JP2015189804A - Conductive composition, conductive film and organic semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition that can provide a conductive film with high conductivity and excellent temporal stability of the conductivity, a conductive film obtained from the conductive composition, and an organic semiconductor device using the conductive film.SOLUTION: The conductive composition comprises a π-conjugated polymer having a repeating unit represented by the general formula (1), an oxidant, a non-conjugated polymer, and a reductant. The mass ratio of the content of the reductant to the content of the oxidant is from 0.001 to 0.5.

Description

  The present invention relates to a conductive composition, a conductive film, and an organic semiconductor device.

In recent years, organic semiconductor devices (for example, organic transistors, photoelectric conversion elements, thermoelectric conversion elements, organic EL, etc.) using organic materials as semiconductors have been actively developed. Research is also being conducted on the use of polymers as organic materials because of process advantages.
For example, Patent Document 1 discloses a polymer compound having a specific structural unit obtained by oxidative polymerization using an oxidizing agent such as iron chloride, and further charge transporting a composition containing the polymer compound. An organic transistor used in the layer is disclosed.

JP2013-170134A

On the other hand, with the enhancement of functionality and miniaturization of organic semiconductor devices, it is required that the organic semiconductor layer (conductive film) exhibit high conductivity stably over time. That is, high electrical conductivity and excellent temporal stability of electrical conductivity are required.
Under these circumstances, the present inventors examined a conductive composition containing a polymer compound (π-conjugated polymer) obtained by oxidative polymerization using an oxidizing agent with reference to Patent Document 1, and as a result, Although the conductivity is high, it has been found that the conductivity decreases with the passage of time, and the stability with time of the conductivity does not satisfy the level required recently.

  Accordingly, in view of the above circumstances, the present invention provides a conductive composition that provides a conductive film having high conductivity and excellent conductivity stability over time, a conductive film obtained from the conductive composition, and It aims at providing the organic-semiconductor device using the said electrically conductive film.

  As a result of intensive studies on the above problems, the present inventors have decomposed the polymer by excess carriers in the π-conjugated polymer generated by the oxidizing agent, and the degradation of the polymer causes a decrease in conductivity over time. I found out that there is a possibility. Furthermore, it has been found that by adding a specific amount of reducing agent to the oxidizing agent, the carrier in the π-conjugated polymer becomes an appropriate amount, and both high conductivity and stability over time of the conductivity are compatible. The present invention is based on these findings and the like, and the specific configuration is as follows.

(1) containing a π-conjugated polymer having a repeating unit represented by the general formula (1) described later, an oxidizing agent, a non-conjugated polymer, and a reducing agent,
The electrically conductive composition whose mass ratio of content of the said reducing agent with respect to content of the said oxidizing agent is 0.001-0.5.
(2) The conductive composition according to (1), wherein the π-conjugated polymer is obtained by polymerization by an oxidative polymerization method in the presence of the oxidizing agent and the non-conjugated polymer.
(3) Conductivity as described in said (1) or (2) whose A ring is a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a cyclopentadiene ring, or a silole ring in the said General formula (1). Composition.
(4) The conductive composition according to any one of (1) to (3), wherein in the general formula (1), n is an integer of 1 to 3.
(5) In the general formula (1), X ¹ and X ³ , or X ¹ and X ⁴ are each independently a sulfur atom, an oxygen atom, or an NR group (where R is a hydrogen atom or an alkyl group). The conductive composition according to any one of the above (1) to (4).
(6) The conductive composition according to any one of (1) to (5), wherein the non-conjugated polymer has a sulfo group.
(7) The above (1) to (6), wherein the oxidizing agent is at least one compound selected from the group consisting of iron (III) salts, copper (II) salts, peroxides, and peracids. The electrically conductive composition in any one of.
(8) The reducing agent comprises a monocyclic aromatic compound, a nitrogen-containing aromatic compound, a sulfur-containing aromatic compound, an aromatic vinyl polymer, an aromatic amine, an aliphatic amine, a nitro compound, a thiol, and a metal complex salt. The conductive composition according to any one of (1) to (7), which is at least one compound selected from the group.
(9) The conductive composition according to any one of (1) to (8), further including a hydrophilic solvent.
(10) The conductive composition according to (9), wherein the hydrophilic solvent has a boiling point of 130 ° C. or higher.
(11) The conductivity according to any one of (1) to (8), obtained by dispersing the π-conjugated polymer, the oxidizing agent, the non-conjugated polymer, and the reducing agent in water. Sex composition.
(12) The above (9) or (9) obtained by dispersing the π-conjugated polymer, the oxidizing agent, the non-conjugated polymer, and the reducing agent in water and further adding the hydrophilic solvent. The electrically conductive composition as described in 10).
(13) A conductive film obtained from the conductive composition according to any one of (1) to (12).
(14) The conductive film according to (13), wherein the carrier concentration is 1 × 10 ^{24 to} 3 × 10 ²⁶ / m ³ .
(15) An organic semiconductor device using the conductive film according to (13) or (14).
(16) An organic semiconductor device comprising a base material, an electrode, and the conductive film according to (13) or (14) in this order.

As shown below, according to the present invention, a conductive composition that provides a conductive film that has high conductivity and excellent conductivity over time, a conductive film obtained from the conductive composition, and An organic semiconductor device using the conductive film can be provided.
In addition, hereinafter, the fact that the stability over time of the conductivity is excellent also simply means that the stability over time is excellent.

It is sectional drawing which shows typically an example of the thermoelectric conversion element of this invention. The arrows in FIG. 1 indicate the direction of the temperature difference applied when the element is used. It is sectional drawing which shows typically an example of the thermoelectric conversion element of this invention. The arrows in FIG. 2 indicate the direction of the temperature difference applied when the element is used. It is sectional drawing which shows typically an example (module) of the thermoelectric conversion element of this invention. FIG. 4A and FIG. 4B are schematic cross-sectional views showing one embodiment of the photoelectric conversion element of the present invention.

Below, the electrically conductive composition of this invention, an electrically conductive film, and an organic-semiconductor device are demonstrated.
In the present specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and includes a mixture thereof.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Conductive composition]
The conductive composition of the present invention (hereinafter also referred to as the composition of the present invention) is a π-conjugated polymer (A) having a repeating unit represented by the following general formula (1), an oxidizing agent (B), A non-conjugated polymer (C) and a reducing agent (D) are contained.
Here, the mass ratio of the content of the reducing agent (D) to the content of the oxidizing agent (B) is 0.001 to 0.5. That is, the mass ratio (D / B) between the content of the oxidizing agent (B) and the content of the reducing agent (D) is 0.001 to 0.5.
Hereinafter, each component contained in the composition of the present invention will be described.

<Π-conjugated polymer (A)>
The π-conjugated polymer (A) is a π-conjugated polymer having a repeating unit represented by the following general formula (1). Here, the π-conjugated polymer refers to a polymer having a structure in which the main chain is conjugated with a lone pair of π electrons or lone electrons.
Since the π-conjugated polymer (A) has high planarity as shown in the following general formula (1), the overlap of π orbitals between polymer molecules is large. As a result, it is presumed that carrier hopping between polymer molecules is promoted, leading to high conductivity of the obtained conductive film.
In addition, when there are a plurality of repeating units represented by the following general formula (1) in the π-conjugated polymer (A), a plurality of repeating units represented by the following general formula (1) may be the same or different. It may be.

In general formula (1), A ring represents a conjugated hydrocarbon ring or a conjugated heterocyclic ring.
Here, the conjugated hydrocarbon ring refers to a hydrocarbon ring having a conjugated structure. The conjugated heterocycle represents a heterocycle having a conjugated structure. The conjugated structure refers to a structure in which two “carbon atoms—carbon atoms (C—C) multiple bonds” are connected via a single bond. The conjugated structure is preferably a structure in which two C—C double bonds are connected via a single bond.
Examples of the conjugated hydrocarbon ring include a benzene ring and a cyclopentadiene ring.
Examples of the conjugated heterocyclic structure include a pyrrole ring, a thiophene ring, a pyridine ring, a silole ring, and a furan ring.
The A ring is preferably a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a cyclopentadiene ring, or a silole ring.

