polymer G.

The polystyrene equivalent number average molecular weight Mn of the polymer G was 3.7 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight Mw was 7.7 × 10 ⁴ .

<Synthesis Example 3> -Synthesis of bis (tri-t-butylphosphine) palladium-
Bis (tri-t-butylphosphine) palladium was obtained from Am. Chem. Soc. 98, 5850-5857 (1976).

<Example 5> -Production of an electroluminescent element using the multilayer structure 1 (Method (A))-
The ITO substrate was washed with chloroform, methanol, an aqueous solution of an alkaline detergent, distilled water, and acetone and then exposed to ozone gas for 1 minute to remove deposits on the surface of the ITO substrate. By immersing this ITO substrate in a THF solution (2.3 g / L) of the composition A containing the polymer 1 and leaving it to stand for 1 day, it is lifted, washed by blowing THF, and dried by blowing Ar gas. Then, a polymer binding layer composed of an aromatic polymer compound having a polystyrene-equivalent number average molecular weight of 7.9 × 10 ³ was produced. At this time, the film thickness of the polymer bond layer is 62 nm, and the orbital energy of LUMO and HOMO of the polymer 1 constituting the polymer bond layer calculated by the B3LYP / 6-31G ^* method of the above method is −1. .70 eV and -4.97 eV. Further, a conductive organic material made of a polymer F having LUMO and HOMO orbital energies calculated by the above method of −1.70 eV and −4.97 eV, respectively, is formed on this film so that the film thickness becomes about 125 nm. After spin coating, 67 nm of gold was vapor-deposited, and current-voltage measurement of the obtained laminated structure 1 was performed. As a result, a current of 9.02 × 10 ⁻⁶ A flowed when a voltage of +4 V was applied. The obtained results are shown in Table 2.

<Example 6> -Preparation of an electroluminescent element using the multilayer structure 2 (Method (A))-
The ITO substrate was washed with chloroform, methanol, an aqueous solution of an alkaline detergent, distilled water, and acetone and then exposed to ozone gas for 1 minute to remove deposits on the surface of the ITO substrate. By immersing this ITO substrate in a THF solution (2.3 g / L) of the composition D containing the polymer 3 and letting it stand for 1 day, pulling it up, washing it with THF, blowing it with Ar gas and drying it. Then, a polymer binding layer composed of an aromatic polymer compound having a polystyrene-equivalent number average molecular weight of 5.2 × 10 ³ was produced. At this time, the film thickness of the polymer bonding layer is 61 nm, and the orbital energy of LUMO and HOMO of the polymer 3 constituting the polymer bonding layer calculated by the B3LYP / 6-31G ^* method of the method is −0. .89 eV and -4.37 eV. Furthermore, a conductive organic material made of polymer F having LUMO and HOMO orbital energies calculated by the above method of −1.70 eV and −4.97 eV, respectively, is formed on this film. After spin-coating to a thickness of about 125 nm, gold was evaporated to 78 nm, and current-voltage measurement of the obtained laminated structure 2 was performed. As a result, when a voltage of +4 V was applied, a current of 1.22 × 10 ⁻⁴ A flowed. The obtained results are shown in Table 2.

<Example 7> -Preparation of an electroluminescent element using the laminated structure 3 (Method (A))-
The ITO substrate was washed with chloroform, methanol, an aqueous solution of an alkaline detergent, distilled water, and acetone and then exposed to ozone gas for 1 minute to remove deposits on the surface of the ITO substrate. This ITO substrate is composed of an aromatic polymer compound having a polystyrene-equivalent number average molecular weight of 7.9 × 10 ³ by spin coating the composition A containing the polymer 1 so as to have a film thickness of about 10 nm. A polymer bonded layer was prepared. The orbital energies of LUMO and HOMO of the polymer 1 constituting the polymer binding layer calculated by the B3LYP / 6-31G ^* method of the above method were −1.70 eV and −4.97 eV. Further, a conductive organic material made of a polymer F having LUMO and HOMO orbital energies calculated by the above method of −1.70 eV and −4.97 eV, respectively, is formed on this film so that the film thickness becomes about 125 nm. After spin coating, 66 nm of gold was vapor-deposited, and current-voltage measurement of the obtained laminated structure 3 was performed. As a result, when a voltage of +4 V was applied, a current of 9.16 × 10 ⁻⁷ A flowed. The obtained results are shown in Table 1.

