TWI655254B - Conductive material and substrate - Google Patents

Abstract

An object of the present invention is to provide a conductive material that has a good film-forming property and can form a conductive film having high transparency, high conductivity, excellent flexibility, and good flatness when a film is formed.

The solution is a conductive material containing: (A) a π -conjugated polymer; and (B) one or more repeating units selected from repeating units a1 to a4 represented by the following general formula (1): And a dopant polymer having a weight average molecular weight in the range of 1,000 to 500,000, and (C) one or more salts selected from silver carboxylates, β -diketones, β -ketoester salts, and carbonates.

Description

Conductive materials and substrates

The present invention relates to a conductive material and a substrate on which a conductive film is formed.

A polymer with a conjugated double bond ( π -conjugated polymer). Although the polymer itself does not show conductivity, it is doped with a suitable anion molecule to exhibit conductivity and become a conductive polymer material (conductive Polymer composition). π -conjugated polymers are poly (acetylene), polythiophene, polyselenophene, polytellurene, polypyrrole, polyaniline and other (hetero) aromatic polymers, and mixtures thereof, etc. For heterogeneous agents, sulfonic acid-based anions are most commonly used. This is because the strong acid sulfonic acid and the π -conjugated polymer interact efficiently with each other.

The sulfonic acid-based anionic dopant is widely used as a sulfonic acid polymer such as polyvinyl sulfonic acid or polystyrene sulfonic acid (PSS) (Patent Document 1). Also, sulfonic acid polymers include vinyl perfluoroalkyl ether sulfonic acids represented by the registered trademark Nafion, which are used in fuel cell applications.

Polystyrene sulfonic acid (PSS), because sulfonic acid continuously exists in monomer units relative to the polymer main chain, so doping to π -conjugated polymers is highly efficient and can also increase doping Dispersibility of the latter π -conjugated polymer in water. This is because the hydrophilicity is maintained due to the presence of an excessive amount of sulfo groups in PSS, and the dispersibility to water is greatly improved.

Polythiophene using PSS as a dopant is expected to be used as a coating-type conductive film material instead of ITO (indium-tin oxide) because of its high conductivity and operation as an aqueous dispersion. However, as described above, PSS is a water-soluble resin and is hardly soluble in organic solvents. Therefore, although polythiophene using PSS as a dopant is also more hydrophilic, it has a low affinity for organic solvents or organic substrates, and is difficult to disperse in organic solvents and form films on organic substrates.

In addition, when polythiophene using PSS as a dopant is used in, for example, a conductive film for organic EL lighting, as described above, polythiophene using PSS as a dopant is very hydrophilic, so it is easy to leave a large amount in the conductive film. And the conductive film formed can easily absorb moisture from the external environment. As a result, there is a problem that the luminous body of the organic EL undergoes a chemical change to decrease the light emitting ability, and as time passes, moisture condenses and becomes a defect, and the life of the entire organic EL device is shortened. Further, polythiophene using PSS as a dopant has large particles in an aqueous dispersion, and has a large unevenness on the surface of the film after the film is formed. When it is used in organic EL lighting, non-luminous light called a dark spot is generated. Part of the problem.

In addition, polythiophene using PSS as a dopant has absorption in a blue region near a wavelength of 500 nm. Therefore, when this material is applied to a transparent substrate such as a transparent electrode, it will be used to make the device function. When the necessary conductivity is compensated by the solid content concentration or film thickness, there is also a problem that it affects the transmittance of the component.

Patent Document 2 proposes a conductive polymer composition formed of a conductive polymer containing a polymer selected from the group consisting of thiophene, selenophene, tellurene, pyrrole, aniline, and polycyclic aromatic compounds. A π -conjugated polymer formed by repeating units of a family compound; and a fluorinated acid polymer that can be wetted with an organic solvent and cation-neutralized by more than 50%. This document shows an aqueous dispersion of a conductive polymer by combining water, a π -conjugated polymer precursor monomer, a fluorinated acid polymer, and an oxidizing agent in an arbitrary order.

However, in such a conventional conductive polymer, particles are aggregated in a dispersion immediately after synthesis, and when an organic solvent with a high conductivity agent is added as a coating material, aggregation is further promoted and filterability is deteriorated. On the other hand, when spin coating is performed without filtration, a flat film cannot be obtained due to the influence of particle agglomerates, and as a result, there is a problem of causing poor coating.

In addition, the development of flexible devices has progressed. The current transparent conductive film suitable for hard devices is widely used ITO, but ITO is a crystalline film, and cracks will occur when it is bent. Therefore, the development of a flexible transparent conductive film that replaces ITO is an urgent task. The film using polythiophene using PSS as a dopant is a flexible and highly transparent film. However, in addition to the dark spot problem described above, it has a problem of low conductivity compared to ITO.

Patent Document 3 discloses a transparent conductive film using silver nanowires. A transparent conductive film using silver nanowires is highly conductive and highly transparent, so it is one of the candidates for a conductive film suitable for flexible devices. but Yes, only the wire part of the silver nanowire will be energized, so when it is applied to organic EL lighting, there will be a problem that only the wire part will emit light, and it will not emit light completely.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-146913

[Patent Document 2] Japanese Patent No. 5264723

[Patent Document 3] Japanese Patent Laid-Open No. 2009-224183

As mentioned above, films with high versatility using polythiophene-based conductive polymers using PSS as a dopant, such as PEDOT-PSS, have the same transparency as ITO and are more flexible than ITO. The problem of low conductivity. In addition, a polythiophene-based conductive polymer using PSS as a dopant has a problem that dark spots are generated when it is applied to organic EL lighting. On the other hand, the transparent conductive film using silver nanowires has the characteristics of transparency, high electrical conductivity, and excellent flexibility. However, when applied to organic EL lighting, only the wire portion will emit light, and there are microscopic uneven light emission. question.

The present invention has been made in view of the above-mentioned facts, and an object thereof is to provide a conductive material having a good film-forming property, and a conductive film having high transparency, high conductivity, excellent flexibility, and good flatness when formed into a film.

In order to solve the above-mentioned problems, the present invention provides a conductive material containing (A) a π-conjugated polymer and (B) containing one selected from repeating units a1 to a4 represented by the following general formula (1) Dopant polymer having the above repeating unit and having a weight average molecular weight in the range of 1,000 to 500,000, and (C) one selected from silver carboxylate, β -diketone, β -ketoester, and carbonate The above salt.

(Wherein R ¹ , R ³ , R ⁵ , and R ⁸ are each independently a hydrogen atom or a methyl group, and R ² , R ⁴ , and R ⁶ are each independently a single bond, an ester group, or may have Either an ether group, an ester group, or both of these are linear, branched, or cyclic hydrocarbon groups having 1 to 12 carbon atoms. R ⁷ is a straight chain having 1 to 4 carbon atoms, For branched alkylene groups, one or two of the hydrogen atoms in R ⁷ may be substituted by fluorine atoms. R ⁹ is a fluorine atom or a trifluoromethyl group. Z ₁ , Z ₂ , and Z ₃ are independent of each other Ground is any of a single bond, phenylene, naphthyl, ether group, and ester group, and Z ₄ is any of a single bond, ether group, and ester group. Y is an oxygen atom or an NH group, and m is 1 Integers of ~ 4. A1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, and 0 <a1 + a2 + a3 + a4 ≦ 1.0 ).

If it is such a conductive material, the film forming property is good, and when forming a film, a conductive film having high transparency, high conductivity, excellent flexibility, and good flatness can be formed.

In this case, the component (B) preferably contains a repeating unit b represented by the following general formula (2).

(Where b is 0 <b <1.0).