In general formula (1), n represents an integer of 0 or more. Especially, the integer of 1-3 is preferable. When n is an integer of 2 or more, a plurality of A rings may be the same or different.
Here, n represents the number of A rings connected by condensing.
For example, in the π-conjugated polymer 1 used in the examples described later, n is 1 and one A ring is a benzene ring.
Further, in the π-conjugated polymer 3 used in Examples described later, n is 2, and two A rings are both benzene rings.
In the π-conjugated polymer 4 used in the examples described later, n is 3 and all three A rings are benzene rings.
In the π-conjugated polymer 7 used in the examples described later, n is 3, 2 of the 3 A rings are silole rings, and 1 A ring is a benzene ring.
Incidentally, when n is 0, indicating that the A ring is not a monocyclic ring containing X ¹ and X ^2, it is a monocyclic ring containing X ³ and X ⁴ are condensed. That is, general formula (1) is represented by the following general formula (n0).

In the general formula (1), X ¹ , X ² , X ³ and X ⁴ are each independently a hetero atom, a hetero atom having a substituent (for example, a substituent W described later), a —CH═CH— group, Or represents a = CH- group. The hetero atom is not particularly limited, but specific examples include a nitrogen atom, an oxygen atom, a sulfur atom, and the like.
X ¹ and X ³ , or X ¹ and X ⁴ are preferably each independently a sulfur atom, an oxygen atom, or an NR group (where R is a hydrogen atom or an alkyl group).

In general formula (1), the monocycle containing X ¹ and X ² and the monocycle containing X ³ and X ⁴ all represent an aromatic ring.
For example, when X ¹ is a —CH═CH— group and X ² is a ═CH— group, the monocycle containing X ¹ and X ² represents a benzene ring. In addition, when X ¹ is a sulfur atom and X ² is a ═CH— group, the monocycle containing X ¹ and X ² represents a thiophene ring.

In general formula (1), R ¹ , R ² , and R ^A are each independently an aryl group (preferably having 5 to 20 carbon atoms), a heteroaryl group (preferably having 5 to 20 ring atoms), alkyl Group (preferably having 1 to 30 carbon atoms), alkoxy group (preferably having 1 to 30 carbon atoms), polyethyleneoxyether group (see the structural formula below), alkylthio group (RS-: R is an alkyl group (preferably having 1 carbon atom) To 30).), A polyethyleneoxythioether group (see the structural formula below), an alkylamino group (R ₁ R ₂ N—: R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group (preferably a carbon number). 1 to 30), wherein at least one of R ₁ and R ₂ represents an alkyl group), or represents a polyethyleneoxyamino group (see the structural formula below).
In the following structural formulas, R represents a hydrogen atom or an alkyl group. n represents an integer of 1 or more (preferably an integer of 1 to 10). The wavy line represents the coupling position.

The carbon atom in R < ¹ >, R < ² > and ^RA may be substituted with an oxygen atom or a sulfur atom.
R ¹ , R ² , and R ^A may be linked to each other at an arbitrary position.
R ¹ , R ² , and R ^A may have a substituent (for example, a substituent W described later).

In the general formula (1), nA represents the number of ^RA substituted on the A ring, and specifically represents an integer of 0 or more. The upper limit of nA is the maximum value of the number of ^{RA that} can be substituted on the A ring. nA is preferably an integer of 0 to 2.
In general formula (1), nB and nC each independently represent an integer of 0 or more. The upper limit of nB is the maximum value of the number of R ^{1 that} can be substituted with a single ring containing X ¹ and X ² . The upper limit of nC is the maximum value of the number of R ^{2 that} can be substituted with a single ring containing X ³ and X ⁴ . nB and nC are preferably each independently an integer of 0 to 2.

  In the general formula (1), an asterisk (star) represents a binding position.

The π-conjugated polymer (A) may have another repeating unit other than the repeating unit represented by the general formula (1).
When the π-conjugated polymer (A) has a plurality of repeating units, the copolymerization mode is not particularly limited, and any of block copolymerization, alternating copolymerization, random copolymerization, and graft copolymerization may be used.
The other repeating unit may be a linking group, an atom, or a combination thereof, which can form a conjugated system of the main chain. Such another repeating unit is not particularly limited, but is preferably at least one repeating unit selected from the group consisting of an ethenylene group, an ethynylene group, an arylene group, and a heteroarylene group.

6-20 are preferable and, as for carbon number of the said arylene group, 6-15 are more preferable. The arylene group is preferably phenylene or naphthylene.
The arylene group has a plurality of aromatic rings bonded to an atom capable of forming a conjugated system of the main chain, preferably a nitrogen atom, and may include a group bonded to the main chain through different aromatic rings. Examples of such a group include a divalent group obtained from triphenylamine, which is bonded to the main chain with a different phenyl group.

  Moreover, 3-20 are preferable and, as for carbon number of the said heteroarylene group, 5-12 are more preferable. The heterocycle constituting the heteroarylene group is not particularly limited, but a 5-membered ring or a 6-membered ring is preferable. The heteroatom constituting the heterocycle is not particularly limited, but a sulfur atom, a nitrogen atom, an oxygen atom, A silicon atom, a selenium atom, etc. are mentioned suitably. Preferred examples of the heteroarylene group include a divalent thiophene ring, a divalent thiazole ring, a divalent oxazole ring, a divalent furan ring, a divalent pyrrole ring, a divalent selenophene ring, and a divalent thiazole ring. Divalent oxazole ring, divalent phosphole ring, divalent phospholine ring, divalent thiadiazole ring, divalent oxadiazole ring, divalent pyrazole ring, divalent imidazole ring, divalent pyridine ring Examples thereof include a divalent pyrazine ring, a divalent pyridazine ring, a divalent triazine ring, a divalent triazole ring, and a divalent tetrazine ring.

The arylene group and heteroarylene group may each be condensed.
The condensed ring may be an aliphatic ring or an aromatic ring, and may be a hydrocarbon ring or a hetero ring. Among these, a ring containing an aromatic ring structure is preferable, and a ring containing an aromatic heterocyclic structure is more preferable.
The aromatic hydrocarbon ring constituting the condensed ring may be a monocyclic hydrocarbon ring having aromaticity, and a benzene ring may be mentioned as the basic ring.
The aromatic heterocycle constituting the condensed ring is not particularly limited as long as it is a monocyclic heterocycle having aromaticity, but a 5-membered aromatic heterocycle or a 6-membered aromatic heterocycle is Preferably mentioned. Examples of the hetero atom constituting the heterocycle include a sulfur atom, a nitrogen atom, an oxygen atom, a silicon atom, and a selenium atom. An oxygen atom, a sulfur atom, and a nitrogen atom are preferable, and a sulfur atom and a nitrogen atom are more preferable. Examples of the 5-membered aromatic heterocycle include thiophene ring, furan ring, pyrrole ring, selenophene ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, triazole ring, thiadiazole ring , Diazole ring, pyridine ring and pyrazine ring. Examples of the 6-membered aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and a triazine ring. Of these, a thiophene ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a thiadiazole ring, a diazole ring, a pyridine ring, and a pyrazine ring are more preferable.

  Examples of the condensed arylene group or heteroarylene group include fluorene, dithienosilole, cyclopentadithiophene, benzodithiophene, thieno [3,4-b] thiophene, [1] benzothieno [3,2-b. ] [1] Benzothiophene, benzofluorene and the like. In the case where the arylene group and the heteroarylene group are condensed, the connecting position connected to the main chain is a ring constituent atom constituting a different ring, even if it is a ring constituent atom constituting the same ring. May be.

  The another repeating unit may have a substituent (for example, substituent W described later).

  The content of the repeating unit represented by the general formula (1) in the π-conjugated polymer (A) is not particularly limited, but is preferably 10% by mass or more, and more preferably 30% by mass or more. The upper limit is not particularly limited and is 100% by mass (that is, a homopolymer of a repeating unit represented by the general formula (1)).