<Comparative Example 1>-Production of an electroluminescent device comprising a comparative polymer film 1 (not a laminated structure)-
The ITO substrate was washed with chloroform, methanol, an aqueous solution of an alkaline detergent, distilled water, and acetone and then exposed to ozone gas for 1 minute to remove deposits on the surface of the ITO substrate. On this ITO substrate, a conductive organic material made of polymer F having LUMO and HOMO orbital energies calculated by the B3LYP / 6-31G ^* method of the above-described method of -1.70 eV and -4.97 eV, respectively, is formed. Was spin-coated so as to be about 125 nm, and then gold was vapor-deposited to 67 nm, and current-voltage measurement of the obtained comparative polymer film 1 was performed.
As a result, when a voltage of +4 V was applied, a current of 7.90 × 10 ⁻⁸ A flowed. The obtained results are shown in Table 2.

<Evaluation>
As is clear from the results shown in Table 2, it can be seen that the laminated structure of the present invention allows a larger amount of current to flow than a comparative polymer film that is not a laminated structure.

<Example 8> -Production of electroluminescent element using laminated structure 4 (method (A))-
The ITO substrate was washed with chloroform, methanol, an aqueous solution of an alkaline detergent, distilled water, and acetone and then exposed to ozone gas for 1 minute to remove deposits on the surface of the ITO substrate. Aluminum was vapor-deposited on the ITO substrate at a thickness of 92 nm, the substrate was immersed in the THF solution (2.3 g / L) of the composition A, allowed to stand for 4 days, then pulled up, washed with THF, washed, and Ar gas was blown. Then, a polymer binding layer composed of an aromatic polymer compound having a polystyrene-equivalent number average molecular weight of 7.9 × 10 ³ was produced. At this time, the film thickness of the polymer bonding layer is 57 nm, and the orbital energy of LUMO and HOMO of the polymer 1 constituting the polymer bonding layer calculated by the B3LYP / 6-31G ^* method of the method is −1. .70 eV and -4.97 eV. Further, a conductive organic material made of a polymer F having LUMO and HOMO orbital energies calculated by the above method of −1.70 eV and −4.97 eV, respectively, is formed on the film so that the film thickness becomes about 85 nm. After spin coating, aluminum was vapor-deposited to 84 nm, and current-voltage measurement of the obtained laminated structure 4 was performed. As a result, a current of 3.31 × 10 ⁻⁶ A flowed when a voltage of +8 V was applied. The obtained results are shown in Table 3.

<Comparative Example 2>-Preparation of an electroluminescent device comprising a comparative polymer film 2 (not a laminated structure)-
The ITO substrate was washed with chloroform, methanol, an aqueous solution of an alkaline detergent, distilled water, and acetone and then exposed to ozone gas for 1 minute to remove deposits on the surface of the ITO substrate. A polymer in which 86 nm of aluminum is vapor-deposited on this ITO substrate, and the orbital energies of LUMO and HOMO calculated by the B3LYP / 6-31G ^* method of the above method are -1.70 eV and -4.97 eV, respectively. After spin-coating a conductive organic material made of F so as to have a film thickness of about 85 nm, 94 nm of aluminum was deposited, and current-voltage measurement of the resulting comparative polymer film 2 was performed. As a result, when a voltage of +8 V was applied, a current of 1.20 × 10 ⁻⁶ A flowed. The obtained results are shown in Table 3.

<Evaluation>
As is clear from the results shown in Table 3, it can be seen that the laminated structure of the present invention allows a larger amount of current to flow than a comparative polymer film that is not a laminated structure.