By including such a repeating unit b, the conductivity can be further improved.

In this case, the component (B) is preferably a block copolymer.

(B) When a component is a block copolymer, electroconductivity can be improved more.

In this case, the component (A) is preferably one or more precursors selected from the group consisting of pyrrole, thiophene, selenophene, tellurene, aniline, polycyclic aromatic compounds, and derivatives thereof. The monomer is polymerized.

If it is such a monomer, since it is easy to superpose | polymerize and stability in air, it is easy to synthesize (A) component.

In this case, the component (C) is preferably any one or more of those represented by the following formulae (3-1) to (3-3).

(In the formula, p is an integer of 1 to 6, R ¹⁰ is a hydrogen atom, a linear, branched, or cyclic p-valent hydrocarbon group having 1 to 30 carbon atoms. When R ¹⁰ is a hydrocarbon group, R ¹⁰ may have Halogen atom, nitrogen atom, hydroxyl group, ether group, ester group, amine group, amido group, urethane group, carbonate group, sulfonate group, thiol group, thioether group, carbonyl group, sulfonyl group , lactone group, the acyl group, a sulfo lactone group, a nitro group .R ^11, R ¹² having 1 to 20 carbon atoms of straight-chain, branched or cyclic alkyl group of carbon atoms of an alkenyl having 2 to 20 Group, alkynyl group having 2 to 20 carbon atoms, or aryl group having 6 to 20 carbon atoms. These R ¹¹ and R ¹² may also have a hydroxyl group, an alkoxy group, an ether group, an ester group, an amine group, and an amidino group. , Sulfonate, halogen, cyano, nitro, carbonate, urethane, thiol, thioether, thioketone, or heteroaromatic ring. R ¹³ is a hydrogen atom, Linear, branched, cyclic alkyl, or phenyl) having 1 to 8 carbon atoms).

If this is the case, a more conductive conductive film can be formed.

In this case, the conductive material is preferably one having dispersibility to water or an organic solvent.

In the present invention, the conductive material is provided. A substrate formed with a conductive film.

As described above, the conductive material of the present invention can be made into a conductive film by coating / filming a substrate or the like.

In addition, the conductive film formed in this manner is excellent in conductivity and transparency, and therefore can be used as a transparent electrode layer.

As described above, a conductive polymer obtained by forming a complex with a dopant polymer of the component (B) containing a sulfo group of a super acid and a π -conjugated polymer of the component (A) is added as The component (C) is a solution obtained from one or more salts selected from silver carboxylate, β -diketone, β -ketoester, and carbonate as the conductive material of the present invention. Good film-forming properties in spin coating. The conductive film formed by using the conductive material of the present invention is excellent in conductivity, transparency, flatness, flexibility, and durability, and has a low surface roughness. Furthermore, if it is such a conductive material, the film-forming property is good regardless of whether it is an organic substrate or an inorganic substrate.

In addition, a conductive film formed of such a conductive material is excellent in conductivity, transparency, flatness, flexibility, and the like, and therefore, it can function as a transparent electrode layer, particularly as a flexible transparent electrode.

As described above, development of a conductive film forming material that can form a conductive film having high conductivity, transparency, excellent flexibility, and good flatness. Subject to demand.

As a result of intensive studies on the above-mentioned subject, the present inventors have found that by using a dopant polymer having a repeating unit having an α-position fluorinated sulfo group Dopant polymer to replace polystyrene sulfonic acid (PSS), which is widely used as a dopant for conductive polymer materials, the superacid dopant polymer and π -conjugated polymer strongly interact with each other Effect, by shifting the visible light absorption region of the π -conjugated polymer, the transparency will be improved, and by the π -conjugated polymer and the dopant polymer being strongly ionic bonded, the light or heat Stability will improve. In addition, it was found that the film-forming property in spin coating is improved, and the flatness at the time of film formation is also good. Furthermore, it was found that a conductive material obtained by combining such a conductive polymer with one or more salts selected from silver carboxylates, β -diketones, β -ketoesters, and carbonates is more effective than conductive polymerization. In the case of a simple substance, the conductivity is higher, and a conductive film having excellent conductivity, transparency, and film flatness can be formed, and the present invention has been completed.

That is, the present invention is a conductive material containing (A) a π -conjugated polymer and (B) containing one or more repeats selected from repeating units a1 to a4 represented by the following general formula (1) unit, and a weight average molecular weight range of 1,000 to 500,000 dopant polymer, and (C) selected from the silver salts of carboxylic acids, salts beta] diketone, ketoester salt beta], more than one kind of carbonate salts .

(Wherein R ¹ , R ³ , R ⁵ , and R ⁸ are each independently a hydrogen atom or a methyl group, and R ² , R ⁴ , and R ⁶ are each independently a single bond, an ester group, or may have Either an ether group, an ester group, or both of these are linear, branched, or cyclic hydrocarbon groups having 1 to 12 carbon atoms. R ⁷ is a straight chain having 1 to 4 carbon atoms, For branched alkylene groups, one or two of the hydrogen atoms in R ⁷ may be substituted by fluorine atoms. R ⁹ is a fluorine atom or a trifluoromethyl group. Z ₁ , Z ₂ , and Z ₃ are independent of each other Ground is any of a single bond, phenylene, naphthyl, ether group, and ester group, and Z ₄ is any of a single bond, ether group, and ester group. Y is an oxygen atom or an NH group, and m is 1 Integers of ~ 4. A1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, and 0 <a1 + a2 + a3 + a4 ≦ 1.0 ).

The present invention is described in detail below, but the present invention is not limited to these.

[(A) π -conjugated polymer]

The conductive material of the present invention contains a π -conjugated polymer as the (A) component. This (A) component is only required to form a π conjugated chain (a structure in which single and double bonds alternately and continuously), and the precursor monomer (organic monomer molecule) is polymerized.

Examples of such precursor monomers include monocyclic aromatic compounds such as pyrrole, thiophene, thiophene vinyl, selenophene, tellurene, phenylene, phenylene vinyl, and aniline. Groups; polycyclic aromatics such as acene and the like; acetylenes and the like, homopolymers or copolymers of these monomers can be used as the (A) component.

Among the above monomers, from the viewpoints of ease of polymerization and stability in the air, especially pyrrole, thiophene, selenophene, tellurene, aniline, polycyclic aromatic compounds, and derivatives thereof Particularly preferred are pyrrole, thiophene, aniline, and derivatives thereof; more particularly, thiophenes are preferred because they have the highest conductivity and transparency in visible light, but are not limited to these.

The conductive material of the present invention, especially when containing polythiophene as the (A) component, has high conductivity and high transparency in visible light, so it can be extended to touch panels, organic EL displays, and organic ELs. Uses such as lighting. On the other hand, when the conductive material of the present invention contains polyaniline as the (A) component, compared with the case of containing polythiophene, the absorption of visible light is large and the conductivity is low, so it is difficult to apply it to displays. However, it is easy to spin-coat for low viscosity, so it can be considered as an electrostatic topcoat to prevent the photoresist upper film caused by electrons in EB lithography.

In addition, although the monomer constituting the π -conjugated polymer can obtain sufficient conductivity even in the unsubstituted form (A) component, in order to improve the conductivity, an alkyl group, a carboxyl group, and a sulfo group can also be used. , Alkoxy, hydroxyl, cyano, halogen atom and other substituted monomers.