The molecular weight of the π-conjugated polymer (A) is not particularly limited, but is preferably 5,000 to 200,000, more preferably 10,000 to 150,000 in terms of weight average molecular weight (Mw).
In addition, in this specification, a weight average molecular weight is a polystyrene conversion value measured by GPC (solvent: THF).

(Production method)
The manufacturing method in particular of (pi) conjugated polymer (A) is not restrict | limited, A well-known method can be utilized. Examples thereof include a method of polymerizing a monomer that becomes a repeating unit represented by the general formula (1) described above by polymerization by an oxidative polymerization method or a coupling polymerization method. Of these, a method of polymerizing by an oxidative polymerization method is preferable.

(Preferred embodiment)
The π-conjugated polymer (A) is preferably obtained by polymerization by an oxidative polymerization method in the presence of an oxidizing agent. Especially, it is more preferable that it is obtained by superposing | polymerizing by an oxidative polymerization method in presence of an oxidizing agent and the nonconjugated polymer (C) mentioned later.
By polymerizing in the presence of the non-conjugated polymer (C), the dispersibility of the π-conjugated polymer (A) and the non-conjugated polymer (C) is improved, so that a carrier path is easily formed, and the resulting conductive film The conductivity is higher.
In addition, it is preferable to use the oxidizing agent used by the oxidation polymerization method also as an oxidizing agent (B) mentioned later. Specific examples and preferred embodiments of the oxidizing agent are the same as those of the oxidizing agent (B) described later.

  Specific examples of the repeating unit represented by the general formula (1) are shown below, but the present invention is not limited thereto. Here, * shows the connection position of a repeating unit.

  In the composition of the present invention, the content of the π-conjugated polymer (A) is not particularly limited, but is preferably 5 to 70% by mass, and 10 to 50% by mass with respect to the total solid content in the composition. More preferably.

<Oxidizing agent (B)>
The oxidizing agent (B) functions as a dopant for the above-described π-conjugated polymer (A). In addition, when the π-conjugated polymer (A) is obtained by polymerization by an oxidative polymerization method in the presence of an oxidant, and the oxidant used in the oxidative polymerization method is also used as the oxidant (B), The oxidizing agent (B) also functions as an oxidizing polymerization agent.

Although it does not restrict | limit especially as an oxidizing agent (B), At least 1 sort (s) of compounds selected from the group which consists of iron (III) salt, copper (II) salt, a peroxide, and a peracid is preferable.
Specific examples of the oxidizing agent (B) include halogen (Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF), Lewis acid (PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr _{3, SO 3),} the transition metal compound _{(FeCl 3, FeOCl, TiCl 4} , ZrCl 4, HfCl 4, NbF 5, NbCl 5, TaCl 5, MoF 5, MoCl 5, WF 6, WCl 6, UF 6, LnCl ₃ (Lan = lanthanoids such as La, Ce, Pr, Nd, Sm, etc.), XeOF ₄ , (NO ₂ ⁺ ) (SbF ₆ ⁻ ), (NO ₂ ⁺ ) (SbCl ₆ ⁻ ), AgClO ₄ , H _{2 IrCl 6, La (NO 3)} 3 · 6H 2 O), O 2, O 3, (NO 2 +) (BF 4 -), FSO 2 OOSO 2 F, iron chloride (III Hexahydrate, anhydrous iron (III) chloride, iron (III) nitrate nonahydrate, anhydrous ferric nitrate, iron (III) sulfate n-hydrate (n = 3-12), iron (III) sulfate Iron (III) salts of inorganic acids such as ammonium dodecahydrate, iron (III) perchlorate n hydrate (n = 1,6), iron (III) tetrafluoroborate; copper (II) chloride Copper (II) salts of inorganic acids such as copper (II) sulfate and copper (II) tetrafluoroborate; nitrosonium tetrafluoroborate; persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; Periodate salts such as potassium iodate; Hydrogen peroxide, potassium hexacyanoferrate (III), tetraammonium cerium sulfate (IV) dihydrate; Iron of organic acids such as iron (III) p-toluenesulfonate ( III) salt; ferric organic sulfonate, And the like.
As the organic sulfonic acid of the ferric organic sulfonate, aromatic sulfonic acids such as benzene sulfonic acid or a derivative thereof, naphthalene sulfonic acid or a derivative thereof, anthraquinone sulfonic acid or a derivative thereof are preferably used.
Examples of the benzenesulfonic acid derivative in the benzenesulfonic acid or derivative thereof include toluenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, methoxybenzenesulfonic acid, ethoxybenzenesulfonic acid, Examples thereof include propoxybenzene sulfonic acid, butoxybenzene sulfonic acid, phenol sulfonic acid, cresol sulfonic acid, and benzene disulfonic acid. Examples of naphthalene sulfonic acid derivatives in naphthalene sulfonic acid or its derivatives include naphthalene disulfonic acid and naphthalene trisulfonic acid. , Methyl naphthalene sulfonic acid, ethyl naphthalene sulfonic acid, propyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, etc. It is, as the anthraquinone sulfonic acid derivatives in anthraquinone sulfonic acid or its derivatives, e.g., anthraquinone disulfonic acid, anthraquinone-trisulfonic acid. Among these aromatic sulfonic acids, toluenesulfonic acid, methoxybenzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, naphthalenetrisulfonic acid and the like are particularly preferable, and paratoluenesulfonic acid and methoxybenzenesulfonic acid are particularly preferable. .
The oxidizing agent (B) is preferably an iron salt (III) of an inorganic acid or an organic acid, or a persulfate, more preferably ammonium persulfate or iron (III) p-toluenesulfonate, and iron p-toluenesulfonate (III). Is more preferable.

  In the composition of the present invention, the content of the oxidizing agent (B) is not particularly limited as long as the mass ratio (D / B) described below is within a predetermined range, but it is 1 to It is preferable that it is 45 mass%, and it is more preferable that it is 5-30 mass%.

In addition, when the π-conjugated polymer (A) is obtained by polymerization by an oxidative polymerization method in the presence of an oxidant, and the oxidant used in the oxidative polymerization method is also used as the oxidant (B), The oxidizing agent (B) includes an oxidizing agent that has reacted during oxidative polymerization.
Therefore, when the oxidizing agent used in the oxidation polymerization method is also used as the oxidizing agent (B), the amount of the oxidizing agent (B) in the composition of the present invention is the amount of the oxidizing agent charged during the oxidation polymerization. However, when an oxidant is further added after the oxidative polymerization to obtain the composition of the present invention, the amount of the oxidant (B) in the composition of the present invention is the same as that of the oxidant charged during the oxidative polymerization and after the oxidative polymerization. Furthermore, it is the total amount with the added oxidizing agent.

<Non-conjugated polymer (C)>
The non-conjugated polymer (C) is not particularly limited as long as it is a polymer (polymer) that does not exhibit conductivity in the conjugated structure of the polymer main chain. The definition of the conjugated structure is as described above. In addition, a nonconjugated polymer (C) functions as a binder and raises the intensity | strength of the electrically conductive film obtained.
The non-conjugated polymer (C) is preferably a ring, group in which the polymer main chain is selected from an aromatic ring (carbocyclic aromatic ring, heteroaromatic ring), an ethynylene bond, an ethenylene bond, and a heteroatom having a lone pair of electrons. Or a polymer other than a polymer composed of atoms, or a polymer that includes these groups and is incorporated in isolation.
The non-conjugated polymer (C) is derived from at least one compound selected from the group consisting of vinyl compounds, (meth) acrylate compounds, carbonate compounds, ester compounds, amide compounds, imide compounds, fluorine compounds and siloxane compounds. Non-conjugated polymers containing components as repeating structures are preferred. These compounds may have a substituent (for example, the above-described substituent W).

  Specific examples of the vinyl compound include styrene, vinyl pyrrolidone, vinyl carbazole, vinyl pyridine, vinyl naphthalene, vinyl phenol, vinyl acetate, styrene sulfonic acid, vinyl arylamines such as vinyltriphenylamine, and vinyl tributylamine. And trialkylamines. In addition to these, for example, olefins having 2 to 4 carbon atoms (ethylene, propylene, butene, etc.), which are olefins corresponding to the constituent components of polyolefin, can be mentioned.