<Example 9> -Production of electroluminescent element using laminated structure 5 (method (B))-
The two ITO substrates were washed with a sodium hydroxide aqueous solution, hydrochloric acid, and water, respectively, and then exposed to ozone gas for 1 minute to remove deposits on the surface of the ITO substrate. Each of these ITO substrates is represented by the following formula:

After being immersed in an ethanol solution (4 mM) of compound H represented by the formula, it was pulled up, washed with ethanol and dried. Next, these substrates were immersed in a toluene solution (15 mM) of bis (tri-t-butylphosphine) palladium, heated at 70 ° C. for 2 hours, pulled up, washed with toluene, and dried. These substrates are then represented by the following formula:

Embedded image A solution of Compound I in THF (25 mM) and an aqueous sodium carbonate solution (2M) mixed in 2: 1 (volume ratio) was stirred for 2 hours at room temperature. Thereafter, the substrate was pulled up, washed with toluene, methanol, and distilled water and dried to prepare a polymer bonding layer on the ITO substrate. The film thickness of this polymer binding layer was 236 nm.

Aromatic polymer compounds constituting the polymer bonding layer on the ITO substrate were recovered by pouring chloroform over one of the two substrates on which the polymer bonding layer was prepared. This collection operation was repeated until the substrate was irradiated with a UV lamp and no luminescence derived from the aromatic polymer compound could be confirmed. The collected washing solution is concentrated, and the molecular weight of the obtained aromatic polymer compound is measured by gel permeation chromatography (GPC) (trade name: Agilent 1100 Series, manufactured by Agilent Technologies, Inc.). Shimadzu Corporation LC-10 series) was analyzed, and the polystyrene-equivalent number average molecular weight Mn was 5.5 × 10 ⁴ and the polystyrene-equivalent weight average molecular weight Mw was 9.9 × 10 ⁴ . . Moreover, the orbital energies of LUMO and HOMO of the aromatic polymer compound calculated by the B3LYP / 6-31G ^* method of the method were −1.70 eV and −4.97 eV.

Next, a conductive organic material made of polymer G having LUMO and HOMO orbital energies calculated by the above method of -1.70 eV and -4.97 eV, respectively, is formed on the polymer bonding layer of another substrate. After spin coating so that the film thickness was about 500 nm, gold was deposited to 100 nm, and current-voltage measurement of the obtained laminated structure 5 was performed. As a result, a current of 1.1 × 10 ⁻⁸ A flowed when a voltage of +3 V was applied, and a current of 1.0 × 10 ⁻⁷ A flowed at + 6V. Table 4 shows the obtained results.

<Comparative Example 3>-Preparation of an electroluminescent element comprising a comparative polymer film 3 (not a laminated structure)-
The ITO substrate was exposed to ozone gas for 1 minute to remove deposits on the surface of the ITO substrate.
On this ITO substrate, a conductive organic material made of a polymer G having LUMO and HOMO orbital energies calculated by the B3LYP / 6-31G ^* method of the above-described method of -1.70 eV and -4.97 eV, respectively, is formed. Was spin-coated so as to be about 500 nm, and then gold was deposited to about 100 nm, and current-voltage measurement of the obtained comparative polymer film 3 was performed. As a result, when a voltage of +3 V was applied, a current of 1.3 × 10 ⁻¹⁰ A flowed and at +6 V, a current of 2.0 × 10 ⁻¹⁰ A flowed. Table 4 shows the obtained results.

<Evaluation>
As is clear from the results shown in Table 4, it can be seen that the laminated structure of the present invention allows a larger amount of current to flow than a comparative polymer film that is not a laminated structure.