Specific examples of pyrrole, thiophene, and aniline monomers Examples include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, and 3-decylpyrrole , 3-dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl-4-carboxypyrrole, 3-methyl-4-carboxyl Ethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3 -Methyl-4-hexyloxypyrrole; thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3- Octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-benzene Thiothiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyl Oxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene 3, 4-2 Methoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-bis Heptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-di-dodecyloxythiophene, 3,4-ethylenedioxythiophene, 3, 4-ethylenedithiothiophene, 3,4-propanedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxy Thiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxymethylthiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutyl Methylthiophene, 3,4- (2,2-dimethylpropanedioxy) thiophene, 3,4- (2,2-diethylpropanedioxy) thiophene, (2,3-dihydrothieno [ 3,4-b] [1,4] Dioxin-2-yl) methanol; aniline, 2-methylbenzene Amine, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2-propylaniline, 3-propylaniline, 2-butylaniline, 3-butylaniline, 2-isobutylaniline , 3-isobutylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-anilinesulfonic acid, 3-anilinesulfonic acid, and the like.

Among them, in terms of resistance value and reactivity, it is particularly selected from pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, and 3,4-ethylenedioxythiophene. One or two of the (co) polymers are more suitable for use. Further, the homopolymer made of pyrrole and 3,4-ethylenedioxythiophene has higher conductivity and is better.

Furthermore, for practical reasons, the repeating number of these repeating units (precursor monomers) in the component (A) is preferably in the range of 2 to 20, and more preferably in the range of 6 to 15.

The molecular weight of the component (A) is preferably about 130 to 5,000.

[(B) Dopant polymer]

The conductive material of the present invention contains a dopant polymer as the (B) component. The dopant polymer of the component (B) contains one or more repeating units selected from repeating units a1 to a4 represented by the following general formula (1). That is, the dopant polymer of the component (B) is a super strong acid polymer containing a fluorinated sulfonic acid.

(Wherein R ¹ , R ³ , R ⁵ , and R ⁸ are each independently a hydrogen atom or a methyl group, and R ² , R ⁴ , and R ⁶ are each independently a single bond, an ester group, or may have Either an ether group, an ester group, or both of these are linear, branched, or cyclic hydrocarbon groups having 1 to 12 carbon atoms. R ⁷ is a straight chain having 1 to 4 carbon atoms, For branched alkylene groups, one or two of the hydrogen atoms in R ⁷ may be substituted by fluorine atoms. R ⁹ is a fluorine atom or a trifluoromethyl group. Z ₁ , Z ₂ , and Z ₃ are independent of each other Ground is any of a single bond, phenylene, naphthyl, ether group, and ester group, and Z ₄ is any of a single bond, ether group, and ester group. Y is an oxygen atom or an NH group, and m is 1 Integers of ~ 4. A1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, and 0 <a1 + a2 + a3 + a4 ≦ 1.0 ).

Specific examples of the monomer to which the repeating unit a1 is given include the following.

(In the formula, R ¹ is the same as described above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine, or fluorene).

Specific examples of the monomer imparted to the repeating unit a2 include the following.

(In the formula, R ³ is the same as described above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine, or fluorene).

Specific examples of the monomer imparted to the repeating unit a3 include the following.

(In the formula, R ⁵ is the same as described above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine, or fluorene).

Specific examples of the monomer imparted to the repeating unit a4 include the following.

(In the formula, R ⁸ is the same as described above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine, or fluorene).

If it is such a (B) component, the filterability and film-forming property of a material, affinity with an organic solvent and a substrate will improve, and the transmittance | permeability after film-forming will increase.

The component (B) is preferably one which further contains a repeating unit b represented by the following general formula (2). By including such a repeating unit b, the conductivity can be further improved.

(Where b is 0 <b <1.0).

Specific examples of the monomer imparted to the repeating unit b include the following.

(In the formula, X ₂ is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine, or fluorene).

When X and X ₂ are amines, (P1a-3) described in paragraph [0048] of Japanese Patent Application Laid-Open No. 2013-228447 can be cited as an example.

Here, as described above, a1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, and 0 <a1 + a2 + a3 + a4 ≦ 1.0, preferably 0.2 ≦ a1 + a2 + a3 + a4 ≦ 1.0. If 0 <a1 + a2 + a3 + a4 ≦ 1.0 (that is, if any one of the repeating units a1 to a4 is contained), the effect of the present invention can be obtained. If 0.2 ≦ a1 + a2 + a3 + a4 ≦ 1.0, you can get better results.

When the repeating unit b is included, from the viewpoint of improving the conductivity, It is preferably 0.3 ≦ b <1.0, and more preferably 0.3 ≦ b ≦ 0.8.

Further, the ratio of the repeating unit a1 + a2 + a3 + a4 to the repeating unit b is preferably 0.2 ≦ a1 + a2 + a3 + a4 ≦ 0.7 and 0.3 ≦ b ≦ 0.8, and more preferably 0.3 ≦ a1 + a2 + a3 + a4 ≦ 0.6 and 0.4 ≦ b ≦ 0.7.

The dopant polymer of the component (B) may have a repeating unit c other than repeating units a1 to a4 and repeating unit b. Examples of the repeating unit c include styrene-based, vinylnaphthalene-based, and ethylene-based polymers. Silane, pinene, indene, vinylcarbazole, etc.

Specific examples of the monomer imparted to the repeating unit c include the following.

Among the monomers provided with the repeating unit c, when a monomer containing fluorine is copolymerized, the conductivity is reduced, but the transparency is improved, the efficiency of hole injection is increased, and the life is increased.

The method of synthesizing the dopant polymer of the component (B) includes, for example, adding a desired monomer among the monomers to which the repeating units a1 to a4, b, and c are given, and adding a radical to an organic solvent. A method of polymerizing an initiator to perform heat polymerization to obtain a dopant polymer of a (co) polymer.

Examples of the organic solvent used in the polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone, and γ-butyrolactone.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), and dimethyl 2,2 '-Azobis (2-methylpropionate), benzamidine peroxide, lauryl peroxide, and the like.

The reaction temperature is preferably 50 to 80 ° C, and the reaction time is preferably 2 to 100 hours, and more preferably 5 to 20 hours.

In the dopant polymer of the component (B), the repeating units a1 to a4 may be provided in one kind or two or more kinds. In order to improve the polymerizability, a combination of a methacrylic type and a styrene type is preferred. monomer.

When two or more kinds of monomers that provide repeating units a1 to a4 are used, the respective monomers may be copolymerized randomly or may be copolymerized in blocks. When used as a block copolymer polymer (block copolymer), an island structure is formed by aggregating repeating portions formed by two or more repeating units a1 to a4, and specificity is generated around the dopant polymer. The advantages of the structure and improved conductivity are expected.

In addition, the monomers that give repeating units a1 to a4, b, and c may follow It is possible to copolymerize organically, or to copolymerize each as a block. At this time, as in the case of the above-mentioned repeating units a1 to a4, as a block copolymer, the advantage of improving conductivity is expected.

When random copolymerization is performed by radical polymerization, generally speaking, a method in which a monomer or a radical polymerization initiator to be copolymerized is mixed and heated to perform polymerization. In the presence of a first monomer and a radical polymerization initiator, polymerization is started, and when a second monomer is added thereafter, one side of the polymer molecule is a structure in which the first monomer is polymerized, and the other is a first polymer. 2 The structure of monomer polymerization. However, in this case, the repeating unit of the first monomer and the second monomer is mixed in the middle portion, which is different from the form of the block copolymer. To form a block copolymer by radical polymerization, living radical polymerization is preferably used.

An active radical polymerization method called RAFT polymerization (Reversible Addition Fragmentation chain Transfer polymerization). The free radicals at the ends of the polymer are often active. Therefore, by starting the polymerization with the first monomer, a second monomer is added at the stage where it is consumed. It can form a diblock copolymer composed of a block of repeating units of the first monomer and a block of repeating units of the second monomer. In addition, when the polymerization is started with the first monomer, and the second monomer is added at the stage where it is consumed, and then the third monomer is added, a triblock copolymer can also be formed.