  Specific examples of (meth) acrylate compounds include unsubstituted alkyl group-containing hydrophobic acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, 2-hydroxyethyl acrylate, 1-hydroxyethyl acrylate, and 2-hydroxypropyl. Acrylate monomers such as acrylates, hydroxyl-containing acrylates such as 3-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1-hydroxybutyl acrylate, and the like And methacrylate monomers in which the acryloyl group is replaced with a methacryloyl group.

Specific examples of polycarbonates containing repeating components derived from carbonate compounds include general-purpose polycarbonates composed of bisphenol A and phosgene, Iupizeta (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), Panlite (trade name, Teijin Chemicals Ltd.) Manufactured) and the like.
Examples of the compound that can constitute the ester compound include polyalcohols, polycarboxylic acids, and hydroxy acids such as lactic acid. Specific examples of polyester include Byron (trade name, manufactured by Toyobo Co., Ltd.) and the like.
Specific examples of polyamides containing a structural component derived from an amide compound as a repeating structure include PA-100 (trade name, manufactured by T & K TOKA Corporation).
As a specific example of polyimide containing a constituent component corresponding to an imide compound as a repeating structure, Solpy 6,6-PI (trade name, manufactured by Solpy Kogyo Co., Ltd.) and the like can be given.
Specific examples of the fluorine compound include vinylidene fluoride and vinyl fluoride.
Specific examples of the polysiloxane containing a component derived from a siloxane compound as a repeating structure include polydiphenylsiloxane and polyphenylmethylsiloxane.

The non-conjugated polymer (C) preferably has an acid group. When the non-conjugated polymer (C) has an acid group, the above-described doping state of the π-conjugated polymer (A) becomes more stable.
It is not particularly restricted but includes groups, carboxyl group (-COOH), a sulfo group _(-SO 3 H), a phosphonic acid group (-PO _{(OH) 2),} and aromatic hydroxyl group (-OH). Of these, a sulfo group is preferable.

  Moreover, it is also preferable that a nonconjugated polymer (C) is the following compounds (P-1 to P-37). In P-1 to P-37, x, y, and z represent mol% of each monomer component, and Mw represents a weight average molecular weight.

  The molecular weight of the non-conjugated polymer (C) is not particularly limited, but is preferably 5000 to 300,000, and more preferably 10,000 to 150,000 in terms of weight average molecular weight (Mw).

  In the composition of the present invention, the content of the non-conjugated polymer (C) is not particularly limited, but is preferably 10 to 75% by mass, and preferably 30 to 65% by mass with respect to the total solid content in the composition. More preferably.

<Reducing agent (D)>
As described above, the reducing agent (D) serves to adjust the carrier concentration in the π-conjugated polymer (A) to an appropriate amount.
Although it does not restrict | limit especially as a reducing agent (D), As the specific example, a monocyclic aromatic compound, nitrogen-containing aromatic compound, sulfur-containing aromatic compound, aromatic vinyl polymer, aromatic amine, aliphatic amine (for example, , Alkylamine), nitro compound, thiol, metal complex salt, thiosulfate, sulfite, hyposulfite, boron compound, aluminum hydride complex, simple metal, reductase (reductase), and derivatives thereof And at least one kind of compound. More specifically, 1,1-bi-2-naphthol, 1,3-di (N-carbazol) propane (DCzPr), 1,4-di (N-carbazolyl) butane (DCzBu), 1,4- diazabicclo [2,2,2] octane, 2,3-dihydroxy-naphthol, 2,7-dihydroxy-naphthol, 2-naphthol, Cr (CN) ₆ ³⁻ , di (N-carbazolyl) methane (DCzMe), Eu ²⁺ , Fe (CN) ₆ ⁴⁻ , Fe ²⁺ , meso-2,4-di (N-carbazolyl) pentane (m-DCzPe), N, N, N ′, N′-tetramethyl-p-phenylenediamine, N, N, N ′, N′-tetramethylben Jin, N, N-diethylaniline, N, _{N-dimethylaniline, N-ethyl-carbazole (EtCz} ), Pt 2 (P 2 O 5) 4 H 8 4-, ReCl 8 2-, Tetrakis (dimethylamino) ethylene ( TDAE), trans-1,2-di (N-carbazolyl) cyclobutane (DCzCBu), anthracene, indene, oxadiazole, oxazole, kadricyclane, diazabicyclooctane, diphenylethylene, triethylamine, triphenylmethane, trimethoxybenzene, Naphthalene, norbornadiene, hydrazone, hydrazine, pyrene, phenanthrene, phenothiazine, perylene, methoxynaphthalene, sodium thiosulfate, sodium sulfite Sodium hydrogen sulfite, potassium hyposulfite, sodium borohydride, diborane, sodium cyanoborohydride, lithium triethylborohydride, lithium tri (boro-butyl) borohydride, diisobutylaluminum hydride, lithium aluminum hydride, hydrogenated Examples thereof include sodium bis (2-methoxyethoxy) aluminum, tributyltin hydride, reduced iron, and metal tin.

The reducing agent (D) is an aliphatic amine (preferably an aliphatic having two or more alkylamino groups (R ₁ R ₂ N—: R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group). An amine), a monocyclic aromatic compound (preferably a monocyclic aromatic compound having a hydroxy group), hydrazine, and a thiol (preferably a dithiol having a hydroxy group). Preferably there is.

  As another suitable aspect of a reducing agent (D), the compound represented by the following general formula (D1) is mentioned, for example.

In general formula (D1), R ¹ and R ¹ ′ each independently represents an alkyl group, and at least one of them is a secondary or tertiary alkyl group. R ² and R ² ′ each independently represent a hydrogen atom or a group that can be substituted on a benzene ring. L represents a —S— group or a —CHR ³ — group, and R ³ represents a hydrogen atom or an alkyl group. X and X ′ each independently represent a hydrogen atom or a group that can be substituted on a benzene ring.

  In the composition of the present invention, the content of the reducing agent (D) is not particularly limited as long as the mass ratio (D / B) described below is within a predetermined range, but it is 0.00% relative to the total solid content in the composition. It is preferable that it is 1-30 mass%, and it is more preferable that it is 1-15 mass%.

<Mass ratio (D / B)>
In the composition of the present invention, the mass ratio (D / B) between the content of the oxidizing agent (B) described above and the content of the reducing agent (D) described above is 0.001 to 0.5. As described above, since the mass ratio (D / B) is in a predetermined range, the carrier in the π-conjugated polymer (A) is in an appropriate amount, and as a result, the obtained conductive film is assumed to exhibit excellent temporal stability. Is done.
The mass ratio (D / B) is preferably 0.005 or more, and more preferably 0.05 or more, because the stability over time is more excellent. Further, the mass ratio (D / B) is preferably 0.3 or less, and more preferably 0.1 or less, because the electrical conductivity becomes higher.
The molar ratio (D / B) between the content of the oxidizing agent (B) described above and the content of the reducing agent (D) described above is not particularly limited, but is preferably 0.005 to 0.3, 0 More preferably, it is 0.05 to 0.1.

<Optional component>
The composition of the present invention may contain other components as long as it is not contrary to the gist of the present invention. Such components include solvents (eg, water, organic solvents), nanoconductive materials, conjugated polymer binders other than the above-described π-conjugated polymer (A), antioxidants, light stabilizers, heat stabilizers, plastics An agent or the like may be contained.
Antioxidants include Irganox 1010 (manufactured by Cigabi Nippon), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GM (Sumitomo Chemical Industries, Ltd.) Manufactured) and the like. Examples of the light-resistant stabilizer include TINUVIN 234 (manufactured by BASF), CHIMASSORB 81 (manufactured by BASF), and Siasorb UV-3853 (manufactured by Sun Chemical). IRGANOX 1726 (made by BASF) is mentioned as a heat-resistant stabilizer. Examples of the plasticizer include Adeka Sizer RS (manufactured by Adeka).

