KR101968806B1 - Conductive material and substrate - Google Patents

Abstract

[PROBLEMS] To provide a conductive material which is excellent in film forming property and can form a conductive film having high transparency, high conductivity, excellent flexibility, and good flatness when a film is formed.
(A) a π conjugated polymer, (B) at least one repeating unit selected from the repeating units a1 to a4 represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000 And (C) at least one salt selected from carboxylic acid salts,? -Diketone salts,? -Ketoester salts, and carbonates.

Description

[0001] CONDUCTIVE MATERIAL AND SUBSTRATE [0002]

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

In a polymer having a conjugated double bond (π conjugated system polymer), the polymer itself does not exhibit conductivity, but when it is doped with a suitable anion molecule, the conductivity is developed to form a conductive polymer material (conductive polymer composition). (hetero) aromatic polymers such as polyacetylene, polythiophene, polyselenophene, polytelulophene, polypyrrole and polyaniline, and mixtures thereof, and the like are used as the π conjugated polymer. As the anion molecules (dopants), sulfonic acid anions Are most often used. This is because sulfonic acid, which is a strong acid, interacts effectively with the? -Conjugate-based polymer.

Sulfonic acid polymers such as polyvinylsulfonic acid and polystyrenesulfonic acid (PSS) are widely used as sulfonic acid anion dopants (Patent Document 1). Sulfonic acid polymers also include vinyl perfluoroalkyl ether sulfonic acids, such as the registered trademark Nifion, which are used in fuel cell applications.

Since polystyrene sulfonic acid (PSS) has sulfonic acid continuously present in the monomer main chain with respect to the main chain of the polymer, doping with respect to the? -Conjugated polymer is highly efficient and dispersion of the? -Conjugated polymer after the doping into water can also be improved . This is because hydrophilicity is maintained by the presence of an excess of sulfo group present in the PSS, and the dispersibility in water is remarkably improved.

Pithiophene with PSS as a dopant is highly conductive and can be handled as an aqueous dispersion, and is expected as a coating type conductive film material to replace ITO (indium-tin oxide). However, as described above, PSS is a water-soluble resin and hardly soluble in an organic solvent. Therefore, even though polythiophene with PSS as a dopant has high hydrophilicity, it has low affinity for organic solvent and organic substrate, and it is difficult to form a film on an organic substrate by dispersing in organic solvent.

When the polythiophene in which PSS is used as a dopant is used, for example, in a conductive film for organic EL lighting, since the hydrophilicity of the polythiophene using PSS as a dopant is very high as described above, a large amount of moisture And the formed conductive film is liable to attract moisture from the outside atmosphere. As a result, there is a problem that the luminous efficiency of the organic EL element is chemically changed by the chemical change of the organic EL element, and the water becomes coherent with the lapse of time, resulting in shortening the lifetime of the entire organic EL device. Further, the polythiophene having PSS as a dopant has a problem in that the surface of the film surface after formation of the film is large due to the large particles in the aqueous dispersion, but a non-light-emitting portion called a dark spot is generated when applied to organic EL illumination.

In addition, polythiophene having PSS as a dopant has absorption in a blue region near a wavelength of 500 nm. Therefore, when the material is applied on a transparent substrate such as a transparent electrode and used, the conductivity required for the device to function is set to a solid concentration There is a problem in that the transmittance as a member is influenced.

Patent Document 2 discloses that a π conjugated polymer formed by a repeating unit selected from thiophene, selenophene, telulophene, pyrrole, aniline, and polycyclic aromatic compound, and an organic solvent, A conductive polymer composition formed by a conductive polymer containing a fluorinated acid polymer neutralized with these cations has been proposed. By combining water, a precursor monomer of a π-conjugated polymer, a fluorinated acid polymer, and an oxidizing agent in an arbitrary order, It is proposed to be an aqueous dispersion of a polymer.

However, in such a conventional conductive polymer, particles are aggregated in the dispersion immediately after synthesis, and addition of an organic solvent which is a highly conductive agent as a coating material accelerates aggregation and deteriorates the filterability. On the other hand, if spin coating is performed without filtration, a flat film can not be obtained due to the influence of the particle agglomerates, and as a result, there is a problem that coating failure occurs.

In addition, development of a flexible device is underway. As a transparent conductive film for hard devices in the current situation, ITO is widely used. ITO is a crystalline film, and cracking occurs when it is bent. Therefore, the development of a flexible transparent conductive film replacing ITO is urgent. A film using polythiophene in which PSS is used as a dopant is a flexible and highly transparent film, but has a problem of low conductivity as compared with ITO in addition to the above-mentioned problem of dark spots.

Patent Document 3 discloses a transparent conductive film using silver nanowires. The transparent conductive film using silver nanowires is one of candidates of conductive films for flexible devices because it has high conductivity and high transparency. However, since the silver nanowire is not energized only in the wire portion, if it is applied to the organic EL illumination, there arises a problem that only the wire portion emits light and the entire surface does not emit light.

Japanese Patent Application Laid-Open No. 2008-146913 Japanese Patent No. 5264723 Japanese Patent Application Laid-Open No. 2009-224183

As described above, a film using a polythiophene-based conductive polymer using PSS as a dopant, such as PEDOT-PSS having high versatility, has transparency equivalent to that of ITO and is flexible compared to ITO but has a low conductivity. Further, a polythiophene-based conductive polymer containing PSS as a dopant has a problem that a dark spot is generated when it is applied to organic EL illumination. On the other hand, the transparent conductive film using silver nanowires has the characteristics of high transparency, high conductivity, and excellent flexibility. However, when applied to organic EL lighting, only the wire portion emits light and microscopic uniform light emission does not occur.

It is an object of the present invention to provide a conductive material which is excellent in film forming property and can form a conductive film having high transparency, high conductivity, excellent flexibility, and good flatness when a film is formed .

In order to solve the above problems,

(A) a? -Conjugated polymer,

(B) a dopant polymer containing at least one repeating unit selected from the repeating units a1 to a4 represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000, and

(C) at least one salt selected from a carboxylate of a silver, a β-diketone salt, a β-keto ester salt and a carbonate

And a conductive material.