After RAFT polymerization, it has the characteristics of forming a narrow-dispersed polymer with a narrow molecular weight distribution (dispersion degree). In particular, when a monomer is added at a time for RAFT polymerization, a polymer with a narrower molecular weight distribution can be formed.

Furthermore, in the dopant polymer of the component (B), the narrow molecular weight distribution (Mw / Mn) is preferably a narrow dispersion of 1.0 to 2.0, particularly preferably 1.0 to 1.5. With a narrow dispersion, it is possible to prevent the transmittance of a conductive film formed by using a conductive material thereof from being lowered.

For RAFT polymerization, a chain transfer agent is necessary, and specifically, 2-cyano-2-propyl thiobenzoate, 4-cyano-4-thiobenzylvaleric acid, and trithio 2-cyano-2-propyldodecyl carbonate, 4-cyano-4-[(dodecylhydrothiothiocarbonyl) hydrothio] pentanoic acid, 2- (dodecyltricarbonate Thiocarbonate) -2-methylpropionic acid, cyanomethyldodecyl thiocarbonate, cyanomethylmethyl (phenyl) thiocarbamate, bis (thiobenzoate) (Fluorenyl) disulfide, bis (dodecylhydrothiothiocarbonyl) disulfide. Among these, 2-cyano-2-propyl thiobenzoate is particularly preferred.

The ratio of repeating units a1 to a4, b, c is preferably 0 <a1 + a2 + a3 + a4 ≦ 1.0, 0 <b <1.0, 0 ≦ c <1.0; more preferably 0.1 ≦ a1 + a2 + a3 + a4 ≦ 0.9, 0.1 ≦ b ≦ 0.9, 0 ≦ c ≦ 0.8; and more preferably 0.2 ≦ a1 + a2 + a3 + a4 ≦ 0.8, 0.2 ≦ b ≦ 0.8, and 0 ≦ c ≦ 0.5.

Furthermore, it is preferable that a1 + a2 + a3 + a4 + b + c = 1.

(B) A dopant polymer having a weight average molecular weight in the range of 1,000 to 500,000, and preferably in the range of 2,000 to 200,000. When the weight-average molecular weight is less than 1,000, it becomes a person with poor heat resistance, and the homogeneity of the composite solution with the component (A) deteriorates. On the other hand, when the weight-average molecular weight exceeds 500,000, the conductivity is deteriorated, the viscosity is increased, the workability is deteriorated, and the dispersibility to water or organic solvents is reduced. low.

The weight-average molecular weight (Mw) is determined by gel permeation chromatography (GPC) using water, dimethylformamide (DMF), and tetrahydrofuran (THF) as solvents. Measured in terms of ethylene glycol or polystyrene.

In addition, as the monomer constituting the dopant polymer of the component (B), a monomer having a sulfo group may be used, but lithium salts, sodium salts, potassium salts, ammonium salts, and sulfonium salts of the sulfo group may also be used as the monomers. The polymer is subjected to polymerization reaction, and is converted to a sulfo group using an ion exchange resin after polymerization.

[(C) Silver carboxylate, β -diketone, β -ketoester, carbonate]

The conductive material of the present invention contains, as component (C), one or more salts (hereinafter also referred to as silver salts) selected from silver carboxylates, β -diketones, β -ketoesters, and carbonates. . In particular, as the (C) component, any one or more of the following formulae (3-1) to (3-3) are preferred.

(In the formula, p is an integer of 1 to 6, R ¹⁰ is a hydrogen atom, a linear, branched, or cyclic p-valent hydrocarbon group having 1 to 30 carbon atoms. When R ¹⁰ is a hydrocarbon group, R ¹⁰ may have Halogen atom, nitrogen atom, hydroxyl group, ether group, ester group, amine group, amido group, urethane group, carbonate group, sulfonate group, thiol group, thioether group, carbonyl group, sulfonyl group , lactone group, the acyl group, a sulfo lactone group, a nitro group .R ^11, R ¹² having 1 to 20 carbon atoms of straight-chain, branched or cyclic alkyl group of carbon atoms of an alkenyl having 2 to 20 Group, alkynyl group having 2 to 20 carbon atoms, or aryl group having 6 to 20 carbon atoms. These R ¹¹ and R ¹² may also have a hydroxyl group, an alkoxy group, an ether group, an ester group, an amine group, and an amidino group. , Sulfonate, halogen, cyano, nitro, carbonate, urethane, thiol, thioether, thioketone, or heteroaromatic ring. R ¹³ is a hydrogen atom, Linear, branched, cyclic alkyl, or phenyl) having 1 to 8 carbon atoms).

When in the above formula (3-1), R ¹⁰ represents a monovalent hydrocarbon group, R ¹⁰ represents a carbon-based number of 1 to 30 linear, branched, or cyclic alkyl group of; linear carbon atoms of 2 to 30 , Branched, or cyclic alkenyl; linear, branched, or cyclic alkynyl having 2 to 30 carbons; or aryl having 6 to 30 carbons.

Specific examples of the carboxylic acid ion used to form the carboxylic acid salt of silver represented by the above formula (3-1) or (3-3) include the following. Among these carboxylic acid ions, the larger the carbon number, the easier it is to dissolve in an organic solvent.

Among the β -dione salts and β -ketoester salts of silver described above, β -diones and β -ketoesters are complexed with silver by enolization. For example, acetoacetone, which is one of the β diones, is enolized as shown below to form a complex with silver.

Β-diones represented by the above formula (3-2) (i.e., Substituted, non-substituted acetoacetones) or β-ketoesters, specifically, the following can be exemplified.

In the present invention, as the component (C), a carbonate of silver can also be suitably used.

In addition, the carboxylate, β -diketone, β -ketoester, and carbonate of the above silver may also be hydrates.

The content of the component (C) is preferably 0.1 to 200 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B). The amount is preferably 0.5 to 100 parts by mass, and even more preferably 1 to 50 parts by mass.

The composite of polythiophene and polystyrene sulfonic acid (PEDOT-PSS) is in the shape of particles. As a result of X-ray analysis, the polythiophene showing conductivity is crystallized, and its surroundings are covered with polystyrene sulfonic acid. The form. The polystyrene sulfonic acid forms a localized charge of the double bond of the polythiophene, thereby increasing the conductivity. Polystyrenesulfonic acid has a function as a dopant for improving the conductivity of polythiophene, and a function of improving the dispersibility to water by coating an insoluble polythiophene. However, polystyrenesulfonic acid is an insulator. Although the polythiophene portion in the particles is highly conductive, when the periphery is covered with a polystyrenesulfonic acid shell of an insulator, the conductivity is low.

When a small amount of a solvent such as ethylene glycol, diethylene glycol, or DMSO is added to the aqueous dispersion of PEDOT-PSS, the conductivity is improved. If it is explained, this is because the shell of the polystyrene sulfonic acid is broken by the addition of the aforementioned solvent, and the electrons of the polythiophene particles are exchanged.

When a salt of silver is added as in the present invention, the (B) component of the super acid and the silver form a salt. This is because when a positively charged metal forms a salt with a more negatively charged super acid, it is more stable in energy. The component (B) is an insulator on the outside of the coated thiophene particles, but since a highly conductive silver salt is adhered to the outside, electron movement between the particles becomes active and the conductivity is improved.