(Hydrophilic solvent (E))
The composition of the present invention preferably further contains a hydrophilic solvent (E) because the conductivity of the resulting conductive film is higher. By adding the hydrophilic solvent (E), it is presumed that the π-conjugated polymer (A) is aligned and the formation of the carrier path is promoted, and as a result, the conductivity is improved.

From the viewpoint of further promoting the alignment of the π-conjugated polymer (A), the hydrophilic solvent (E) preferably has a high boiling point (specifically, 130 ° C. or higher). By setting the hydrophilic solvent (E) to a high boiling point, it is presumed that the evaporation rate of the solvent during the film-forming drying process is moderately suppressed, and as a result, the arrangement of the π-conjugated polymer (A) is further promoted.
The upper limit of the boiling point of the hydrophilic solvent (E) is not particularly limited, but is preferably 300 ° C. or lower.

  The hydrophilic solvent (E) is not particularly limited as long as it is a hydrophilic solvent. For example, ether group-containing compounds such as tetrahydrofuran, for example, lactone group-containing compounds such as γ-butyrolactone and γ-valerolactone, such as caprolactam, N -Methylcaprolactam, N, N-dimethylacetamide, N-methylacetamide, N, N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide, N-methylpyrrolidone (NMP), N-octylpyrrolidone, Amide or lactam group-containing compounds such as pyrrolidone, for example sulfolane (tetramethylene sulfone), sulfones and sulfoxides such as dimethyl sulfoxide (DMSO), sugars or sugar derivatives such as sucrose, glucose, fructose, lactose Body, eg sugar alcohols such as sorbitol, mannitol, furan derivatives such as 2-furancarboxylic acid, 3-furancarboxylic acid, and / or dialcohols such as ethylene glycol, glycerol, diethylene glycol or triethylene glycol or Preferable examples include aliphatic ether compounds such as polyalcohol, dimethoxyethane, diethylene glycol dimethyl ether, and polyethylene glycol dialkyl ether, and phenol compounds such as dimethoxyphenol, m-cresol, o-cresol, p-cresol, phenol, and naphthol. These hydrophilic solvents may be used alone or in combination of two or more.

  In the composition of the present invention, the content of the hydrophilic solvent (E) is not particularly limited, but is preferably 10% by mass or more, and 50% by mass or more with respect to the total solid content in the composition. Is more preferable, and it is further more preferable that it is 100 mass% or more. The upper limit is not particularly limited, but is preferably 10 times (1000% by mass) or less of the total solid content.

(Nano conductive material)
The composition of the present invention may contain a nanoconductive material from the viewpoint of the electrical conductivity and physical strength of the obtained conductive film.
As said nano electroconductivity material, the carbon material (henceforth a nano carbon material) which has electroconductivity, a metal material (henceforth a nano metal material) etc. are mentioned.
The nano-conductive material is a nano-carbon material or nano-metal material, which will be described later, carbon nanotube (hereinafter also referred to as CNT), carbon nano-fiber, graphite, graphene, nano-carbon material of carbon nanoparticles, and metal nano A wire is preferable, and a carbon nanotube is particularly preferable from the viewpoint of improving conductivity and improving dispersibility in a solvent.
A nano electroconductivity material may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as a nano electroconductive material, you may use together at least 1 type of nano carbon material and nano metal material, and may use together 2 types of nano carbon materials or nano metal materials, respectively. .

(Conjugated polymer binder)
The composition of the present invention may contain a conjugated polymer binder as a conductive auxiliary agent from the viewpoint of the conductivity of the obtained conductive film.
The conjugated polymer binder is a compound having a structure in which the main chain is conjugated with a π electron or a lone pair of lone electrons, and is not particularly limited as long as it is a conjugated polymer other than the above-described π conjugated polymer (A).

  Such conjugated polymer binders include thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-arylene compounds, p-arylene vinylene compounds, p-arylene ethynylene compounds, p-full. Olenylene vinylene compound, fluorene compound, aromatic polyamine compound (also referred to as arylamine compound), polyacene compound, polyphenanthrene compound, metal phthalocyanine compound, p-xylylene compound, vinylene sulfide compound, m At least selected from the group consisting of -phenylene compounds, naphthalene vinylene compounds, p-phenylene oxide compounds, phenylene sulfide compounds, furan compounds, selenophene compounds, azo compounds and metal complex compounds. It includes conjugated polymer containing a repeating structural constituents derived from one compound.

  Among these, thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, p-phenylene ethynylene compounds, fluorene compounds, and arylamine compounds. A conjugated polymer containing a structural component derived from at least one compound selected from the group as a repeating structure is preferred.

There is no particular limitation on the substituent that each of the above compounds can have, but considering the compatibility with other components and the type of dispersion medium that can be used, the dispersibility of the conjugated polymer binder in the dispersion medium is improved. It is preferable to select and introduce those which can be obtained.
As an example of the substituent, when an organic solvent is used as a dispersion medium, in addition to a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkyl group, an alkoxyalkyleneoxy group, an alkoxyalkyleneoxyalkyl group, A crown ether group, an aryl group or the like can be preferably used. These groups may further have a substituent. The number of carbon atoms of the substituent is not particularly limited, but is preferably 1 to 12, more preferably 4 to 12, and particularly a long-chain alkyl group, alkoxy group, thioalkyl group, alkoxyalkylene having 6 to 12 carbon atoms. An oxy group and an alkoxyalkyleneoxyalkyl group are preferable.
On the other hand, when an aqueous medium is used as the dispersion medium, it is preferable to introduce a hydrophilic group such as a carboxylic acid group, a sulfonic acid group, a hydroxyl group, or a phosphoric acid group at the terminal of each monomer or the above substituent. In addition, dialkylamino group, monoalkylamino group, amino group, carboxyl group, ester group, amide group, carbamate group, nitro group, cyano group, isocyanate group, isocyano group, halogen atom, perfluoroalkyl group, perfluoro An alkoxy group or the like can be introduced as a substituent, which is preferable.
The number of substituents that can be introduced is not particularly limited, and one or more substituents can be appropriately introduced in consideration of dispersibility, compatibility, conductivity, and the like of the conjugated polymer binder.

  As the conjugated polymer binder, the “conductive polymer” described in paragraphs [0014] to [0047] of JP2012-251132A can be suitably used, and the contents thereof are preferably incorporated in the present specification. It is.

  The molecular weight of the conjugated polymer binder is preferably 3000 to 200,000, more preferably 5000 to 100,000 in terms of weight average molecular weight.

<Substituent W>
It describes about the substituent W in this specification.
Examples of the substituent W include a hydrogen atom, an alkyl group (for example, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.), a cycloalkyl group (for example, cyclopentyl, Cyclohexyl, etc.), alkenyl groups (eg, vinyl, allyl, etc.), alkynyl groups (eg, ethynyl, propargyl, etc.), aromatic hydrocarbon ring groups (also called aromatic carbocycle, aryl, etc., for example, phenyl, p-chlorophenyl, etc. , Mesityl, tolyl, xylyl, naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenylyl, etc.), aromatic heterocyclic groups (5- or 6-membered aromatic heterocyclic groups are preferred, Ring heteroatoms are Sulfur atom, nitrogen atom, oxygen atom, silicon atom, boron, selenium atom is preferable, for example, pyridyl, pyrimidinyl, furyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrazolyl, pyrazinyl, triazolyl (for example, 1,2,4-triazole-1 -Yl, 1,2,3-triazol-1-yl, etc.), oxazolyl, benzoxazolyl, thiazolyl, isoxazolyl, isothiazolyl, furazanyl, thienyl, quinolyl, benzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, indolyl, carbazolyl , Carborinyl, diazacarbazolyl (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl, pyridazinyl, triazinyl, quinazolinyl Phthalazinyl, borol, azaborine, etc.), a heterocyclic group (a non-aromatic heterocyclic group, which may be a saturated ring or an unsaturated ring, preferably a 5- or 6-membered ring, Sulfur atom, nitrogen atom, oxygen atom, silicon atom and selenium atom are preferable, for example, pyrrolidyl, imidazolidyl, morpholyl, oxazolidyl etc.), alkoxy group (for example, methoxy, ethoxy, propyloxy, pentyloxy, hexyloxy, octyloxy, Dodecyloxy etc.), cycloalkoxy groups (eg cyclopentyloxy, cyclohexyloxy etc.), aryloxy groups (eg phenoxy, naphthyloxy etc.), alkylthio groups (eg methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodo De Silthio, etc.), cycloalkylthio groups (eg, cyclopentylthio, cyclohexylthio, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl, ethyloxycarbonyl, butyloxycarbonyl, octyloxycarbonyl) , Dodecyloxycarbonyl, etc.), aryloxycarbonyl groups (eg, phenyloxycarbonyl, naphthyloxycarbonyl, etc.), sulfamoyl groups (eg, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylamino) Sulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminos Honiru, 2-pyridyl aminosulfonyl, etc.),