(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, an ether group or an ester group Branched or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either one or both of R ^{7 and} R ^7, R ⁷ is a straight or branched alkylene group having 1 to 4 carbon atoms, and R ^{7 is a} there may be one or two of the hydrogen atoms is substituted with a fluorine atom. R ⁹ is a methyl group a fluorine atom or a trifluoromethyl group. Z _1, Z ₂ and Z ₃ are a single bond, each independently, a naphthyl phenyl group, a naphthyl group, An ether group or an ester group and Z ₄ is any of a single bond, an ether group and an ester group, Y is an oxygen atom or an NH group, and m is an integer of from 1 to 4. a1, a2, a3 and a4 A1? 1.0, 0? A2? 1.0, 0? A3? 1.0, 0? A4? 1.0, 0 <a1 + a2 + a3 + a4? .0)

When such a conductive material is used, it is possible to form a conductive film having good film-forming properties and having high transparency, high conductivity, excellent flexibility, and good flatness when formed.

At this time, the component (B) preferably contains the repeating unit b represented by the following general formula (2).

(Wherein b is 0 < b < 1.0)

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

Also, at this time, the component (B) is preferably a block copolymer.

If the component (B) is a block copolymer, the conductivity can be further improved.

It is also preferable that the component (A) is obtained by polymerizing at least one precursor monomer selected from the group consisting of pyrrole, thiophene, selenophene, telulophen, aniline, polycyclic aromatic compounds, and derivatives thereof .

If such a monomer is used, the polymerization is easy and the stability in air is good, so component (A) can be easily synthesized.

Also, at this time, it is preferable that the component (C) is at least one of those represented by the following formulas (3-1) to (3-3).

(Wherein, p is an integer from 1 to 6, R ¹⁰ is a hydrogen atom, a carbon number is 1 to 30 linear, branched, monovalent cyclic p hydrocarbon group, R ¹⁰ is a hydrocarbon group, R ¹⁰ in the halogen atom , A nitrogen atom, a hydroxyl group, an ether group, an ester group, an amino group, an amide group, a carbamate group, a carbonate group, a sulfonate group, a thiol group, a sulfide group, a carbonyl group, a sulfonyl group, R ¹¹ and R ¹² each independently represent a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 20 an aryl group, these R ^11, R ¹² in the hydroxyl group, an alkoxy group, an ether group, an ester group, an amino group, an amide group, a sulfonic acid ester group, a halogen atom, a cyano group, a nitro group, a carbonate group, a carbamate Group, a thiol group, a sulfide group, R ¹³ is a hydrogen atom, a straight, branched, cyclic alkyl group having 1 to 8 carbon atoms, or a phenyl group)

If this is the case, a conductive film having higher conductivity can be formed.

Also, at this time, it is preferable that the conductive material has dispersibility in water or an organic solvent.

Further, the present invention provides a substrate on which a conductive film is formed by the conductive material.

As described above, the conductive material of the present invention can be applied to a substrate or the like to form a conductive film.

Also, since the conductive film thus formed is excellent in conductivity and transparency, it can function as a transparent electrode layer.

As described above, as the conductive material of the present invention, the conductive polymer in which the dopant polymer of the component (B) containing the sulfo group of the super strong acid and the π conjugated polymer of the component (A) A solution in which at least one salt selected from silver carboxylate,? -Diketone salt,? -Ketoester salt, and carbonate is added has good film-forming properties in the filterability and spin coat. Further, the conductive film formed by film formation using the conductive material of the present invention has good conductivity, transparency, flatness, flexibility, durability, and low surface roughness. Further, if such a conductive material is used, the film-forming property is good for both the organic substrate and the inorganic substrate.

Further, since the conductive film formed by such a conductive material has excellent conductivity, transparency, flatness, flexibility, and the like, it can function as a transparent electrode layer, in particular, as a flexible transparent electrode.

As described above, there has been a demand for development of a conductive film forming material capable of forming a conductive film having high conductivity, transparency, excellent flexibility, and good flatness.

As a result of intensive studies on the above problems, the present inventors have found that, instead of polystyrene sulfonic acid (PSS) widely used as a dopant of a conductive polymer material, a dopant polymer having a repeating unit having a sulfo group fluorinated at the? By using the dopant polymer having a repeating unit, the dopant polymer of the super strong acid strongly interacts with the pi conjugated polymer, and the visible light absorption region of the pi conjugated polymer shifts to improve the transparency and the pi conjugated polymer and the dopant polymer And found that stability against light and heat is improved by strongly ion-binding. Further, it was found that the film forming property in the spin coat was improved, and the flatness at the time of film formation was also improved. Conductive materials obtained by combining at least one salt selected from a carboxylic acid salt, a? -Diketone salt, a? -Ketoester salt, and a carbonate with such a conductive polymer have higher conductivity than a case of a conductive polymer, Transparency, flatness of the film, and the like can be formed, thereby completing the present invention.

That is,

(A) a? -Conjugated polymer,

(B) a dopant polymer containing at least one repeating unit selected from the repeating units a1 to a4 represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000, and

(C) at least one salt selected from a carboxylate of a silver, a β-diketone salt, a β-keto ester salt and a carbonate

. &Lt; / RTI &gt;

(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, an ether group or an ester group Branched or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either one or both of R ^{7 and} R ^7, R ⁷ is a straight or branched alkylene group having 1 to 4 carbon atoms, and R ^{7 is a} there may be one or two of the hydrogen atoms is substituted with a fluorine atom. R ⁹ is a methyl group a fluorine atom or a trifluoromethyl group. Z _1, Z ₂ and Z ₃ are a single bond, each independently, a naphthyl phenyl group, a naphthyl group, An ether group or an ester group and Z ₄ is any of a single bond, an ether group and an ester group, Y is an oxygen atom or an NH group, and m is an integer of from 1 to 4. a1, a2, a3 and a4 A1? 1.0, 0? A2? 1.0, 0? A3? 1.0, 0? A4? 1.0, 0 <a1 + a2 + a3 + a4? .0)

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[(A)? Conjugated polymer]

The conductive material of the present invention includes a π conjugated polymer as the component (A). The component (A) may be a polymer obtained by polymerization of a precursor monomer (organic monomer molecule) forming a π conjugated system chain (a structure in which single bonds and double bonds are alternately continuous).

Examples of such precursor monomers include monocyclic aromatic compounds such as pyrrole, thiophene, thiophene vinylene, selenophene, telulopentane, phenylene, phenylene vinylene and aniline; Polycyclic aromatic compounds such as acen; Acetylene, and the like. A homopolymer or copolymer of these monomers can be used as the component (A).