[Other ingredients] (Surfactant)

In the present invention, a surfactant may be added in order to improve the wettability of a substrate such as a substrate. Examples of such a surfactant include nonionic, cationic, and anionic surfactants. Specific examples include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylate, sorbitan ester, and polyoxyethylene sorbitan ester. ; Cationic surfactants such as alkyltrimethylammonium chloride, alkylbenzylammonium chloride, etc .; alkyl or alkylallyl sulfate, alkyl or alkylallyl sulfonate, dioxane Anionic surfactants such as sulfosuccinate; zwitterionic surfactants such as amino acid type and betaine type; acetylene alcohol type surfactants; hydroxyl groups are alkylated with polyethylene oxide or polypropylene oxide The obtained ethynyl surfactant and the like.

(Highly conductive agent)

In the present invention, it is also possible to add an organic solvent as a highly conductive agent different from the main solvent for the purpose of improving the conductivity of the conductive material. Examples of such additional solvents include polar solvents, and specific examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dimethylsulfinium (DMSO), and dimethylformamide ( DMF), N-methyl-2-pyrrolidone (NMP), cyclobutane, ethyl carbonate and mixtures thereof. The addition amount is preferably 1.0 to 30.0% by mass, and particularly preferably 3.0 to 10.0% by mass.

(Neutralizing agent)

In the present invention, the pH of the conductive material in the aqueous solution is acidic. It is also possible to add JP 2006-96975 for the purpose of neutralization The nitrogen-containing aromatic cyclic compounds described in paragraphs [0033] to [0045] in the gazette, and the cations described in paragraph [0127] described in Japanese Patent No. 5264723, control the pH to neutral. By making the pH of the solution near neutral, it is possible to prevent the generation of rust when applied to a printing machine.

[Conductive material]

The conductive material of the present invention is one containing the π -conjugated polymer of the component (A), the dopant polymer of the component (B), and the silver salt of the component (C), The dopant polymer forms a complex by a π -conjugated polymer coordinated with the component (A).

The conductive material of the present invention is preferably one having dispersibility to water or an organic solvent. For inorganic or organic substrates (substrates having an inorganic film or an organic film formed on the substrate surface), spin-coating or film-forming properties can be achieved. The flatness becomes good.

(Manufacturing method of conductive material)

The method for producing the conductive material (solution) of the present invention is not particularly limited. For example, the conductive polymerization of the π -conjugated polymer containing the component (A) and the dopant polymer containing the component (B) It is produced by adding a silver salt of the component (C) to a complex (solution).

The composite of component (A) and component (B) can be obtained by, for example, adding a monomer (compared to component A) as a raw material for component (A) by adding an aqueous solution of component (B) or a water / organic solvent mixed solution of component (B). Preferably pyrrole, thiophene, aniline, or derivatives thereof), adding an oxidizing agent and It can be obtained by oxidative polymerization according to the oxidative catalyst.

As the oxidant and oxidation catalyst, peroxodisulfate (persulfate) such as ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate), potassium peroxodisulfate (potassium persulfate) and the like can be used. Salt); transition metal compounds such as iron (III) chloride, iron (III) sulfate, copper (II) chloride; metal oxides such as silver oxide and cesium oxide; peroxides such as hydrogen peroxide and ozone; Organic peroxides such as benzamyl peroxide; oxygen.

The reaction solvent used in the oxidative polymerization may be water or a mixed solvent of water and a solvent. The solvent used here is preferably a solvent that can be mixed with water and can dissolve or disperse the components (A) and (B). Examples include N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfinium, and hexamethylphosphoniumtrifluoride. Polar solvents such as amines; alcohols such as methanol, ethanol, propanol, butanol; ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, D-glucose, D -Glycol alcohol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, etc. Alcohols; carbonate compounds such as ethylene carbonate and propylene carbonate; cyclic ether compounds such as dioxane and tetrahydrofuran; dialkyl ethers, ethylene glycol monoalkyl ethers, and ethylene glycol dialkyl ethers Chain ethers such as propylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether; heterocyclic rings such as 3-methyl-2-oxazolidinone Compounds; nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, and the like. These solvents may be used alone or as a mixture of two or more. The blending amount of these water-miscible solvents is preferably 50% of the total reaction solvent. Amount% or less.

In addition to the dopant polymer of the component (B), an anion which can be doped to the π -conjugated polymer of the component (A) may be used in combination. As such an anion, an organic acid is preferred from the viewpoint of adjusting the doping characteristics of the π -conjugated polymer, the dispersibility of the conductive material, heat resistance, and environmental resistance characteristics. Examples of the organic acid include organic carboxylic acids, phenols, and organic sulfonic acids.

Organic carboxylic acids can be used for aliphatic, aromatic, cyclic aliphatic, and the like containing one or more carboxyl groups. Examples include formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid. , Trifluoroacetic acid, nitroacetic acid, triphenylacetic acid, etc.

Examples of the phenols include phenols such as cresol, phenol, and xylenol.

Organic sulfonic acid can be used for those containing one or more sulfonic acid groups in aliphatic, aromatic, cyclic aliphatic, etc. Examples of those containing one sulfonic acid group include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, and 1-octane. Alkanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecansulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2 -Naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 3-aminopropanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, p -Toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid Acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, ten Monoalkylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, cetylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4 -Aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1 -Sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene- 1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-acetamidin-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzene Sulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8 -A sulfonic acid group-containing sulfonic acid compound such as chloronaphthalene-1-sulfonic acid, a naphthalenesulfonic acid formaldehyde liquid polycondensate, a melaminesulfonic acid formaldehyde liquid polycondensate, and the like.

Examples of those containing two or more sulfonic acid groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, m-benzenedisulfonic acid, and o-benzenedisulfonic acid. Acid, p-benzene disulfonic acid, toluene disulfonic acid, xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid Acid, diethylbenzenedisulfonic acid, dibutylbenzenedisulfonic acid, naphthalenedisulfonic acid, methylnaphthalenedisulfonic acid, ethylnaphthalenedisulfonic acid, dodecylnaphthalenedisulfonic acid, pentadecyl Naphthalene disulfonic acid, butyl naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalene Disulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, anthracene disulfonic acid, butyl anthracene disulfonic acid, 4-acetamidin-4'-isothiocyanatostilbene -2,2'-disulfonic acid, 4-acetamidamine-4'-maleimidoimidostilbene-2,2'-disulfonic acid, 1-ethoxyfluorenyl-3,6, 8-trisulfone Acid, 7-amino-1,3,6-naphthalenetrisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, 3-amino-1,5,7-naphthalenetrisulfonic acid, etc. .

The anions other than the component (B) may be added to the solution containing the raw material monomer of the component (A), the component (B), the oxidizing agent and / or the oxidative polymerization catalyst before the polymerization of the component (A). It can be added to a conductive polymer composite (solution) containing the (A) component and (B) component after polymerization.

The composite of the component (A) and the component (B) obtained in this way can be finely granulated with a homogenizer, a ball mill, or the like, as needed, and used.

It is preferable to use a mixing and dispersing machine capable of imparting high shearing force to the fine granulation. Examples of the mixing and dispersing machine include a homogenizer, a high-pressure homogenizer, and a bead mill. Among them, a high-pressure homogenizer is particularly preferred.

Specific examples of the high-pressure homogenizer include NanoVater manufactured by Yoshida Machinery Industrial Corporation, Microfluidizer manufactured by Powrex Corporation, and Ultimizer manufactured by SUGINO MACHINE Corporation.

Examples of the dispersion treatment using a high-pressure homogenizer include a treatment in which the composite solution before the dispersion treatment is subjected to high-pressure confrontation, and a treatment in which the pressure is passed through a nozzle or a slit.

Before or after fine granulation, impurities can also be removed by filtration, ultrafiltration, dialysis, etc., and refined with cation exchange resin, anion exchange resin, clamp resin, and the like.