An acyl group (for example, acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, acryloyl, methacryloyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), an acyloxy group (for example, Acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.), amide groups (eg, methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, Cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octyl Carbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), carbamoyl groups (eg, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2 -Ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), ureido groups (eg methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, Naphthylureido, 2-pyridylaminoureido, etc.), sulfinyl groups (eg For example, methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl, etc.), alkylsulfonyl groups (for example, methylsulfonyl, ethylsulfonyl, butylsulfonyl, Cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino group (amino group, alkylamino group, alkenylamino group) , Arylamino group, heterocyclic amino group, for example, amino, ethylamino, dimethylamino, butyla Mino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc., cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl, triisopropylsilyl, triphenylsilyl) , Phenyldiethylsilyl, etc.).
Each of these groups may further have a substituent, and examples of the substituent include the above-described substituents. Examples thereof include an aralkyl group in which an alkyl group is substituted with an aryl group, and a hydroxyalkyl group in which an alkyl group is substituted with a hydroxy group. In addition, when the substituent W further has a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring.

<The manufacturing method of the composition of this invention>
The method for producing the composition of the present invention is not particularly limited. For example, it can prepare by mixing each said component. More specifically, the reaction can be performed at normal temperature and pressure using a normal mixing apparatus or the like. For example, each component may be dissolved or dispersed by stirring, shaking, kneading in a solvent. Sonication may be performed to promote dissolution and dispersion.

(Preferred embodiment)
As a suitable aspect of the manufacturing method of the composition of the present invention, for example, π-conjugated polymer (A), oxidizing agent (B), non-conjugated polymer (C), and reducing agent (D) are added to water. A method of dispersing is mentioned.
Moreover, as another suitable aspect of the manufacturing method of the composition of this invention, pi conjugated polymer (A), an oxidizing agent (B), a nonconjugated polymer (C), and a reducing agent (for example) are added to water. And a method of adding a hydrophilic solvent (E).

Moreover, as another suitable aspect of the manufacturing method of the composition of this invention, the method provided with the following oxidation polymerization process and the following mixing process is mentioned, for example.
(1) Oxidative polymerization step: a π-conjugated polymer having a repeating unit represented by the above general formula (1) by polymerizing by an oxidative polymerization method in the presence of an oxidizing agent (B) and a non-conjugated polymer (C). Step (2) for obtaining a polymer composition containing (A) (2) Mixing step: Step for obtaining a conductive composition by mixing the polymer composition and the reducing agent (D) However, the content of the oxidizing agent (B) The mass ratio (D / B) between the amount and the content of the reducing agent (D) is 0.001 to 0.5.
In addition, in the said method, an oxidizing agent (B) has a role as an oxidation polymerization agent of (pi) conjugated polymer (A), and a role as a dopant.
The mixing step is preferably a step of further mixing the hydrophilic solvent (E).

[Conductive film]
The electrically conductive film of this invention is an electrically conductive film obtained from the composition of this invention mentioned above.
Although the thickness of the electrically conductive film of this invention is not restrict | limited in particular, it is preferable that it is 0.01-100 micrometers, and it is more preferable that it is 0.02-30 micrometers. The thickness of the conductive film is obtained by measuring the thickness of the conductive film at any 10 points and arithmetically averaging them.
The carrier concentration of the conductive film of the present invention is preferably 1 × 10 ^{24 to} 3 × 10 ²⁶ / m ³ . Especially, it is preferable that it is 1 * 10 < ²⁶ > piece / m < ³ > or less, and it is more preferable that it is 5 * 10 < ²⁵ > piece / m < ³ > or less from the reason for which the temporal stability of the electrically conductive film obtained is more excellent. Among these, it is preferably 5 × 10 ²⁴ pieces / m ³ or more, more preferably 1 × 10 ²⁵ pieces / m ³ or more, because the conductivity of the obtained conductive film is higher.
In addition, in this specification, the carrier concentration (pieces / m ³ ) of the conductive film is a value measured using a Hall effect measuring device ResiTest 8300 (manufactured by Toyo Corporation).

The method for forming the conductive film of the present invention is not particularly limited. For example, the method etc. which apply | coat the composition of this invention on a board | substrate are mentioned.
The coating method is not particularly limited, and known coating methods such as spin coating, extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, ink jet printing, etc. The method can be used.
After apply | coating the composition of this invention on a board | substrate, you may provide a heating process and a drying process as needed, and may evaporate a solvent.

[Organic semiconductor devices]
The organic semiconductor device of the present invention is an organic semiconductor device using the above-described conductive film of the present invention. Examples of such an organic semiconductor device include a thermoelectric conversion element, a photoelectric conversion element, an organic thin film transistor, an organic EL, a liquid crystal display, and a solar cell.
Hereinafter, the thermoelectric conversion element of the present invention and the photoelectric conversion element of the present invention will be described.

<Thermoelectric conversion element>
If the thermoelectric conversion element of this invention is equipped with the electrically conductive film of this invention mentioned above as a thermoelectric conversion layer, the structure will not be restrict | limited in particular.
A preferable embodiment of the thermoelectric conversion element is an element including a base material (substrate) and the thermoelectric conversion layer provided on the base material, and more preferably further includes an electrode for electrically connecting them. An element, more preferably an element having a pair of electrodes provided on a substrate and the thermoelectric conversion layer between the electrodes.
In the thermoelectric conversion element of the present invention, the thermoelectric conversion layer may be one layer or two or more layers.

  Below, the whole structure of the suitable aspect of the thermoelectric conversion element of this invention is demonstrated using FIGS. 1-3 which are sectional drawings which show typically an example of the thermoelectric conversion element of this invention.

The thermoelectric conversion element 10 shown in FIG. 1 is an element that includes a first base material 11, a first electrode 12, a thermoelectric conversion layer 14, a second electrode 13, and a second base material 15 in this order. It is. The thermoelectric conversion layer 14 is the above-described conductive film of the present invention.
Here, the thermoelectric conversion element 10 shown in FIG. 1 is an aspect which obtains an electromotive force (voltage) using the temperature difference of the direction shown by the arrow.

The thermoelectric conversion element 20 shown in FIG. 2 has a first electrode 22 and a second electrode 23 on a part of the first substrate 21, and the first substrate 21 and the first electrode 22. And it is an element provided on the 2nd electrode 23 with the thermoelectric conversion layer 24 and the 2nd base material 25 in this order. The thermoelectric conversion layer 24 is the above-described conductive film of the present invention.
Here, the thermoelectric conversion element 20 shown in FIG. 2 is an aspect which obtains an electromotive force (voltage) using the temperature difference of the direction shown by the arrow.

  In the present invention, as shown in FIG. 3, the base material 31 common to the thermoelectric conversion elements 30 adjacent to each other is used, the second electrode 33 in one thermoelectric conversion element 30, and other thermoelectric conversion elements adjacent to the second electrode 33. It is good also as the module 300 which connected each thermoelectric conversion element 30 in series by electrically connecting with 30 1st electrodes 32. The thermoelectric conversion layer 34 is the above-described conductive film of the present invention.