Of these monomers, pyrrole, thiophene, selenophene, telulophen, aniline, polycyclic aromatic compounds, and derivatives thereof are preferable from the viewpoints of ease of polymerization and stability in air, and pyrrole, thiophene, Is particularly preferable. In particular, thiophenes are preferred because they have the highest conductivity and high transparency in visible light, but the present invention is not limited thereto.

In the case where the conductive material of the present invention contains the polythiophene as the component (A), since it has the characteristics of high conductivity and high transparency in visible light, it can be used as a touch panel, an organic EL display, . On the other hand, in the case where the conductive material of the present invention contains polyaniline as the component (A), application in display relation is difficult because of high absorption in visible light and low conductivity compared with the case of containing polythiophene, It is conceivable to use a top coat for preventing electrification of the upper layer resist film by electrons in EB lithography because of easy spin coating.

Further, the component (A) can obtain sufficient conductivity even when the monomers constituting the π conjugated polymer are unsubstituted. However, in order to further increase the conductivity, the component (A) may be substituted with an alkyl group, a carboxyl group, a sulfo group, an alkoxy group, a hydroxy group, The substituted monomers may be used.

Specific examples of the monomers of the pyrrole, thiophene and aniline include, for example, pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3- Carboxypyrrole, 3-methyl-4-carboxypyrrole, 3-methyl-4-carboxypyrrole, 3- But are not limited to, ethyl pyrrole, 3-methyl-4-carboxybutyl pyrrole, 3-hydroxypyrrolone, 3-methoxypyrrole, 3- Hexyloxycaproyl; Examples of the thiophene-based compound include thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, , 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3-hexylthiophene, 3-decyloxythiophene, 3-octyldecylthiophene, 3-octyloxythiophene, 3-decyloxythiophene, Diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4- 3,4-ethylenedithiophene, 3,4-ethylenedithiothiophene, 3,4-ethylenedithiophene, 3,4-ethylenedioxythiophene, 3,4- Methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3- 3-methyl-4-carboxyethylthiophene, 3,4- (2,2-dimethylpropylene dioxy) thiophene, 3, 4- (2,2-diethylpropylene dioxy) thiophene, (2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-yl) methanol; Aniline, 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2-propylaniline, 3-propylaniline, Isobutyl aniline, 2-methoxy aniline, 2-ethoxy aniline, 2-aniline sulfonic acid, 3-aniline sulfonic acid and the like.

Among them, a (co) polymer comprising one or two selected from the group consisting of pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, Value, and reactivity. Furthermore, the homopolymer of pyrrole and 3,4-ethylenedioxythiophene is more preferable because of its high conductivity.

Also, 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 includes a dopant polymer as the component (B). The dopant polymer of the component (B) comprises at least one repeating unit selected from the 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 acidic 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, an ether group or an ester group Branched or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either one or both of R ^{7 and} R ^7, R ⁷ is a straight or branched alkylene group having 1 to 4 carbon atoms, and R ^{7 is a} there may be one or two of the hydrogen atoms is substituted with a fluorine atom. R ⁹ is a methyl group a fluorine atom or a trifluoromethyl group. Z _1, Z ₂ and Z ₃ are a single bond, each independently, a naphthyl phenyl group, a naphthyl group, An ether group or an ester group and Z ₄ is any of a single bond, an ether group and an ester group, Y is an oxygen atom or an NH group, and m is an integer of from 1 to 4. a1, a2, a3 and a4 A1? 1.0, 0? A2? 1.0, 0? A3? 1.0, 0? A4? 1.0, 0 <a1 + a2 + a3 + a4? .0)

Specific examples of the monomer giving the repeating unit a1 include the following.

(Wherein R ¹ is as defined above and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine or a sulfonium)

Specific examples of the monomer giving the repeating unit a2 include the following.

(Wherein R ³ is as defined above and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine or a sulfonium)

Specific examples of the monomer giving the repeating unit a3 include the following.

(Wherein R ⁵ is as defined above and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine or a sulfonium)

Specific examples of the monomer giving the repeating unit a4 include the following.

(Wherein R ⁸ is as defined above and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine or a sulfonium)

Such a component (B) improves the filterability of the material and the film-forming property, affinity to the organic solvent and the substrate, and the transmittance after the film formation is improved.

(B) preferably further comprises a repeating unit b represented by the following general formula (2). By including such a repeating unit b, the conductivity can be further improved.

(Wherein b is 0 < b < 1.0)

Specific examples of the monomer giving the repeating unit b include the following.

(Wherein X ₂ is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine or a sulfonium)

When X and X ₂ are amines, examples thereof include (P1a-3) described in paragraph [0048] of JP-A-2013-228447.

Here, as described above, a1, a2, a3 and a4 satisfy 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. The effect of the present invention is obtained when 0 < a1 + a2 + a3 + a4 &lt; = 1.0 (i.e., when any one of the repeating units a1 to a4 is included) Is obtained.

When the repeating unit b is contained, it is preferable that 0.3? B < 1.0 and 0.3? B? 0.8 are more preferable from the viewpoint of improvement of conductivity.

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, more preferably 0.3? A1 + a2 + a3 + And more preferably 0.4? B? 0.7.

The dopant polymer of the component (B) may have a repeating unit c other than the repeating units a1 to a4 and the repeating unit b, and examples of the repeating unit c include styrene type, vinyl naphthalene type, vinyl silane type, Naphthylene, indene, vinylcarbazole, and the like.

Specific examples of the monomer giving the repeating unit c include the following.

When the monomer containing fluorine is copolymerized among the monomers giving the repeating unit c, the conductivity is lowered, but the transparency is improved, and the hole injection efficiency is increased and the number of steps is increased.

As a method for synthesizing the dopant polymer of the component (B), for example, a method of adding a desired monomer among the monomers imparting the above-mentioned repeating units a1 to a4, b and c to a radical polymerization initiator in an organic solvent, , A method of obtaining a dopant polymer of (co) polymer.

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

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis Benzoyl peroxide, lauroyl peroxide, and the like.

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

In the dopant polymer of the component (B), one kind or two or more kinds of monomers which give the repeating units a1 to a4 may be used, but it is preferable to combine methacrylic type and styrene type monomers in order to improve the polymerizability.

When two or more kinds of monomers imparting the repeating units a1 to a4 are used, the respective monomers may be randomly copolymerized or may be copolymerized in a block. In the case of using a block copolymer polymer (block copolymer), even when repeating portions containing two or more kinds of repeating units a1 to a4 are aggregated to form a sea-island structure, a specific structure is generated around the dopant polymer, An improvement advantage is expected.