<Example 10> -Production of electroluminescent element using laminated structure 6 (method (B))-
Each of the two silver substrates has the following formula:

After being immersed in an ethanol solution (4 mM) of compound H represented by the formula, it was pulled up, washed with ethanol and dried. Next, these substrates were immersed in a toluene solution (15 mM) of bis (tri-t-butylphosphine) palladium, heated at 70 ° C. for 2 hours, pulled up, washed with toluene, and dried. These substrates are then represented by the following formula:

Embedded image A solution of Compound I in THF (25 mM) and an aqueous sodium carbonate solution (2M) mixed in 2: 1 (volume ratio) was stirred for 2 hours at room temperature. Thereafter, the substrate was pulled up, washed with toluene, methanol, and distilled water and dried to prepare a polymer bonding layer on the silver substrate. The film thickness of this polymer binding layer was 152 nm.

Aromatic polymer compounds constituting the polymer bonding layer on the silver substrate were collected by pouring chloroform over one of the two substrates on which the polymer bonding layer was prepared. This collection operation was repeated until the substrate was irradiated with a UV lamp and no luminescence derived from the aromatic polymer compound could be confirmed. The collected washing liquid is concentrated, and the molecular weight of the obtained aromatic polymer compound is determined by gel permeation chromatography (GPC) (Shimadzu Corporation) equipped with a fluorescence detector (trade name: Agilent 1100 Series, manufactured by Agilent Technologies). As a result of analysis using a Seisakusho LC-10 series, the polystyrene-equivalent number average molecular weight Mn was 8.5 × 10 ⁴ and the polystyrene-equivalent weight average molecular weight Mw was 1.57 × 10 ⁵ . Moreover, the orbital energies of LUMO and HOMO of the aromatic polymer compound calculated by the B3LYP / 6-31G ^* method of the method were −1.70 eV and −4.97 eV.

Next, a conductive organic material made of polymer G having LUMO and HOMO orbital energies calculated by the above method of -1.70 eV and -4.97 eV, respectively, is formed on the polymer bonding layer of another substrate. After spin coating so that the film thickness was about 500 nm, aluminum was deposited by about 200 nm, and current-voltage measurement of the obtained laminated structure 6 was performed. As a result, a current of 4.8 × 10 ⁻¹⁰ A flowed when a voltage of −4 V was applied. The results obtained are shown in Table 5.

<Comparative Example 4>-Production of an electroluminescent device comprising a comparative polymer film 4 (not a laminated structure)-
On a silver substrate, a conductive organic material made of polymer G having LUMO and HOMO orbital energies calculated by the B3LYP / 6-31G ^* method of the above-described method of −1.70 eV and −4.97 eV, respectively, is formed. After spin-coating so as to be about 500 nm, about 200 nm of aluminum was deposited, and current-voltage measurement of the obtained comparative polymer film 4 was performed. As a result, a current of 1.1 × 10 ⁻¹¹ A flowed when a voltage of −4 V was applied. The results obtained are shown in Table 5.

<Evaluation>
As is clear from the results shown in Table 5, it can be seen that the laminated structure of the present invention allows a larger amount of current to flow than a comparative polymer film that is not a laminated structure.

  As described above, according to the compound of the present invention, it is possible to form a polymer binding layer through which electricity efficiently flows from the electrode, and according to the laminated structure of the present invention, the polymer is bonded to the electrode. Electricity can efficiently flow from the electrode to the polymer bonding layer through the bonding portion of the aromatic polymer compound, and further, electricity can be efficiently transferred from the polymer bonding layer to the conductive organic material layer through the terminal portion of the aromatic polymer compound. It becomes possible to flow.

  Therefore, the laminated structure of the present invention is useful as an electroluminescent element with low driving voltage and low power consumption.

