TWI670343B - Conductive polymer composite and substrate - Google Patents

Abstract

The present invention provides a conductive film conductive polymer composite which is excellent in filterability and excellent in film formability by spin coating, and which has high transparency and flatness when formed into a film, and is characterized in that it contains the following components. (A) a π-conjugated polymer, and (B) a dopant polymer having a repeating unit a represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 500,000; (wherein R ¹ is a hydrogen atom or a methyl group, R ² is a fluorine atom or a trifluoromethyl group, a Z-based single bond or -C(=O)-O-, m is an integer of 1 to 4, and a is 0. <a≦1.0).

Description

Conductive polymer composite and substrate

The present invention relates to a substrate in which a conductive film is formed by a conductive polymer composite and a conductive polymer composite.

The conjugated double bond has a polymer (π-conjugated polymer), and the polymer itself does not exhibit conductivity, but is electrically conductive by doping with an appropriate anionic molecule to form a conductive polymer material (conductive polymer composition) ()). As the π-conjugated polymer, a (heterocyclic) aromatic polymer such as polyacetylene, polythiophene, polyselenol, polydecene, polypyrrole or polyaniline, and the like are used as an anionic molecule (dopant). The most commonly used sulfonic acid anion. This is because the strong acid sulfonic acid and the above π conjugated polymer effectively interact with each other.

As the sulfonic acid-based anion dopant, a sulfonic acid polymer such as polyvinylsulfonic acid or polystyrenesulfonic acid (PSS) is widely used (Patent Document 1). Further, the sulfonic acid polymer also has a vinyl perfluoroalkyl ether sulfonic acid represented by the registered trademark Nafion, which is used for a fuel cell.

Because of the polystyrene for the polymer backbone sulfonic acid homopolymer The sulfonic acid (PSS) sulfonic acid is continuously present as a monomer unit, and the doping of the π-conjugated polymer is high, and the doped π-conjugated polymer can also enhance the dispersibility for water. . This maintains hydrophilicity by the presence of a sulfonic acid group present in the excess of PSS, significantly increasing the dispersibility to water.

Polythiophene having PSS as a dopant is highly conductive and can be handled as an aqueous dispersion. It is expected to replace ITO (indium-tin oxide) as a coating-type conductive film material, but as the above-mentioned PSS-based water-soluble resin, it hardly Dissolved in an organic solvent. Therefore, the polythiophene having PSS as a dopant is also highly hydrophilic, but has low affinity for an organic solvent or an organic substrate, is difficult to disperse into an organic solvent, and forms a film on an organic substrate.

Further, when a polythiophene having a PSS as a dopant is used for, for example, a conductive film for organic EL illumination, since the hydrophilicity of the polythiophene having PSS as a dopant as described above is very high, a large amount of moisture remains in the conductive film, and The formed conductive film easily captures moisture from the external environment. As a result, the organic EL illuminator undergoes a chemical change to lower the luminescence ability, and as time elapses, the condensed water becomes a defect, and the life of the entire organic EL device becomes short. Further, there is a problem that the polythiophene having PSS as a dopant has large particles in an aqueous dispersion, and the surface of the film after the film formation has large irregularities, or is suitable for organic EL illumination to produce an unluminated color called a dark spot. section.

In addition, since the polythiophene having PSS as a dopant is absorbed in a cyan region having a wavelength of about 500 nm, the material is applied to a transparent substrate such as a transparent electrode, and is used for the function of the device by using a solid concentration or a film thickness. When the conductivity is required, there is also a penetration of the component. The rate is causing the problem.

Patent Document 2 proposes to use a π-conjugated polymer formed by a repeating unit selected from the group consisting of thiophene, selenophene, anthracene, pyrrole, aniline, and a polycyclic aromatic compound to wet the organic solvent, and to contain 50% or more is a conductive polymer composition formed of a conductive polymer of a fluorinated acid polymer in which a cation is neutralized, and Patent Document 2 discloses that water, a π-conjugated polymer is combined in any order. The precursor monomer, the fluorinated acid polymer, and the oxidizing agent become an aqueous dispersion of the conductive polymer.

However, there is a problem that the particles of the conventional conductive polymer are aggregated in the dispersion liquid after the synthesis, and further, when the organic solvent which is a high conductivity agent is added as a coating material, aggregation is promoted, and the filtration property is changed. difference. When spin coating was performed in an unfiltered state, a flat film was not obtained due to the influence of particle agglomerates, and as a result, coating failure was caused.