<Photoelectric conversion element>
If the photoelectric conversion element of this invention is equipped with the electrically conductive film of this invention mentioned above as a photoelectric converting layer, a hole transport layer, or an electron carrying layer, the structure will not be restrict | limited in particular.
Below, one embodiment of the photoelectric conversion element of this invention is demonstrated using drawing.

FIG. 4 is a schematic cross-sectional view of one embodiment of the photoelectric conversion element of the present invention.
The photoelectric conversion element 110a shown in FIG. 4A includes a conductive film 111 functioning as a lower electrode, a hole transport layer 116A formed on the lower electrode 111, and a photoelectric conversion layer formed on the hole transport layer 116A. 112 and a transparent conductive film 115 functioning as an upper electrode are stacked in this order.
FIG. 4B shows a configuration example of another photoelectric conversion element. The photoelectric conversion element 110b shown in FIG. 4B has a configuration in which a hole transport layer 116A, a photoelectric conversion layer 112, an electron transport layer 116B, and an upper electrode 115 are stacked in this order on a lower electrode 111. . Note that the stacking order of the hole transport layer 116A, the photoelectric conversion layer 112, and the electron transport layer 16B in FIGS. 4A and 4B may be reversed depending on the application and characteristics.

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

<Manufacture of conductive composition>
(Example 1-1)
Monomer (1 g) that becomes a repeating unit of the following π-conjugated polymer 1 after polymerization, ammonium persulfate (1.1 g) as the oxidizing agent (B), and polystyrenesulfonic acid (3 g) as the non-conjugated polymer (C) in tetrahydrofuran (50 ml) The monomer was subjected to oxidative polymerization by stirring for 28 hours in a nitrogen atmosphere at room temperature to synthesize the following π-conjugated polymer 1. Thereafter, tetrakis (dimethylamino) ethylene (0.3 g) as a reducing agent (D) was added to the reaction solution, and the mixture was stirred at room temperature under nitrogen for 3 hours. The solvent was distilled off from the reaction solution using a rotary evaporator, and a black solid was taken out. The obtained black solid was sufficiently washed with pure water and methanol by filtration under reduced pressure in a nitrogen atmosphere. Further, sodium dodecyl sulfate (0.1 g) was added as a surfactant to the black solid after washing (4.1 g) and dispersed in 250 ml of sufficiently degassed pure water. Thereafter, dimethyl sulfoxide (7.5 ml) was added as a hydrophilic solvent (E) and stirred for 2 hours under a nitrogen atmosphere at room temperature. The following π-conjugated polymer 1, ammonium persulfate, polystyrene sulfonic acid, tetrakis (dimethylamino) ethylene and dimethyl were added. A conductive composition (a conductive composition of Example 1-1) containing sulfoxide and water was obtained.

(Examples 1-2 to 1-8, Comparative Examples 1-1 to 1-2, Examples 2-1 to 2-4, Examples 3-1 to 3-5, Comparative Examples 3-1 to 3-4 Examples 4-1 to 4-9)
Instead of the monomer that becomes the repeating unit of the π-conjugated polymer 1 after polymerization, the monomer that becomes the repeating unit of the π-conjugated polymer shown in Tables 1 to 4 below is used, and the oxidizing agent (B), the reducing agent (D), And a conductive composition (Examples 1 to 2-8, Comparative Example) according to the same procedure as Example 1-1 except that the compounds shown in Tables 1 to 4 below were used as the hydrophilic solvent (E). 1-1 to 1-2, Examples 2-1 to 2-4, Examples 3-1 to 3-5, Comparative Examples 3-1 to 3-4, Compositions of Examples 4-1 to 4-9 )
In Comparative Example 1-2, oxidative polymerization was performed without blending polystyrene sulfonic acid.
Moreover, in Examples 3-1 to 3-5 and Comparative Examples 3-2 to 3-4, the amount of the reducing agent (D) added so that the mass ratio (D / B) becomes a value shown in Table 3. Adjusted.
In Comparative Example 3-1, no reducing agent (D) was added.

<Preparation of conductive film and its evaluation>
(Preparation of conductive film)
Each conductive composition obtained was spin-coated on a glass substrate (size: 4 cm × 3 cm) cleaned with UV ozone, and then dried and annealed at 130 ° C. for 20 minutes in a nitrogen atmosphere. A conductive film was formed on a glass substrate.

(Evaluation of conductivity)
The conductivity of each obtained conductive film was evaluated. Specifically, the surface resistivity (unit: Ω / □) was measured using a “low resistivity meter: Loresta GP” (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the film thickness ( Unit: cm) was measured, and the conductivity (S / cm) was calculated from the following formula. The results are shown in Tables 1 to 4 (initial conductivity). The results were expressed as an index with the conductivity of Comparative Example 1-1 as 100. The larger the index, the higher the conductivity (initial conductivity).
In addition, about the comparative example 1-2, the obtained electrically conductive film could not be evaluated weakly.
(Conductivity) = 1 / ((Surface resistivity) × (Film thickness))

(Evaluation of stability over time of conductivity)
The number of days required for the conductivity to decrease to 80% of the initial conductivity at 40 ° C. in the atmosphere was measured. The results are shown in Tables 1 to 4 (Stability with time). Here, “> 30” indicates that the number of days exceeds 30 days. “> 60” indicates that the number of days exceeds 60 days. “> 120” indicates that the number of days exceeds 120 days. The longer the number of days, the better the temporal stability of conductivity.
In addition, about the comparative example 1-2, the obtained electrically conductive film could not be evaluated weakly.

In Tables 1 to 4, numerals 1 to 7 and 101 described in “π-conjugated polymer” represent the following π-conjugated polymers 1 to 7 and 101, respectively. In addition, Mw of each π-conjugated polymer is as follows.
Π-conjugated polymer 1: Mw = 39,000
Π-conjugated polymer 2: Mw = 83,000
Π-conjugated polymer 3: Mw = 62,000
Π-conjugated polymer 4: Mw = 28,000
Π-conjugated polymer 5: Mw = 26,000
Π-conjugated polymer 6: Mw = 105,000
Π-conjugated polymer 7: Mw = 12,000
Π-conjugated polymer 101: Mw = 50,000

  In Tables 1 to 4, “PSS” described in “Non-conjugated polymer (C)” represents polystyrene sulfonic acid.

In Tables 1 to 4, the abbreviations for “hydrophilic solvent (E)” represent the following.
DMSO: dimethyl sulfoxide EG: ethylene glycol NMP: N-methylpyrrolidone

In Tables 1 to 4, “D / B” represents the mass ratio (D / B) described above.
In Tables 1 to 4, “carrier concentration” is the carrier concentration of the conductive film. The method for measuring the carrier concentration is as described above.

As can be seen from Tables 1 to 4, the π-conjugated polymer (A) having the repeating unit represented by the general formula (1), the oxidizing agent (B), the non-conjugated polymer (C), and the reducing agent (D). All of the examples of the present application in which the mass ratio (D / B) of the content of the oxidizing agent (B) and the content of the reducing agent (D) is 0.001 to 0.5 are high in conductivity. Rate and excellent stability over time.
From the comparison of Examples 2-1 to 2-4, Examples 2-1 to 2-3 containing the hydrophilic solvent (E) showed higher conductivity. Especially, Examples 2-1 and 2-2 whose boiling point of a hydrophilic solvent (E) is 130 degreeC or more showed much higher electrical conductivity.
From the comparison of Examples 3-1 to 3-5, Examples 3-2 to 3-5 having a mass ratio (D / B) of 0.005 or more showed more excellent temporal stability. Especially, Examples 3-3 to 3-5 whose mass ratio (D / B) is 0.05 or more showed further superior temporal stability. Among them, Examples 3-3 and 3-4 having a mass ratio (D / B) of 0.3 or less showed higher conductivity. Among them, Example 3-3 having a mass ratio (D / B) of 0.1 or less showed higher conductivity.
From the comparison of Examples 4-1 to 4-9, Examples 4-1 to 4-7 using compounds other than the art complex as the reducing agent (D) showed more excellent temporal stability. Among them, Examples 4-1 to 4-6 using a compound containing no metal atom as the reducing agent (D) showed further excellent temporal stability. Among them, Examples 4-1 to 4-4 in which at least one compound selected from the group consisting of an aliphatic amine, a monocyclic aromatic compound, hydrazine, and a thiol is used as the reducing agent (D) are particularly used. Excellent stability over time.