Claims (23)

An electrode, a polymer binding layer disposed on the electrode, and a conductive organic material layer disposed on the polymer binding layer,
The polymer binding layer has the following formula (I):

(In the formula, Ar is a conjugated divalent group which may have a substituent, and when there are a plurality of them, they may be the same or different, and n is an integer of 1 or more. .)
And an aromatic polymer compound having a polystyrene-reduced number average molecular weight of 1 × 10 ³ or more and 1 × 10 ⁸ or less,
The polymer bonding layer is bonded to the electrode through a chemical bond between the aromatic polymer compound and the electrode surface,
The number average molecular weight in terms of polystyrene of the conductive organic material constituting the layer adjacent to the polymer bonding layer in the conductive organic material layer is 3 × 10 ² or more and 1 × 10 ⁸ or less.
Laminated structure.   The film thickness of the polymer bonding layer is 0.1 nm to 100 μm, and the film thickness of a layer adjacent to the polymer bonding layer in the conductive organic material layer is 0.1 nm to 1 cm. The laminated structure described.   The orbital energy of the lowest unoccupied molecular orbital (LUMO) of the aromatic polymer compound is −4.0 eV or more and −0.5 eV or less and / or the orbital energy of the highest occupied molecular orbital (HOMO) of the aromatic polymer compound. The laminated structure according to claim 1, wherein is from −6.0 eV to −4.0 eV.   The difference between the LUMO orbital energy of the aromatic polymer compound and the LUMO orbital energy of the conductive organic material constituting the layer adjacent to the polymer bonding layer in the conductive organic material layer is −2.5 eV or more. +2.5 eV or less and / or HOMO orbital energy of the aromatic polymer compound and HOMO orbital energy of the conductive organic material constituting the layer adjacent to the polymer bonding layer in the conductive organic material layer The layered structure according to any one of claims 1 to 3, wherein the difference is -1.5 eV or more and +1.5 eV or less.   The laminated structure according to any one of claims 1 to 4, wherein a terminal group of the aromatic polymer compound is chemically bonded to a reactive group present on the electrode surface.   The laminated structure according to any one of claims 1 to 5, wherein the electrode includes at least one electrically conductive compound selected from the group consisting of base metals, noble metals, and oxides thereof. The polymer binding layer has the following formula (II):

(In the formula, Ar ¹ is a divalent group having an aromatic ring, G is an r + p valent group having an aromatic ring, X ¹ is a terminal group, and r is an integer of 1 to 10, n and p are each independently an integer of 1 or more, and when r is 2 or more, a plurality of existing E ^a may be the same or different, and exist when n is 2 or more. A plurality of Ar ¹ may be the same or different, and when p is 2 or more, a plurality of X ^{1 present} may be the same or different, and E ^a is a mercapto group, hydroxy Group, carboxyl group, sulfonic acid group, phosphonic acid group, trialkoxysilyl group, trihydroxysilyl group, chlorocarbonyl group, chlorophosphonic acid group, chlorosulfonic acid group, cyanato group, isocyanato group, amino group, substituted amino group and Substituted disul Is a monovalent group selected from the group consisting of I de group.)
It is formed by immersing an electrode in a solution containing a conjugated polymer represented by the formula (1) at a concentration of 0.0001% by mass or more and / or applying the solution to the electrode. The laminated structure according to any one of the above. The polymer binding layer is formed on the surface of the solution in the following formula (III):

(In the formula, G is an r + p-valent group having an aromatic ring, X ^a is a halogen atom or —SO ₃ Q ^a (where Q ^a represents an alkyl group or an aryl group, and the alkyl group and the aryl are substituted) And r is an integer of 1 or more and 10 or less, p is an integer of 1 or more, and when p is 2 or more, a plurality of X present ^a may be the same or different, and E is a mercapto group, hydroxy group, carboxyl group, sulfonic acid group, phosphonic acid group, trialkoxysilyl group, trihydroxysilyl group, chlorocarbonyl group, chlorophosphonic acid A monovalent group selected from the group consisting of a group, a chlorosulfonic acid group, a cyanato group, an isocyanato group, an amino group, a substituted amino group and a substituted disulfide group, and a reactive group present on the electrode surface It is a linking group formed by a chemical bond.)
In the presence of an electrode to which a group represented by formula (IV) is bonded, the following formula (IV):