Further, a polythiophene type using PSS as a dopant can also be used as a hole injection layer. At this time, a hole injection layer is provided between the transparent electrode such as ITO and the light-emitting layer. In order to ensure conductivity by the transparent electrode at the bottom, high conductivity is not required in the hole injection layer. There is no need for dark spots or high hole transmission capability in the hole injection layer.

[Advanced technical literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent No. 5264723

As described above, the polythiophene-based conductive polymer having a PSS such as a highly-preferable PEDOT-PSS as a dopant has high conductivity but absorbs in the visible light region and has poor transparency, and is condensed in an aqueous dispersion state. The problem is high, and it is difficult to carry out filtration and refining, and there is a problem that film formation property by spin coating or surface roughness of a film formation part is bad.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a conductive polymer composite which is excellent in filterability, has good film formability by spin coating, and has high transparency and good flatness when formed into a film. Conductive film.

In order to solve the above problems, the present invention provides a conductive polymer composite comprising the following components: (A) a π-conjugated polymer, and (B) a repeating unit a 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,

(wherein R ¹ is a hydrogen atom or a methyl group, R ² is a fluorine atom or a trifluoromethyl group, a Z-based single bond or -C(=O)-O-, m is an integer of 1 to 4, and a is 0. <a≦1.0).

When the conductive polymer composite is used as described above, the filterability is good, and the film formation property of the organic or inorganic substrate by spin coating is also good, and when the film is formed, a conductive film having high transparency and good flatness can be formed.

In this case, the repeating unit a in the component (B) is preferably one or more selected from the group consisting of the repeating units a1 and a2 shown in the following general formulas (1-1) and (1-2).

(wherein R ^1-1 and R ^1-2 each independently represent a hydrogen atom or a methyl group, and R ^2-1 and R ^2-2 each independently represent a fluorine atom or a trifluoromethyl group, and m ₁ and m ₂ are each Each independently represents an integer from 1 to 4, and a1 and a2 are 0≦a1≦1.0, 0≦a2≦1.0, 0<a1+a2≦1.0).

As described above, the component (B) is preferably as described above, and the filterability and film formability of the material and the affinity for the organic solvent or the substrate are also improved, and the transmittance after film formation is also improved.

Further, in this case, the component (B) further preferably has a repeating unit b represented by the following general formula (2).

(wherein b is 0 < b < 1.0).

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

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

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

Further, in this case, the component (A) is selected from the group consisting of pyrrole, thiophene, selenophene, porphin, aniline, polycyclic aromatic compound, and one or more kinds of precursor monomers in a group of such derivatives. Better.

If it is such a monomer, it is easy to polymerize, and since the stability in air is good, the component (A) can be easily synthesized.

Further, in this case, the conductive polymer composite system preferably has dispersibility in water or an organic solvent.

Moreover, the present invention provides a substrate of a conductive film formed by the above conductive polymer composite.

As described above, the conductive polymer composite system of the present invention can form a conductive film by coating or film formation on a substrate or the like.

Moreover, since the conductive film formed as described above is electrically conductive and excellent in transparency, it can have a function as a transparent electrode layer.

As described above, in the conductive polymer composite of the present invention, the dopant polymer of the (B) component containing a sulfonic acid group of a super acid is formed by complexing with the π-conjugated polymer of the component (A). In the low-viscosity state, the filterability is good, the film formation property by spin coating is good, and the durability is high, transparency, flatness, and conductivity can be formed by light or heat lifting stability when forming a film. A good conductive film. In addition, when the conductive polymer composite is used, the affinity for the organic solvent and the organic substrate is good, and the film formation property of either the organic substrate or the inorganic substrate is good.

Moreover, the conductive film formed by such a conductive polymer composite is excellent in transparency and the like, and has a function as a transparent electrode layer.

[Formation of the Invention]

As described above, the required filterability is good, and the film formation property by spin coating is also good, and the formation of a material for forming a conductive film of a conductive film having high transparency and good flatness can be formed when a film is formed.

As a result of careful examination by the inventors of the present invention, it has been found that polystyrenesulfonic acid (PSS), which is widely used as a dopant for a conductive polymer material, has a fluorine atom or a trifluoromethyl group. a dopant polymer of a repeating unit of benzenesulfonic acid, a dopant polymer of a super acid and a π-conjugated polymer strongly interact with each other, and a visible light absorption region of the π-conjugated polymer shifts to improve transparency. Strong ionic bonding with a π-conjugated polymer and a dopant polymer to enhance light or heat stability. In addition, since the film forming property by spin coating is improved by the filter property, and the flatness is further improved when the film is further formed, the present invention has been completed.