  On the other hand, Comparative Example 1-1 containing no π-conjugated polymer (A) (containing a π-conjugated polymer other than the π-conjugated polymer (A)) was insufficient in conductivity and stability over time. Further, Comparative Example 1-2 not containing the non-conjugated polymer (C) was insufficient in strength. Further, Comparative Example 3-1, which did not contain a reducing agent (D), had insufficient stability over time. In addition, Comparative Example 3-2 containing the reducing agent (D) but having a mass ratio (D / B) of less than 0.001 also had insufficient temporal stability. Further, Comparative Example 3-3 containing a reducing agent (D) but having a mass ratio (D / B) exceeding 0.5 was insufficient in conductivity and stability over time.

<Production and evaluation of organic thermoelectric conversion element>
(Production of element)
Single-walled carbon nanotubes (4 mg) were added to each of the conductive compositions (5 g) of the examples, and ultrasonic waves were applied for 30 minutes to disperse the single-walled carbon nanotubes, thereby obtaining a composition liquid A for forming a thermoelectric conversion layer. It was. This thermoelectric conversion layer forming composition liquid A is applied to the electrode surface on a glass substrate (thickness: 0.8 mm) having gold (thickness 20 nm, width: 5 mm) on one side surface as a first electrode by screen printing. And heated at 80 ° C. for 30 minutes to remove the solvent. Then, the electrically conductive film used as the thermoelectric conversion layer with a film thickness of 2.6 micrometers and a magnitude | size of 8 mm x 8 mm was formed by making it dry under room temperature vacuum for 10 hours. Thereafter, a glass substrate (electrode thickness: 20 nm, electrode width: 5 mm, glass substrate thickness: 0.8 mm) on which gold was vapor-deposited as a second electrode was formed on the thermoelectric conversion layer. Were bonded at 80 ° C. so as to be in contact with the thermoelectric conversion layer to produce an organic thermoelectric conversion element.

(Evaluation of thermoelectromotive force)
The 1st electrode of the produced organic thermoelectric conversion element was installed on the hotplate maintained at constant temperature, and the Peltier device for temperature control was installed on the 2nd electrode. While keeping the temperature of the hot plate constant (100 ° C.), the temperature of the Peltier element was lowered to give a temperature difference of 2 ° C. between both electrodes. At this time, it was confirmed that a thermoelectromotive force (μV) was generated between both electrodes.

<Production and Evaluation of Organic Photoelectric Conversion Device>
(Production of element)
Each conductive composition of the example used as a hole transport layer was spin-coated (3000 rpm) on a glass-ITO substrate that had been cleaned and treated with UV-ozone, and heated at 140 ° C. for 30 minutes to prepare a conductive film. . Subsequently, a mixture of 10 mg poly (3-hexylthiophene) and 10 mg PC71BM ([6,6] -phenyl-C71-butyric acid methyl ester) was added to 1 mL of chlorobenzene containing 1% by mass of 1.8-diiodooctane. Dissolved in. This solution was applied onto the conductive film by spin coating (1000 rpm) and dried to prepare a photoelectric conversion layer having a thickness of 80 nm. LiF (1 nm) and aluminum (100 nm) were sequentially deposited on the photoelectric conversion layer to form an upper electrode, thereby obtaining an organic photoelectric conversion element.

(Evaluation of performance)
The performance of the produced organic photoelectric conversion element was evaluated as follows.
The obtained element was evaluated for current density-voltage (JV) characteristics using a SMU2400 type IV measuring apparatus manufactured by Keithley under a nitrogen atmosphere. Using a filtered xenon lamp light from Oriel (Oriel) manufactured solar simulator approximated to AM1.5G spectrum of 100 mW / cm ^2. It was confirmed that voltage generation and current flow were performed in the above apparatus.

10, 20, 30 Thermoelectric conversion element 11, 21 First substrate 12, 22, 32 First electrode 13, 23, 33 Second electrode 14, 24, 34, Thermoelectric conversion layer 15, 25 Second group Material 31 Base material 300 Module 110a, 110b Photoelectric conversion element 111 Lower electrode (conductive film)
112 Photoelectric conversion layer 115 Upper electrode (transparent conductive film)
116A hole transport layer 116B electron transport layer

Claims (16)

A π-conjugated polymer having a repeating unit represented by the following general formula (1), an oxidizing agent, a non-conjugated polymer, and a reducing agent;
The electrically conductive composition whose mass ratio of content of the said reducing agent with respect to content of the said oxidizing agent is 0.001-0.5.

(In the formula, A ring represents a conjugated hydrocarbon ring or a conjugated heterocyclic ring, and n represents an integer of 0 or more. X ¹ , X ² , X ³ , and X ⁴ are each independently a hetero atom or a substituent. And represents a hetero atom, —CH═CH— group, or ═CH— group, wherein R ¹ , R ² , and R ^A are each independently an aryl group, a heteroaryl group, an alkyl group, an alkoxy group, or a polyethyleneoxyether group. , An alkylthio group, a polyethyleneoxythioether group, an alkylamino group, or a polyethyleneoxyamino group, and the carbon atoms in R ¹ , R ² , and R ^A may be substituted with an oxygen atom or a sulfur atom. R ¹ , R ² , and R ^A may be linked to each other at any position, and nA, nB, and nC each independently represent an integer of 0 or more.)   The conductive composition according to claim 1, wherein the π-conjugated polymer is obtained by polymerization by an oxidative polymerization method in the presence of the oxidizing agent and the non-conjugated polymer.   The electrically conductive composition of Claim 1 or 2 whose A ring is a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a cyclopentadiene ring, or a silole ring in the said General formula (1).   The conductive composition according to any one of claims 1 to 3, wherein in the general formula (1), n is an integer of 1 to 3. In the general formula (1), X ¹ and X ³ , or X ¹ and X ⁴ are each independently a sulfur atom, an oxygen atom, or an NR group (where R is a hydrogen atom or an alkyl group). Item 5. The conductive composition according to any one of Items 1 to 4.   The conductive composition according to claim 1, wherein the non-conjugated polymer has a sulfo group.   The oxidant is at least one compound selected from the group consisting of iron (III) salts, copper (II) salts, peroxides, and peracids. The electroconductive composition as described.   The reducing agent is selected from the group consisting of monocyclic aromatic compounds, nitrogen-containing aromatic compounds, sulfur-containing aromatic compounds, aromatic vinyl polymers, aromatic amines, aliphatic amines, nitro compounds, thiols, and metal complex salts. The electrically conductive composition of any one of Claims 1-7 which is at least 1 sort (s) of compound.   Furthermore, the electroconductive composition of any one of Claims 1-8 containing a hydrophilic solvent.   The electrically conductive composition of Claim 9 whose boiling point of the said hydrophilic solvent is 130 degreeC or more.   The conductive composition according to claim 1, which is obtained by dispersing the π-conjugated polymer, the oxidizing agent, the non-conjugated polymer, and the reducing agent in water.   The conductive material according to claim 9 or 10, obtained by dispersing the π-conjugated polymer, the oxidizing agent, the non-conjugated polymer, and the reducing agent in water, and further adding the hydrophilic solvent. Sex composition.   The electrically conductive film obtained from the electrically conductive composition of any one of Claims 1-12. The electrically conductive film of Claim 13 whose carrier concentration is 1 * 10 < ²⁴ > ^-3 * 10 < ²⁶ > piece / m < ³ >.   The organic-semiconductor device using the electrically conductive film of Claim 13 or 14.   An organic-semiconductor device provided with a base material, an electrode, and the electrically conductive film of Claim 13 or 14 in this order.