The total content of the component (A) and the component (B) in the conductive material solution is preferably 0.05 to 5.0% by mass. If the total content of (A) component and (B) component is 0.05% by mass or more, it can be obtained When the conductivity is sufficient to be 5.0% by mass or less, a uniform conductive coating film can be easily obtained.

The content of the component (B) is preferably an amount in the range of 0.1 to 10 mol, and more preferably 1 to 7 mol, relative to 1 mol of the (A) component. The amount of the range. When the sulfo group in the component (B) is 0.1 mol or more, the doping effect on the component (A) is high, and sufficient conductivity can be secured. In addition, if the sulfo group in the component (B) is 10 mol or less, the content of the component (A) will also be moderate, and sufficient conductivity can be obtained.

If it is the conductive material of the present invention as described above, the filterability and the film-forming property by spin coating are good, and a conductive film having high transparency and low surface roughness can be formed.

[Conductive film]

The conductive material (solution) obtained as described above can be formed as a conductive film by being applied to a processing object such as a substrate. Examples of the method for applying the conductive material (solution) include coating by a spin coater, bar coater, dipping, corner wheel coating, spray coating, roll coating, and screen printing. , Flexographic printing, gravure printing, inkjet printing, etc. After coating, a conductive film can be formed by performing a hot-air circulating furnace, heat treatment with a hot plate, or IR, UV irradiation, or the like.

As described above, the conductive material of the present invention can be made into a conductive film by coating / filming a substrate or the like. In addition, the conductive film formed in this manner is excellent in conductivity and transparency, and thus can be used as a transparent electrode layer. And those who function. Furthermore, the conductive material of the present invention also functions as a hole injection layer. The conductive material of the present invention is coated on a transparent conductive film such as ITO, silver nanowire, silver wiring, etc. as a hole injection layer, and a hole transport layer, a light emitting layer, and an electron injection layer are formed thereon. ,cathode. When applied as a hole injection layer, high conductivity is not necessarily required.

The ITO system produced by sputtering or the like is used as a transparent electrode. However, since it is a crystalline film, when it is bent, the crystal disintegrates, which reduces the conductivity and breaks. Therefore, it is difficult to apply ITO to a flexible device. On the other hand, the conductive film based on the conductive material of the present invention does not break or reduce conductivity even if it is bent, so it can be used as a conductive film for flexible devices.

[Substrate]

The present invention also provides a substrate on which a conductive film is formed from the conductive material of the present invention described above.

Examples of the substrate include glass substrates, quartz substrates, blank photomask substrates, resin substrates, compound semiconductor wafers such as silicon wafers, gallium arsenic wafers, indium phosphorus wafers, and flexible substrates. Moreover, it can also be used as an antistatic overcoat layer by coating on a photoresist film.

As described above, if it is a complex of a dopant polymer containing (B) component containing a sulfo group containing a super acid, a π -conjugated polymer of component (A), and a silver salt of component (C) The conductive material of the present invention has good filterability and film-forming property by spin coating, and when formed into a film, it can form transparency, flexibility, flatness, durability, and good conductivity, and its surface is rough. Low degree of conductive film. Moreover, if it is such a conductive material, it is a film with good film-forming property regardless of an organic substrate and an inorganic substrate.

In addition, a conductive film formed of such a conductive material is excellent in conductivity, transparency, and the like, and therefore, it can function as a transparent electrode layer.

[Example]

Hereinafter, the present invention will be specifically described using synthesis examples, preparation examples, comparative preparation examples, examples, and comparative examples, but the present invention is not limited to these.

[Synthesis of Dopant Polymer] (Synthesis examples 1 to 9)

Under a nitrogen environment, a solution of each monomer and 2,2'-azobis (isobutyric acid) dimethyl in methanol stirred at 64 ° C was stirred for 8 hours, and then cooled to room temperature while vigorously Ethyl acetate was added dropwise while stirring. The generated solid was obtained by filtration, and dried under vacuum at 50 ° C for 15 hours. The obtained white polymer was dissolved in pure water, and the cations of the monomers were exchanged for hydrogen atoms with an ion exchange resin to be converted into sulfo groups.

In this way, the dopant polymers 1 to 9 shown below were synthesized.

Dopant polymer 1

Weight average molecular weight (Mw) = 29,900

Molecular weight distribution (Mw / Mn) = 1.91

Dopant polymer 2

Weight average molecular weight (Mw) = 31,000

Molecular weight distribution (Mw / Mn) = 1.89

Dopant polymer 3

Weight average molecular weight (Mw) = 24,000

Molecular weight distribution (Mw / Mn) = 1.76

Dopant polymer 4

Weight average molecular weight (Mw) = 39,300

Molecular weight distribution (Mw / Mn) = 1.91

Dopant polymer 5

Weight average molecular weight (Mw) = 41,100

Molecular weight distribution (Mw / Mn) = 1.98

Dopant polymer 6

Weight average molecular weight (Mw) = 53,000

Molecular weight distribution (Mw / Mn) = 1.81

Dopant polymer 7

Weight average molecular weight (Mw) = 52,000

Molecular weight distribution (Mw / Mn) = 1.79

Dopant polymer 8

Weight average molecular weight (Mw) = 21,000

Molecular weight distribution (Mw / Mn) = 1.30

Dopant polymer 9

Weight average molecular weight (Mw) = 41,100

Molecular weight distribution (Mw / Mn) = 1.79

[Preparation of conductive polymer composite dispersion] (Preparation Example 1)

A solution obtained by dissolving 3.82 g of 3,4-ethylenedioxythiophene and 12.5 g of dopant polymer 1 in 1,000 mL of ultrapure water was mixed at 30 ° C.

While maintaining the mixed solution thus obtained at 30 ° C, while stirring, slowly add an oxidation catalyst solution of 8.40 g of sodium persulfate and 2.3 g of iron (III) sulfate dissolved in 100 mL of ultrapure water, and stir for 4 hours to make Its response.

1,000 mL of ultrapure water was added to the obtained reaction solution, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment solution subjected to the above-mentioned filtration treatment, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of ions were added thereto. Water was exchanged and about 2,000 mL of liquid was removed using ultrafiltration. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment solution, and about 2,000 mL of the treatment solution was removed using an ultrafiltration method. This operation was repeated 5 times, and filtration was performed using a regenerated cellulose filter (manufactured by ADVANTEC) having a pore diameter of 0.45 μm to obtain 1.3% by mass of a blue conductive polymer composite dispersion liquid 1.

The ultrafiltration conditions are as follows.

Differential molecular weight of ultrafiltration membrane: 30K

Cross flow

Supply liquid flow rate: 3,000mL / min

Membrane partial pressure: 0.12Pa

Moreover, in other preparation examples, ultrafiltration was performed under the same conditions.

(Preparation example 2)

In addition to changing 12.5g of dopant polymer 1 to 10.0g of dopant polymer 2, changing the amount of 3,4-ethylenedioxythiophene to 2.41g, and the amount of sodium persulfate A conductive polymer composite dispersion liquid 2 was prepared in the same manner as in Preparation Example 1 except that the content was changed to 5.31 g and the blending amount of iron (III) sulfate was changed to 1.50 g.

(Preparation Example 3)

In addition to changing 12.5 g of dopant polymer 1 to 12.0 g of dopant polymer 3, changing the blending amount of 3,4-ethylenedioxythiophene to 2.72 g, and blending amount of sodium persulfate The conductive polymer composite dispersion liquid 3 was prepared in the same manner as in Preparation Example 1 except that the content was changed to 6.00 g and the blending amount of iron (III) sulfate was changed to 1.60 g.