The monomers imparting the repeating units a1 to a4, b, and c may be randomly copolymerized, or each may be copolymerized with a block. Also in this case, as in the case of the repeating units a1 to a4 described above, it is expected that the conductivity is improved by using a block copolymer.

When random copolymerization is carried out by radical polymerization, a method of mixing the monomers to be copolymerized and a radical polymerization initiator and then carrying out polymerization by heating is generally used. When the polymerization is initiated in the presence of the first monomer and the radical polymerization initiator and then the second monomer is added, the structure in which the first monomer is polymerized on one side of the polymer molecule and the second monomer is polymerized on the other side do. However, in this case, since the repeating units of the first monomer and the second monomer are mixed in the middle part, they are different in shape from the block copolymer. In order to form a block copolymer in radical polymerization, living radical polymerization is preferably used.

The living radical polymerization method referred to as RAFT polymerization (Reversible Addition Fragmentation chain transfer polymerization) is a method in which the radicals at the end of the polymer are always present so that the polymerization is initiated in the first monomer and the second monomer is added in the consumed step, It is possible to form a diblock copolymer with a block of repeating units of one monomer and a block of repeating units of the second monomer. It is also possible to initiate polymerization in the first monomer, to add the second monomer in the step in which it is consumed, and then to form a triblock copolymer when the third monomer is added.

When the RAFT polymerization is carried out, a narrow-dispersion polymer having a narrow molecular weight distribution (degree of dispersion) is formed. In particular, when RAFT polymerization is carried out by adding monomers alone, a polymer having a narrower molecular weight distribution can be formed .

In the dopant polymer of the component (B), the molecular weight distribution (Mw / Mn) is preferably 1.0 to 2.0, and more preferably 1.0 to 1.5. If it is narrow dispersion, the transmittance of the conductive film formed by the conductive material using it can be prevented from being lowered.

In order to carry out the RAFT polymerization, a chain transfer agent is required. Specific examples thereof include 2-cyano-2-propylbenzothioate, 4-cyano-4-phenylcarbonylthioylthiopentanoic acid, 2- 4-cyano-4 - [(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, 2- (dodecylthiocarbonothioylthio) -2-methylpropanoic acid, (Thiobenzoyl) disulfide, bis (dodecylsulfanylthiocarbonyl) disulfide, and the like can be given as examples. Of these, 2-cyano-2-propylbenzothioate is particularly preferable.

The ratio of the repeating units a1 to a4, b, and 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, more preferably 0.2? a1 + a2 + a3 + a4? 0.8, 0.2? b? 0.8, and 0? c?

It is also preferable that a1 + a2 + a3 + a4 + b + c = 1.

The dopant polymer of component (B) has a weight average molecular weight in the range of 1,000 to 500,000, preferably in the range of 2,000 to 200,000. If the weight average molecular weight is less than 1,000, the heat resistance becomes poor and the uniformity of the composite solution with the component (A) deteriorates. On the other hand, when the weight average molecular weight exceeds 500,000, not only the conductivity is deteriorated but also the viscosity is increased and the workability is deteriorated and the dispersibility in water or organic solvent is lowered.

The weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using water, dimethylformamide (DMF) or tetrahydrofuran (THF) as a solvent in terms of polyethylene oxide, polyethylene glycol or polystyrene.

As the monomer constituting the dopant polymer of the component (B), a monomer having a sulfo group may be used, but a polymerization reaction is carried out using a lithium salt, a sodium salt, a potassium salt, an ammonium salt or a sulfonium salt of a sulfo group as a monomer, It may be converted into a sulfo group by using an ion exchange resin.

[(C) silver carboxylate,? -Diketone salt,? -Ketoester salt, carbonate]

The conductive material of the present invention includes at least one kind of salt (hereinafter, also referred to as silver salt) selected from a carboxylic acid salt of a silver, a β-diketone salt, a β-keto ester salt and a carbonate as a component (C). Particularly, the component (C) is preferably at least one of those represented by the following formulas (3-1) to (3-3).

(Wherein, p is an integer from 1 to 6, R ¹⁰ is a hydrogen atom, a carbon number is 1 to 30 linear, branched, monovalent cyclic p hydrocarbon group, R ¹⁰ is a hydrocarbon group, R ¹⁰ in the halogen atom , A nitrogen atom, a hydroxyl group, an ether group, an ester group, an amino group, an amide group, a carbamate group, a carbonate group, a sulfonate group, a thiol group, a sulfide group, a carbonyl group, a sulfonyl group, R ¹¹ and R ¹² each independently represent a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 20 an aryl group, these R ^11, R ¹² in the hydroxyl group, an alkoxy group, an ether group, an ester group, an amino group, an amide group, a sulfonic acid ester group, a halogen atom, a cyano group, a nitro group, a carbonate group, a carbamate Group, a thiol group, a sulfide group, R ¹³ is a hydrogen atom, a straight, branched, cyclic alkyl group having 1 to 8 carbon atoms, or a phenyl group)

In the formula (3-1), when R ¹⁰ represents a monovalent hydrocarbon group, R ¹⁰ represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic alkyl group having 2 to 30 carbon atoms An alkenyl group of 2 to 30 carbon atoms, a straight chain, branched or cyclic alkynyl group of 2 to 30 carbon atoms, or an aryl group of 6 to 30 carbon atoms.

Specific examples of the carboxylic acid ion for forming the carboxylic acid salt represented by the above formula (3-1) or (3-3) include the following. Of these carboxylic acid ions, the more the carbon number is, the more easily it is dissolved in an organic solvent.

In the above-mentioned β-diketone salts and β-keto ester salts, β-diketones and β-keto esters are enolized to form silver complexes. For example, acetylacetone, which is one of? -Diketones, is enolized as shown below to form a silver complex.

Specific examples of? -Diketones (i.e., substituted or unsubstituted acetylacetones) or? -Keto esters represented by the above formula (3-2) include the following.

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

The silver carboxylate,? Diketone salt,? Ketoester salt and carbonate may be hydrates.