(In the formula, Ar ¹ is a divalent group having an aromatic ring, M is a halogen atom, a hydrogen atom, —B (OQ ¹ ) ₂ (where Q ¹ is independently a hydrogen atom, an alkyl group, or an aryl group). Represents a ring formed by bonding to each other, the alkyl and the aryl group may have a substituent, and —Si (Q ² ) ₃ (where Q ² is an alkyl group). Or an alkoxy group, wherein the alkyl group and the alkoxy group may have a substituent, -Sn (Q ³ ) ₃ (where Q ³ is an alkyl group which may have a substituent). A group represented by —SO ₃ Q ^a (wherein Q ^a is an alkyl group or an aryl group, and the alkyl group and the aryl group may have a substituent), or —Z ¹ (Z ² ) _m (where Z ¹ is a metal atom or metal And Z ² is a counter anion), and two Ms may be the same or different.)
The laminated structure according to any one of claims 1 to 6, which is formed by polycondensation of an aromatic compound represented by the formula (1) using a polymerization catalyst or an equivalent reactant. The polymer binding layer has the following formula (V):

(In the formula, Ar ¹ is a divalent group having an aromatic ring, G is an r + p valent group having an aromatic ring, X ¹ is a terminal group, and r is an integer of 1 to 10, n and p are each independently an integer of 1 or more, and when r is 2 or more, a plurality of existing E may be the same or different. When n is 2 or more, a plurality of existing E Ar ¹ may be the same or different, and when p is 2 or more, a plurality of X ^{1 present} may be the same or different, and E is a mercapto group, a hydroxy group, Carboxyl group, sulfonic acid group, phosphonic acid group, trialkoxysilyl group, trihydroxysilyl group, chlorocarbonyl group, chlorophosphonic acid group, chlorosulfonic acid group, cyanato group, isocyanato group, amino group, substituted amino group and substituted disulfide A linking group formed by a chemical bond between a monovalent group selected from the group consisting of groups and a reactive group present on the surface of the electrode.)
The laminated structure according to any one of claims 1 to 8, which has a structure represented by:   The bonding group E in the formula (V) is at least one selected from the group consisting of a covalent bond, a coordinate bond, a hydrogen bond and an ionic bond between the monovalent group and a reactive group present on the electrode surface. The laminated structure according to claim 9, which is a bonding group formed by:   The monovalent group is a monovalent group selected from the group consisting of a mercapto group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a chlorocarbonyl group, a chlorophosphonic acid group, and a chlorosulfonic acid group. The laminated structure according to 10.   G in the formula (V) has a monocyclic ring which may have a substituent, a condensed ring which may have a substituent, a ring assembly which may have a substituent, and a substituent. The laminated structure according to any one of claims 9 to 11, which is at least one r + p-valent group selected from the group consisting of optionally bridged polycycles. The r + p-valent group is represented by the following formulas (1) to (16):

The laminated structure according to claim 12, comprising at least one of a heterocyclic ring and an aromatic ring represented by the formula:   The laminated structure according to claim 13, wherein the r + p-valent group includes one heterocyclic ring represented by the formula (5).   R in the formula (V) is an integer of 1 or more and 3 or less (provided that G in the formula (V) is a monocyclic aromatic ring structure and the number of carbon atoms constituting the ring structure is 2) In the laminated structure according to claim 9, r is 1, and r is 1 or 2 when the number of carbon atoms is 3. 15. Ar ¹ in the formula (V) is represented by the following formula (VI):

Wherein R ⁵ is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the alkyl group, the aryl group, the arylalkyl group and the monovalent heterocyclic group are R ⁶ may have a substituent, and R ⁶ is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group , Arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, carbamoyl group, imide residue, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Group, the alkyl group, the alkoxy group, the alkylthio group, the aryl group. The aryloxy group, the arylthio group, the arylalkyl group, the arylalkoxy group, the arylalkylthio group, the arylalkenyl group, the arylalkynyl group, the acyl group, the acyloxy group, the carbamoyl group, and the monovalent group. The heterocyclic group may have a substituent, and a plurality of R ⁵ and R ⁶ may be the same or different, and R ⁵ and an alkyl group which may have a substituent. When a plurality of R ⁶ are present, they may be bonded to each other to form a ring.)
Is contained in an amount of 0.1% by mass or more based on the total mass of all repeating units in the aromatic polymer compound constituting the polymer binding layer, and / or the following formula (VII ):