(Preparation Example 4)

In addition to changing 12.5g of dopant polymer 1 to 11.8g of dopant polymer 4, 8.40g of sodium persulfate to 4.50g of ammonium persulfate, and 3,4-ethylenedioxythiophene Except that the blending amount was changed to 2.04 g, and the blending amount of iron (III) sulfate was changed to 1.23 g, it was the same as that in Preparation Example 1. In the same manner, a conductive polymer composite dispersion liquid 4 was prepared.

(Preparation Example 5)

In addition to changing 12.5 g of dopant polymer 1 to 11.0 g of dopant polymer 5, changing 8.40 g of sodium persulfate to 5.31 g of ammonium persulfate, and changing Except that the blending amount was changed to 2.41 g and the blending amount of iron (III) sulfate was changed to 1.50 g, it was prepared in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion liquid 5.

(Preparation Example 6)

In addition to changing 12.5g of dopant polymer 1 to 13.0g of dopant polymer 6, 8.40g of sodium persulfate to 5.31g of ammonium persulfate, and 3,4-ethylenedioxythiophene Except that the blending amount was changed to 2.41 g, and the blending amount of iron (III) sulfate was changed to 1.50 g, it was prepared in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion liquid 6.

(Preparation Example 7)

In addition to changing 12.5g of dopant polymer 1 to 12.8g of dopant polymer 7, 8.40g of sodium persulfate to 5.31g of ammonium persulfate, and 3,4-ethylenedioxythiophene Except that the blending amount was changed to 2.41 g, and the blending amount of iron (III) sulfate was changed to 1.50 g, it was prepared in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion liquid 7.

(Preparation Example 8)

In addition to changing 12.5g of dopant polymer 1 to 11.0g of dopant polymer 8, changing 8.40g of sodium persulfate to 5.31g of ammonium persulfate, and 3,4-ethylenedioxythiophene Except that the blending amount was changed to 2.41 g, and the blending amount of iron (III) sulfate was changed to 1.50 g, it was prepared in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion liquid 8.

(Preparation Example 9)

A solution obtained by dissolving 3.87 g of 3,4-dimethoxythiophene and 10.0 g of the dopant polymer 2 in 1,000 mL of ultrapure water was mixed at 30 ° C.

While maintaining the mixed solution thus obtained at 30 ° C, while stirring, slowly add an oxidation catalyst solution of 8.40 g of sodium persulfate and 2.3 g of iron (III) sulfate dissolved in 100 mL of ultrapure water, and stir for 4 hours to make Its response.

1,000 mL of ultrapure water was added to the obtained reaction solution, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment solution subjected to the above-mentioned filtration treatment, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of ions were added thereto. Water was exchanged and about 2,000 mL of liquid was removed using ultrafiltration. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained processing solution, and about 2,000 mL of the processing solution was removed using an ultrafiltration method. This operation was repeated 5 times, and filtration was performed using a regenerated cellulose filter (manufactured by ADVANTEC) having a pore diameter of 0.45 μm to obtain 1.3% by mass of a blue conductive polymer composite dispersion liquid 9.

(Preparation Example 10)

In addition to changing 12.5g of dopant polymer 1 to 9.0g of dopant polymer 9, changing the blending amount of 3,4-ethylenedioxythiophene to 2.41g, and the blending amount of sodium persulfate The conductive polymer composite dispersion liquid 10 was prepared in the same manner as in Preparation Example 1 except that the content was changed to 5.31 g and the blending amount of iron (III) sulfate was changed to 1.50 g.

(Preparation Example 11)

Mix 4.62 g of (2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-yl) methanol at 30 ° C and dissolve 10.0 g of dopant polymer 2 in 1,000 A solution of mL of ultrapure water.

While maintaining the mixed solution thus obtained at 30 ° C, while stirring, slowly add an oxidation catalyst solution of 8.40 g of sodium persulfate and 2.3 g of iron (III) sulfate dissolved in 100 mL of ultrapure water, and stir for 4 hours to make Its response.

1,000 mL of ultrapure water was added to the obtained reaction solution, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment solution subjected to the above-mentioned filtration treatment, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of ions were added thereto. Water was exchanged and about 2,000 mL of liquid was removed using ultrafiltration. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained processing solution, and about 2,000 mL of the processing solution was removed using an ultrafiltration method. This operation was repeated 5 times, and filtration was performed using a regenerated cellulose filter (manufactured by ADVANTEC) having a pore diameter of 0.45 μm to obtain 1.3% by mass of a blue conductive polymer composite dispersion liquid 11.

(Preparation Example 12)

A solution obtained by dissolving 4.16 g of 3,4-propanedioxythiophene and 10.0 g of dopant polymer 2 in 1,000 mL of ultrapure water was mixed at 30 ° C.

While maintaining the mixed solution thus obtained at 30 ° C, while stirring, slowly add an oxidation catalyst solution of 8.40 g of sodium persulfate and 2.3 g of iron (III) sulfate dissolved in 100 mL of ultrapure water, and stir for 4 hours to make Its response.

1,000 mL of ultrapure water was added to the obtained reaction solution, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment solution subjected to the above-mentioned filtration treatment, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of ions were added thereto. Water was exchanged and about 2,000 mL of liquid was removed using ultrafiltration. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained processing solution, and about 2,000 mL of the processing solution was removed using an ultrafiltration method. This operation was repeated 5 times, and filtration was performed using a regenerated cellulose filter (manufactured by ADVANTEC) having a pore diameter of 0.45 μm to obtain 1.3% by mass of a blue conductive polymer composite dispersion liquid 12.

(Comparative Preparation Example 1)

At 30 ° C, 5.0 g of 3,4-ethylenedioxythiophene and a solution obtained by diluting 83.3 g of an aqueous polystyrenesulfonic acid solution (18.0% by mass of Aldrich) with 250 mL of ion-exchanged water were mixed. In addition, it was prepared in the same manner as in Preparation Example 1 to obtain 1.3% by mass of a blue comparative conductive polymer composite dispersion liquid 1 (PEDOT-PSS dispersion liquid). This comparative conductive polymer composite dispersion liquid 1 contains only polystyrenesulfonic acid as a dopant polymer.

[Examples and Comparative Examples] (Examples 1 to 17)

The 1.3% by mass of conductive polymer composite dispersion liquids 1-12 obtained in Preparation Examples 1-12, organic solvents, surfactant FS-31 manufactured by DuPont, and silver salts were each composed as shown in Table 1. The conductive materials were mixed and prepared as Examples 1 to 17, respectively. In addition, in Table 1, DMSO represents dimethyl sulfene.

(Comparative example 1)

1.3% by mass of the comparative conductive polymer composite dispersion liquid 1, water, organic solvent, and surfactant FS-31 manufactured by DuPont, were prepared in Comparative Preparation Example 1, and mixed with the composition described in Table 1 to prepare a conductive material. Sexual material, as Comparative Example 1.

(Comparative example 2)

Without adding a silver salt, 1.3% by mass of the conductive polymer composite dispersion liquid 1, water, organic solvent, and surfactant FS-31 manufactured by DuPont obtained in Formulation Example 1 were used. A conductive material was mixed and prepared as Comparative Example 2.

The conductive materials of Examples and Comparative Examples prepared as described above were evaluated as follows.

(Formation of conductive film)

First, 1.0 mL of a conductive material was dropped on a SiO ₂ wafer having a diameter of 4 inches (100 mm), and the whole was spin-coated with a spinner after 10 seconds. The spin coating conditions of Examples 1 to 17 and Comparative Examples 1 and 2 were adjusted so that the film thickness became 100 ± 5 nm. After coating, it was baked at 120 ° C for 5 minutes in a precision thermostat, and the conductive film was obtained by removing the solvent. The obtained conductive film was visually observed, and it was investigated whether a flat film was obtained. The results are shown in Table 1.