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

The composite of polythiophene and polystyrenesulfonic acid (PEDOT-PSS) has a particle shape. As a result of the X-ray analysis, it is said that the conductive polythiophene is crystallized and polystyrene sulfonic acid covers the periphery. The polystyrene sulfonic acid forms a localized polaron of the charge of the double bonds of the polythiophene, thereby improving the conductivity. Polystyrene sulfonic acid has a function as a dopant for improving conductivity of polythiophene and a function for improving dispersibility in water by covering insoluble polythiophene. However, polystyrene sulfonic acid is an insulator. The polythiophene moiety in the particles is highly conductive, but the conductivity is low when the surroundings are covered with the shell of polystyrene sulfonic acid of the insulating material.

When a small amount of a solvent such as ethylene glycol, diethylene glycol, or DMSO is added to the aqueous dispersion of PEDOT-PSS, conductivity is improved. This is explained by the fact that by the addition of the above-mentioned solvent, the shell of the polystyrenesulfonic acid is broken and electrons of the polythiophene particles are exchanged.

When a silver salt is added as in the present invention, a silver salt is formed with the component (B) of super acid. This is because the positive charge metal is energetically stable in that it forms a salt with a supercharged acid which is negatively charged. The component (B) is an insulator covering the outside of the thiophene particle, but since highly conductive silver salt adheres to the outside, migration of electrons between the particles becomes active and conductivity is improved.

[Other components]

(Surfactants)

In the present invention, a surfactant may be added to increase the wettability of a substrate or the like to a workpiece. Examples of such surfactants include nonionic, cationic and anionic surfactants. Specific examples thereof include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene carboxylic acid ester, sorbitan ester and polyoxyethylene sorbitan ester, alkyltrimethyl ammonium chloride , Alkylbenzylammonium chloride, anionic surfactants such as alkyl or alkylallylsulfates, alkyl or alkylallylsulfonates and dialkylsulfosuccinates, amphoteric surfactants such as amino acid type and betaine type, A surfactant, an acetylenic alcohol surfactant, and an acetylenic alcohol surfactant in which the hydroxyl group is polyethylene oxide or polypropylene oxide.

(Advanced telephone system)

In the present invention, an organic solvent as a highly conductive agent may be added separately from the main solvent for the purpose of improving the conductivity of the conductive material. Specific examples of such an additive solvent include polar solvents such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dimethylsulfoxide (DMSO), dimethylformamide (DMF), N-methyl- (NMP), sulfolane, ethylene carbonate, and mixtures thereof. The addition amount is preferably 1.0 to 30.0 mass%, particularly preferably 3.0 to 10.0 mass%.

(corrector)

In the present invention, the pH in the aqueous solution of the conductive material indicates acidity. For the purpose of neutralizing this, the nitrogen-containing aromatic cyclic compound described in paragraphs [0033] to [0045] of Japanese Patent Laid-Open Publication No. 2006-96975 and the cation described in paragraph [0127] described in Japanese Patent No. 5264723 were added The pH can also be adjusted to neutral. By making the pH of the solution near neutral, the occurrence of rust can be prevented when applied to a printing machine.

[Conductive material]

The conductive material of the present invention comprises the above-mentioned π conjugated polymer as the component (A), the dopant polymer as the component (B) and the silver salt as the component (C), and the dopant polymer as the component (B) ) Component of the? -Conjugate-based polymer to form a complex.

The conductive material of the present invention preferably has dispersibility in water or an organic solvent, and is excellent in spin-coat film-forming property and flatness of the film on an inorganic or organic substrate (substrate on which an inorganic film or an organic film is formed on the substrate surface) have.

(Method for producing conductive material)

The method for producing the conductive material (solution) of the present invention is not particularly limited. For example, the conductive polymer composite (solution) containing the π conjugated polymer as the component (A) and the dopant polymer as the component (B) Can be prepared by adding a silver salt as the component (C).

The complex of the component (A) and the component (B) can be obtained by, for example, mixing a monomer (B) or a monomer serving as a raw material of the component (A) , Thiophene, aniline, or derivative monomers thereof), adding an oxidizing agent and, if necessary, an oxidation catalyst, and carrying out oxidative polymerization.

Examples of the oxidizing agent and the oxidizing catalyst include peroxodisulfate (persulfate) such as ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate) and potassium peroxodisulfate (persulfate) Transition metal compounds such as iron, ferric sulfate and cupric chloride, metal oxides such as silver oxide and cesium oxide, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen and the like.

As the reaction solvent used in the oxidation polymerization, water or a mixed solvent of water and a solvent may be used. The solvent used here is preferably a solvent capable of dissolving or dispersing the component (A) and the component (B), which is miscible with water. Polar solvents such as N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide and hexamethylphosphoric triamide, alcohols such as methanol, ethanol, Butanol and the like; alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, , Polyvalent aliphatic alcohols such as 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol, carbonate compounds such as ethylene carbonate and propylene carbonate, Cyclic ether compounds such as ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether And heterocyclic compounds such as 3-methyl-2-oxazolidinone, and nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, and the like. These solvents may be used alone or in a mixture of two or more. The blending amount of these water-miscible solvents is preferably 50 mass% or less of the total reaction solvent.

In addition to the dopant polymer of the component (B), an anion capable of doping the component (A) into the π conjugated polymer may be used in combination. As such an anion, an organic acid is preferable from the viewpoints of adjusting the dedoping property from the π conjugated polymer, the dispersibility of the conductive material, the heat resistance, and the environmental characteristics. Examples of the organic acid include an organic carboxylic acid, a phenol, and an organic sulfonic acid.

As the organic carboxylic acid, aliphatic, aromatic, cyclic aliphatic or the like containing one or more carboxyl groups can be used. For example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, Acetic acid and the like.

The phenols include phenols such as cresol, phenol and xylenol.

As the organic sulfonic acid, aliphatic, aromatic, cyclic aliphatic, and the like, which contain one or two or more sulfonic acid groups can be used. 1-heptanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-nonanesulfonic acid, 1-butanesulfonic acid, Decanedicarboxylic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, cholestane methanesulfonic acid, Amino-2-naphthol-7-sulfonic acid, 3-aminopropanesulfonic acid, N-cyclohexyl-sulfonic acid, There may be mentioned sulfonic acids such as benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, Benzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, Aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-sulfonic acid, 4-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, Sulfonic acid, 4-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene sulfonic acid, 2-methylbenzene-1-sulfonic acid, 4-acetamido-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid 1-naphthalene sulfonic acid, 8-chloronaphthalene-1-sulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate And sulfonic acid compounds containing sulfonic acid groups such as sulfonic acid groups.