(Wherein, ^{R 6} has the same meaning as ^{R 6} in formula (VI).)
The repeating unit represented by formula (1) is contained in an amount of 0.1% by mass or more based on the total mass of all repeating units in the aromatic polymer compound constituting the polymer binding layer. The laminated structure according to any one of the above.   The mole percentage of the repeating unit represented by the formula (VI) and the repeating unit represented by the formula (VII) with respect to the total of all repeating units in the aromatic polymer compound constituting the polymer binding layer. The laminated structure according to claim 16, wherein the total of the percentage and the mole percentage is 10 mol% or more and 100 mol% or less. On the electrode, the following formula (I):

(In the formula, Ar is a conjugated divalent group which may have a substituent, and when there are a plurality of them, they may be the same or different, and n is an integer of 1 or more. .)
The number average molecular weight in terms of polystyrene is 1 × 10 ³ or more and 1 × 10 ⁸ or less, and the aromatic polymer compound is chemically bonded to the electrode surface. Forming a polymer binding layer,
Forming a layer composed of a conductive organic material having a polystyrene-equivalent number average molecular weight of 3 × 10 ² or more and 1 × 10 ⁸ or less on the polymer binding layer;
The manufacturing method of the laminated structure containing this.   The electronic device containing the laminated structure as described in any one of Claims 1-17.   The electronic device according to claim 19, which is a light emitting device.   The electronic device according to claim 19, which is a photoelectric conversion device. Formula (VIII) below

(In the formula, Ar ¹ is a divalent group having an aromatic ring, X ¹ is a terminal group, n is an integer of 1 or more, Ar ¹⁵ is an i + p valent group having an aromatic ring, and i And p are each independently an integer of 1 or more, i + p is 2 or more and 20 or less, Y is an oxygen atom, sulfur atom, imino group, substituted imino group, ethenylene group, substituted ethenylene group or ethynylene group, j Is 0 or 1, and R ⁷ is a hydrogen atom, alkyl group, alkylthio group, aryl group, arylthio group, arylalkyl group, arylalkylthio group, arylalkenyl group, arylalkynyl group, silyl group, substituted silyl group, acyl group Or a monovalent heterocyclic group, the alkyl group, the alkylthio group, the aryl group, the arylthio group, the arylalkyl group, the arylalkyl The thio group, the arylalkenyl group, the arylalkynyl group, the acyl group, and the monovalent heterocyclic group may have a substituent, and two R ⁷ may be the same or different. It may be bonded to each other to form a ring.)
A conjugated polymer represented by Following formula (IX):

(In the formula, Ar ¹⁵ is an i + p-valent group having an aromatic ring, i and p are each independently an integer of 1 or more, i + p is 2 or more and 20 or less, and X ^a is a halogen atom or —SO _3. Q ^a (wherein Q ^a represents an alkyl group which may have ^a substituent), Y represents an oxygen atom, sulfur atom, imino group, substituted imino group, ethenylene group, substituted ethenylene A group or an ethynylene group, j is 0 or 1, and R ⁷ is a hydrogen atom, alkyl group, alkylthio group, aryl group, arylthio group, arylalkyl group, arylalkylthio group, arylalkenyl group, arylalkynyl group, silyl group Group, substituted silyl group, acyl group or monovalent heterocyclic group, the alkyl group, the alkylthio group, the aryl group, the arylthio group, the aryl Alkyl group, the arylalkylthio group, the arylalkenyl group, the arylalkynyl group, the acyl group and the monovalent heterocyclic group may have a substituent, the two R ⁷ have the same May be different from each other and may be bonded to each other to form a ring.)
A conjugated compound represented by