(Conductivity)

The conductivity (S / cm) of the obtained conductive film is the surface resistivity (Ω / □) and film thickness measured using Hiresta-UP MCP-HT450 and Loresta-GP MCP-T610 (both manufactured by Mitsubishi Chemical Corporation). Obtained from the measured value. The results are shown in Table 1.

(Transmittance)

In the conductive film obtained as described above, the transmittance of light with a wavelength of 550 nm at FT = 100 nm was calculated from the refractive index (k) measured by a spectroscopic ellipsometry (VASE) with a variable incident angle. The results are shown in Table 1.

(Flexibility)

The flexibility of the conductive films obtained using the conductive materials of Examples and Comparative Examples was evaluated as follows.

The conductive material was spin-coated on a flexible glass having a thickness of 50 μm and 5 cm square, and baked at 120 ° C. for 5 minutes to produce a conductive film having a thickness of 100 nm. The flexible glass substrate was bent 10 times with a curvature (R) of 120 degrees, and it was visually observed whether a crack was generated in the film. The results are shown in Table 1.

[Evaluation of conductive materials]

As shown in Table 1, a dopant polymer containing polythiophene as a π -conjugated polymer, a dopant polymer containing one or more repeating units selected from repeating units a1 to a4, a carboxylate with silver, and β After the diketone salt or carbonate examples 1 to 17 were applied by a spin coater, a flat and uniform coating film was obtained. In addition, it was confirmed that by adding a carboxylate salt, a β -diketone salt, or a carbonate salt of silver, the conductivity was increased. In addition, it became clear that the flexibility and the transmittance of visible light at λ = 550 nm were also good.

On the other hand, Comparative Example 1 containing a dopant polymer containing only polystyrene sulfonic acid and not containing a silver salt, had high conductivity, but generated streaks on the film. In Comparative Example 2 containing a dopant polymer containing repeating unit a1 and containing no silver salt, a flat and uniform coating film was obtained, but the conductivity was poor.

As described above, it is obvious that if the conductive material of the present invention is used, the film forming property on spin coating is good, and a conductive film having high transparency, high conductivity, excellent flexibility, and good flatness can be formed.

The present invention is not limited to the embodiments described above. The above-mentioned embodiment is an example, as long as it has substantially the same configuration as the technical idea described in the patent application scope of the present invention and exhibits the same effect, it is included in the technical scope of the present invention.

Claims (10)

A conductive material characterized by containing (A) a π-conjugated polymer and (B) containing one or more repeating units selected from repeating units represented by the following general formula (1), and having a weight average molecular weight of Dopant polymers in the range of 1,000 to 500,000, and (C) one or more salts selected from silver carboxylates, β-diketones, β-ketoesters, and carbonates; (Wherein R ¹ , R ³ , R ⁵ , and R ⁸ are each independently a hydrogen atom or a methyl group, and R ² , R ⁴ , and R ⁶ are each independently a single bond, an ester group, or may have Either an ether group, an ester group, or both of these are linear, branched, or cyclic hydrocarbon groups having 1 to 12 carbons; R ⁷ is a linear having 1 to 4 carbons, Branched alkylene groups. Among the hydrogen atoms in R ⁷ , one or two may be substituted by fluorine atoms; R ⁹ is a fluorine atom or a trifluoromethyl group; Z ₁ , Z ₂ , and Z ₃ are independent of each other. Ground is any one of a single bond, phenylene, naphthyl, ether group, and ester group; Z ₄ is any of a single bond, ether group, and ester group; Y is an oxygen atom or an NH group, and m is 1 Integers of ~ 4; a1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, and 0 <a1 + a2 + a3 + a4 ≦ 1.0 ). For example, the conductive material of claim 1, wherein the component (B) contains a repeating unit represented by the following general formula (2); (Where b is 0 <b <1.0). The conductive material according to claim 1, wherein the component (B) is a block copolymer. The conductive material according to claim 2, wherein the component (B) is a block copolymer. The conductive material according to any one of claim 1 to claim 4, wherein the component (A) is selected from the group consisting of pyrrole, thiophene, selenophene, tellurene, aniline, polycyclic aromatic compounds, and the like Polymers in which one or more precursor monomers of a group of derivatives are polymerized. The conductive material according to any one of claims 1 to 4, wherein the component (C) is any one or more of the following formulae (3-1) to (3-3); R ^{10 _{- (COO -) p (Ag}} +) p (3-1) (In the formula, p is an integer of 1 to 6, R ¹⁰ is a hydrogen atom, a linear, branched, or cyclic p-valent hydrocarbon group having 1 to 30 carbon atoms. When R ¹⁰ is a hydrocarbon group, R ¹⁰ may have Halogen atom, nitrogen atom, hydroxyl group, ether group, ester group, amine group, amido group, urethane group, carbonate group, sulfonate group, thiol group, thioether group, carbonyl group, sulfonyl group , lactone group, the acyl group, a sulfo lactone group, a nitro group; R ^11, R ¹² having 1 to 20 carbon atoms of straight-chain, branched or cyclic alkyl group of carbon atoms of an alkenyl having 2 to 20 Group, alkynyl group having 2 to 20 carbon atoms, or aryl group having 6 to 20 carbon atoms. These R ¹¹ and R ¹² may also have a hydroxyl group, an alkoxy group, an ether group, an ester group, an amine group, and an amidino group. , A sulfonate group, a halogen atom, a cyano group, a nitro group, a carbonate group, a urethane group, a thiol group, a thioether group, a thioketone group, or a heteroaromatic ring; R ¹³ is a hydrogen atom, Linear, branched, cyclic alkyl, or phenyl) having 1 to 8 carbon atoms). Item 5 of electrically conductive material, wherein the component (C), is represented by any one among the following formula (3-1) to (3-3) more than one kind of ^{request; R 10 - (COO -)} p (Ag ⁺ ) _p (3-1) (In the formula, p is an integer of 1 to 6, R ¹⁰ is a hydrogen atom, a linear, branched, or cyclic p-valent hydrocarbon group having 1 to 30 carbon atoms. When R ¹⁰ is a hydrocarbon group, R ¹⁰ may have Halogen atom, nitrogen atom, hydroxyl group, ether group, ester group, amine group, amido group, urethane group, carbonate group, sulfonate group, thiol group, thioether group, carbonyl group, sulfonyl group , lactone group, the acyl group, a sulfo lactone group, a nitro group; R ^11, R ¹² having 1 to 20 carbon atoms of straight-chain, branched or cyclic alkyl group of carbon atoms of an alkenyl having 2 to 20 Group, alkynyl group having 2 to 20 carbon atoms, or aryl group having 6 to 20 carbon atoms. These R ¹¹ and R ¹² may also have a hydroxyl group, an alkoxy group, an ether group, an ester group, an amine group, and an amidino group. , A sulfonate group, a halogen atom, a cyano group, a nitro group, a carbonate group, a urethane group, a thiol group, a thioether group, a thioketone group, or a heteroaromatic ring; R ¹³ is a hydrogen atom, Linear, branched, cyclic alkyl, or phenyl) having 1 to 8 carbon atoms). The conductive material according to any one of claim 1 to claim 4, wherein the aforementioned conductive material is one having dispersibility to water or an organic solvent. A substrate characterized in that a conductive film is formed from a conductive material according to any one of claim 1 to claim 8. The substrate according to claim 9, wherein the conductive film is a member that functions as a transparent electrode layer.