Examples of the sulfonic acid group having two or more sulfonic acid groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, m-benzenedisulfonic acid, o-benzenedisulfonic acid, p-benzenedisulfonic acid, , Aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, diethylbenzene disulfonic acid, dibutylbenzene disulfonic acid, naphthalene disulfonic acid, Amino naphthalene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, dodecyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, butyl naphthalene disulfonic acid, 2-amino- Amino-1,5-naphthalene disulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, anthracene disulfonic acid, butyl anthracene disulfonic acid, 4-acetamido-4'-isothiocyanato Benz-2,2'-disulfonic acid, 4-acetamido-4'-maleimidylstilbene-2,2'-disulfonic acid, 1 -Acetoxypyrrole-3,6,8-trisulfonic acid, 7-amino-1,3,6-naphthalenetrisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, 3- 7-naphthalenetrisulfonic acid, and the like.

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

The composite of the component (A) and the component (B) obtained as described above can be used by atomization using a homogenizer or a ball mill if necessary.

For atomization, it is preferable to use a mixed dispersing machine capable of imparting a high shear force. Examples of the mixed dispersing machine include a homogenizer, a high-pressure homogenizer, and a bead mill, and a high-pressure homogenizer is preferable.

Specific examples of the high-pressure homogenizer include a nano-beder manufactured by Yoshida Kikai Kogyo Co., a microfluidizer manufactured by Powlex Co., and an ultimizer manufactured by Suginomachin Co.,

Examples of the dispersion treatment using a high-pressure homogenizer include a treatment for causing the composite solution before the dispersion treatment to collide against each other at a high pressure, a treatment for passing the composite solution before passing through the orifice or slit under high pressure, and the like.

The impurities may be removed by filtration, ultrafiltration, dialysis or the like before or after atomization and purified by cation exchange resin, anion exchange resin, chelate resin or 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. When the total content of the component (A) and the component (B) is 0.05 mass% or more, sufficient conductivity is obtained. When the total content is 5.0 mass% or less, a uniform conductive coating film is easily obtained.

The content of the component (B) is preferably such that the amount of the sulfo group in the component (B) is in the range of 0.1 to 10 moles relative to 1 mole of the component (A), more preferably 1 to 7 moles . When the amount of the sulfo group in the component (B) is 0.1 mol or more, the doping effect on the component (A) is high, so that sufficient conductivity can be secured. When the amount of the sulfo group in the component (B) is 10 mol or less, the content of the component (A) is also appropriate, and sufficient conductivity is obtained.

With the conductive material of the present invention as described above, it is possible to form a conductive film having good film formability in filtration property and spin coat, high transparency and low surface roughness.

[Conductive film]

The conductive material (solution) obtained as described above can be applied to a workpiece such as a substrate to form a conductive film. Examples of the application method of the conductive material (solution) include coating with a spin coater or the like, bar coater, immersion, comma coat, spray coat, roll coat, screen printing, flexo printing, gravure printing, . After the application, a conductive film can be formed by a heat treatment with a hot air circulation path, a hot plate, or the like, or by IR, UV irradiation, or the like.

As described above, the conductive material of the present invention can be applied to a substrate or the like to form a conductive film. Also, since the conductive film thus formed is excellent in conductivity and transparency, it can function as a transparent electrode layer. The conductive material of the present invention also has a function as a hole injection layer. The conductive material of the present invention is applied as a hole injecting layer on a transparent conductive film such as ITO, silver nanowire, or silver wiring, and a hole transporting layer, a light emitting layer, an electron injecting layer, and a cathode are formed thereon. When applied as a hole injection layer, high conductivity is not necessarily required.

ITO produced by sputtering or the like is used as a transparent electrode, but since it is a crystalline film, if it is bent, the crystal is collapsed and the conductivity is lowered and broken. 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 can be used as a conductive film for a flexible device because it does not break or deteriorate in conductivity even if bent.

[Board]

Further, the present invention provides a substrate on which a conductive film is formed by the above-described conductive material of the present invention.

Examples of the substrate include a glass substrate, a quartz substrate, a photomask blank substrate, a resin substrate, a silicon wafer, a compound semiconductor wafer such as a gallium arsenide wafer and an indium-phosphorous wafer, and a flexible substrate. It is also possible to apply it to a photoresist film and use it as an antistatic topcoat.

As described above, in the case of the conductive material of the present invention containing the complex of the dopant polymer of component (B) containing the sulfo group of super strong acid with the π conjugated polymer of component (A) and the salt of silver of component (C) , The film forming property in the filterability and the spin coat is good and when the film is formed, a conductive film having good transparency, flexibility, flatness, durability and conductivity and low surface roughness can be formed. In addition, if such a conductive material is used, the film-forming property is good for both the organic substrate and the inorganic substrate.

Further, since the conductive film formed by such a conductive material is excellent in conductivity, transparency, and the like, it can function as a transparent electrode layer.

[Example]

Hereinafter, the present invention will be described in detail with reference to Synthesis Examples, Preparation Examples, Comparative Preparation Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

[Synthesis of dopant polymer]

(Synthesis Examples 1 to 9)

A solution of each monomer and dimethyl 2,2'-azobis (isobutyrate) in methanol stirred at 64 ° C under a nitrogen atmosphere was stirred for 8 hours, cooled to room temperature, and added dropwise with vigorous stirring to ethyl acetate . The resulting solid was collected by filtration, vacuum dried at 50 ° C for 15 hours, and the resulting white polymer was dissolved in pure water. The cation of the monomer was exchanged with a hydrogen atom using an ion exchange resin and converted into a sulfo group.

In this way, 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 Complex Dispersion]

(Preparation example 1)

3.82 g of 3,4-ethylenedioxythiophene and 12.5 g of the dopant polymer 1 dissolved in 1,000 mL of ultrapure water were mixed at 30 占 폚.

8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while maintaining the resulting mixed solution at 30 DEG C with stirring and reacted for 4 hours with stirring .

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. This operation was repeated three 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 filtration treatment, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of ion exchange Water was added and about 2,000 mL of solution was removed by ultrafiltration. This operation was repeated three 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 by ultrafiltration. This operation was repeated five times and filtration was performed using a regenerated cellulose filter (manufactured by ADVANTEC CORPORATION) having a pore diameter of 0.45 mu m to obtain 1.3 wt% of a conductive polymer composite dispersion 1 of blue color.

Ultrafiltration conditions were as follows.

Fractional molecular weight of ultrafiltration membrane: 30K

Crossflow

Feed flow rate: 3,000 mL / min

Membrane partial pressure: 0.12 Pa

Ultrafiltration was carried out under the same conditions in the other preparations.

(Preparation example 2)

12.5 g of the dopant polymer 1 was changed to 10.0 g of the dopant polymer 2, the amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, the amount of sodium persulfate was changed to 5.31 g and the amount of ferric sulfate was changed to 1.50 g , A preparation was conducted in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion 2.

(Preparation Example 3)

12.5 g of the dopant polymer 1 was changed to 12.0 g of the dopant polymer 3, the amount of 3,4-ethylenedioxythiophene was changed to 2.72 g, the amount of sodium persulfate was changed to 6.00 g, and the amount of ferric sulfate was changed to 1.60 g , The preparation was carried out in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion 3.

(Preparation example 4)

12.5 g of the dopant polymer 1 was changed to 11.8 g of the dopant polymer 4, 8.40 g of sodium persulfate was changed to 4.50 g of ammonium persulfate, the amount of 3,4-ethylenedioxythiophene was adjusted to 2.04 g, The preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.23 g to obtain Conductive Polymer Complex Dispersion 4.

(Preparation Example 5)

12.5 g of the dopant polymer 1 was changed to 11.0 g of the dopant polymer 5, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, the blending amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, The preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.50 g to obtain a conductive polymer composite dispersion 5.

(Preparation example 6)

12.5 g of the dopant polymer 1 was changed to 13.0 g of the dopant polymer 6, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, the blending amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, The preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.50 g to obtain a conductive polymer composite dispersion 6.

(Preparation Example 7)

12.5 g of the dopant polymer 1 was changed to 12.8 g of the dopant polymer 7, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, the blending amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, The preparation was conducted in the same manner as in Preparation Example 1, except that the amount of the mixture was changed to 1.50 g to obtain a conductive polymer composite dispersion 7.

(Preparation Example 8)

12.5 g of the dopant polymer 1 was changed to 11.0 g of the dopant polymer 8, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, the amount of 3,4-ethylenedioxythiophene was adjusted to 2.41 g, The preparation was carried out in the same manner as in Preparation Example 1 except that the amount of the mixture was changed to 1.50 g to obtain a conductive polymer composite dispersion 8.

(Preparation example 9)

A solution prepared 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.

8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while maintaining the resulting mixed solution at 30 DEG C with stirring and reacted for 4 hours with stirring .

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. This operation was repeated three 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 filtration treatment, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of ion exchange Water was added and about 2,000 mL of solution was removed by ultrafiltration. This operation was repeated three 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 by ultrafiltration. This operation was repeated five times and filtration was conducted using a regenerated cellulose filter (manufactured by ADVANTEC CORPORATION) having a pore diameter of 0.45 mu m to obtain 1.3 wt% of a conductive polymer composite dispersion 9 of blue color.

(Preparation Example 10)

12.5 g of the dopant polymer 1 was changed to 9.0 g of the dopant polymer 9, the amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, the amount of sodium persulfate was changed to 5.31 g, and the amount of ferric sulfate was changed to 1.50 g , A preparation was conducted in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion 10.

(Preparation Example 11)

A solution obtained by dissolving 4.62 g of (2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-yl) methanol and 10.0 g of the dopant polymer 2 in 1000 mL of ultrapure water , And mixed at 30 캜.

8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while maintaining the resulting mixed solution at 30 DEG C with stirring and reacted for 4 hours with stirring .

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. This operation was repeated three 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 filtration treatment, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of ion exchange Water was added and about 2,000 mL of solution was removed by ultrafiltration. This operation was repeated three 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 by ultrafiltration. This operation was repeated five times and filtration was performed using a regenerated cellulose filter (manufactured by ADVANTEC CORPORATION) having a pore diameter of 0.45 mu m to obtain a dispersion liquid 11 of a conductive polymer complex having a blue color of 1.3 mass%.

(Preparation Example 12)

A solution of 4.16 g of 3,4-propylenedioxythiophene and 10.0 g of the dopant polymer 2 dissolved in 1,000 mL of ultrapure water was mixed at 30 占 폚.

8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while maintaining the resulting mixed solution at 30 DEG C with stirring and reacted for 4 hours with stirring .

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. This operation was repeated three 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 filtration treatment, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of ion exchange Water was added and about 2,000 mL of solution was removed by ultrafiltration. This operation was repeated three 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 by ultrafiltration. This operation was repeated five times and filtration was conducted using a regenerated cellulose filter (manufactured by ADVANTEC CORPORATION) having a pore diameter of 0.45 mu m to obtain a 1.3 wt% blue conductive polymer composite dispersion 12.

(Comparative Preparation Example 1)

5.0 g of 3,4-ethylenedioxythiophene and 83.3 g of polystyrene sulfonic acid aqueous solution (18.0 mass% of Aldrich) were diluted with 250 ml of ion-exchanged water and mixed at 30 占 폚. Other than that, the preparation was carried out in the same manner as in Preparation Example 1 to obtain 1.3 wt% of a blue comparative conductive polymer composite dispersion 1 (PEDOT-PSS dispersion). This comparative conductive polymer composite dispersion 1 contains only polystyrene sulfonic acid as a dopant polymer.

[Examples and Comparative Examples]

(Examples 1 to 17)

A conductive material was prepared by mixing the 1.3 wt% conductive polymer composite dispersion 1 to 12 obtained in Preparation Examples 1 to 12, the organic solvent, the surfactant FS-31, and the silver salt, manufactured by DuPont Co., Respectively. In Table 1, DMSO represents dimethylsulfoxide.

(Comparative Example 1)

A conductive material was prepared by mixing 1.3 mass% of the comparative conductive polymer composite dispersion 1 obtained in Comparative Preparation Example 1, water, an organic solvent, and a surfactant FS-31 manufactured by DuPont Co., Respectively.

(Comparative Example 2)

A conductive material was prepared by mixing 1.3 wt% of the conductive polymer composite dispersion 1 obtained in Preparation Example 1, water, an organic solvent, and a surfactant FS-31, manufactured by DuPont, in the same composition as shown in Table 1 without adding silver salt, 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 onto a 4-inch (100 mm) diameter SiO ₂ wafer, and after 10 seconds, the whole was spin-coated using a spinner. The spin coating conditions in Examples 1 to 17 and Comparative Examples 1 and 2 were adjusted so that the film thickness was 100 ± 5 nm. After the application, the substrate was baked at 120 DEG C for 5 minutes in a precision thermostat, and the solvent was removed to obtain a conductive film. The obtained conductive film was observed with naked eyes to see whether a flat film was obtained. The results are shown in Table 1.

(Conductivity)

The conductivity (S / cm) of the conductive film thus obtained was measured in terms of the surface resistivity (Ω / square) measured using Hiresta-UP MCP-HT450, Loresta-GP MCP-T610 (all Mitsubishi Kagaku) ) And the measured value of the film thickness. The results are shown in Table 1.

(Transmittance)

From the refractive index (k) measured by the spectroscopic ellipsometer (VASE) having the variable angle of incidence, the transmittance of the conductive film thus obtained to a light beam having a wavelength of 550 nm at FT = 100 nm was calculated. The results are shown in Table 1.

(Flexibility)

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 rectangular flexible glass having a thickness of 50 占 퐉 and a side length of 5 cm and baked at 120 占 폚 for 5 minutes to prepare a conductive film having a thickness of 100 nm. The flexible glass substrate was bent at a curvature R of 120 degrees ten times to visually observe whether or not cracks were generated in the film. The results are shown in Table 1.

[Evaluation of conductive material]

As shown in Table 1, as a π conjugated polymer, a polythiophene, a dopant polymer containing at least one repeating unit selected from repeating units a1 to a4, and a carboxylate, β-diketone salt or carbonate including silver When Examples 1 to 17 were applied by a spin coater, a flat and uniform coating film was obtained. It was also confirmed that the conductivity was enhanced by adding a carboxylic acid salt, a? -Diketone salt or a carbonate of silver. It has also been found that flexibility and transmittance to visible light at? = 550 nm are also improved.

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

As described above, it has been found that the conductive material of the present invention can form a conductive film having good film formability in a spin coat, high transparency, high conductivity, excellent flexibility, and good flatness.

The present invention is not limited to the above-described embodiments. The above embodiment is an example, and anything that has substantially the same structure as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims (10)

(A) a? -Conjugated polymer,
(B) a dopant polymer containing at least one repeating unit represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000, and
(C) at least one salt selected from a carboxylate of a silver, a β-diketone salt, a β-keto ester salt and a carbonate
And a conductive material.

(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, an ether group or an ester group Branched or cyclic hydrocarbon group having 1 to 12 carbon atoms which may or may not contain either one or both of R ^{7 and} R ⁸ is a straight or branched alkylene group having 1 to 4 carbon atoms, R ⁷ is not one or two of the hydrogen atoms are replaced or substituted with a fluorine atom in. R ⁹ is a methyl group a fluorine atom or a trifluoromethyl group. Z _1, Z ₂ and Z ₃ are independently selected stage each bond, a phenylene group , naphthyl group, an ether group, any one of an ester group, Z ₄ is any one of a single bond, an ether group, an ester group. Y is an oxygen atom or a NH group, m is an integer from 1 to 4. a1, a2, a3 and a4 satisfy 0? a1? 1.0, 0? a2? 1.0, 0? a 1.0, 0? A4? 1.0 and 0 <a1 + a2 + a3 + a4? 1.0) The conductive material according to claim 1, wherein the component (B) further comprises a repeating unit represented by the following general formula (2).

(Wherein 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 method according to any one of claims 1 to 4, wherein the component (A) is at least one selected from the group consisting of pyrrole, thiophene, selenophen, telulophen, aniline, polycyclic aromatic compounds, Wherein the precursor monomer is polymerized. The conductive material according to any one of claims 1 to 4, wherein the component (C) is at least one of those represented by the following formulas (3-1) to (3-3).

(Wherein, p is an integer from 1 to 6, R ¹⁰ is a straight-chain hydrogen atoms, having 1 to 30 carbon atoms, branched, or a monovalent cyclic p hydrocarbon group, when R ¹⁰ is a hydrocarbon group, a halogen while R ¹⁰ An amino group, an amide group, a carbamate group, a carbonate group, a sulfonate ester group, a thiol group, a sulfide group, a carbonyl group, a sulfonyl group, a lactone group, a lactam group, alcohol tongi, does not have or has a nitro group. R ^11, R ¹² is an alkynyl group having 1 to 20 carbon atoms of straight, branched alkyl or cyclic alkenyl group having 2 to 20, 2 to 20 carbon atoms, or carbon atoms, and 6 to 20 aryl group, and these R ^11, R ¹² in the hydroxyl group, an alkoxy group, an ether group, an ester group, an amino group, an amide group, a sulfonic acid ester group, a halogen atom, a cyano group, a nitro group, a carbonate group, a carboxylic A benzoyl group, a thiol group, R ¹³ represents a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 8 carbon atoms, or a phenyl group) The conductive material according to any one of claims 1 to 4, wherein the conductive material has dispersibility in water or an organic solvent. A substrate comprising a conductive film formed by the conductive material according to any one of claims 1 to 4. The substrate according to claim 8, wherein the conductive film functions as a transparent electrode layer. The conductive material according to claim 5, wherein the component (C) is at least one selected from the group consisting of the following formulas (3-1) to (3-3).

(Wherein, p is an integer from 1 to 6, R ¹⁰ is a straight-chain hydrogen atoms, having 1 to 30 carbon atoms, branched, or a monovalent cyclic p hydrocarbon group, when R ¹⁰ is a hydrocarbon group, a halogen while R ¹⁰ An amino group, an amide group, a carbamate group, a carbonate group, a sulfonate ester group, a thiol group, a sulfide group, a carbonyl group, a sulfonyl group, a lactone group, a lactam group, alcohol tongi, does not have or has a nitro group. R ^11, R ¹² is an alkynyl group having 1 to 20 carbon atoms of straight, branched alkyl or cyclic alkenyl group having 2 to 20, 2 to 20 carbon atoms, or carbon atoms, and 6 to 20 aryl group, and these R ^11, R ¹² in the hydroxyl group, an alkoxy group, an ether group, an ester group, an amino group, an amide group, a sulfonic acid ester group, a halogen atom, a cyano group, a nitro group, a carbonate group, a carboxylic A benzoyl group, a thiol group, R ¹³ represents a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 8 carbon atoms, or a phenyl group)