That is, the present invention is a conductive polymer composite characterized by comprising the following components: (A) a π-conjugated polymer, and (B) a repeating unit a represented by the following general formula (1), a dopant polymer having a weight average molecular weight ranging from 1,000 to 500,000,

(wherein R ¹ is a hydrogen atom or a methyl group, R ² is a fluorine atom or a trifluoromethyl group, a Z-based single bond or -C(=O)-O-, m is an integer of 1 to 4, and a is 0. <a≦1.0).

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

[(A) π conjugated polymer]

The conductive polymer composite system of the present invention contains a π-conjugated polymer as the component (A). The component (A) may be formed by polymerizing a precursor monomer (organic monomer molecule) as long as a π-conjugated chain (a structure in which a single bond and a double bond are alternately continuous) is formed.

Examples of such a precursor monomer include pyrrole and thiophene. Monocyclic aromatics such as thiophene ethylene, selenophene, porphin, phenene, styrene, and aniline; polycyclic aromatics such as acenes; acetylenes, etc. A single polymer or a copolymer of the body is used as the component (A).

Among the above monomers, it is easy to polymerize, and in terms of stability in air, pyrrole, thiophene, selenophene, porphin, aniline, polycyclic aromatic compound, and these derivatives are preferred, pyrrole, thiophene The aniline and the derivatives are particularly preferred, but are not limited thereto.

When the conductive polymer composite system of the present invention contains, as a component (A), in particular, a polythiophene, it has a high conductivity and a high transparency in a visible light region, and can be developed toward a touch panel or an organic EL display, organically. EL lighting and other uses. On the other hand, although the conductive polymer composite system of the present invention contains polyaniline as the component (A), it is difficult to apply to the display-related field because the absorption of the visible light region is large and the conductivity is lower than that of the polythiophene. It has low viscosity and is easy to spin coating, and it can be used for the application of the top coat of the upper film to prevent the charge of electrons in EB development.

In addition, even if the single component of the π-conjugated polymer is unsubstituted, sufficient conductivity can be obtained in the component (A), but in order to further improve conductivity, an alkyl group, a carboxyl group, or a sulfonic acid group can also be used. a monomer substituted with an alkoxy group, a hydroxyl group, a cyano group, a halogen atom or the like.

Specific examples of the monomers of the azoles, thiophenes, and anilines include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, and 3-butylpyrrole. , 3-octylpyrrole, 3-mercaptopyridyl Ol, 3-dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl-4-carboxypyrrole, 3-methyl-4- Carboxyethylpyrrole, 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-mercaptothiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3- Phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3- Hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydrocarbyl Thiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxy Thiophene, 3,4-diheptyloxythiophene, 3, 4-dioctyloxythiophene, 3,4-dimethoxythiophene, 3,4-dodedodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-ethylenedithiothiophene, 3,4 - propylene dioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl 4-carboxythiophene, 3-methyl-4-carboxymethylthiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, 3,4-(2, 2-Dimethylpropionioxy)thiophene, 3,4-(2,2-diethylpropionioxy)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, 2-butyl Aniline, 3-butylaniline, 2-isobutyl Aniline, 3-isobutylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-anilinesulfonic acid, 3-anilinesulfonic acid, and the like.

Wherein the (co)polymer is one or two selected from the group consisting of pyrrole, thiophene, N-methylpyrrole, 3.methylthiophene, 3-methoxythiophene, and 3,4-ethylenedioxythiophene. It is suitable for use in terms of resistance value and reactivity. Further, a single polymer of pyrrole or 3,4-ethylenedioxythiophene is more preferable because it has high conductivity.

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

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

[(B) dopant polymer]

The conductive polymer composite system of the present invention contains a dopant polymer as the component (B). The dopant polymer of the component (B) contains a repeating unit a represented by the following general formula (1), and a super-strong acid polyanion of benzenesulfonic acid substituted with a fluorine atom or a trifluoromethyl group.

(wherein R ¹ is a hydrogen atom or a methyl group, R ² is a fluorine atom or a trifluoromethyl group, a Z-based single bond or -C(=O)-O-, m is an integer of 1 to 4, and a is 0. <a≦1.0).

In the general formula (1), R ¹ is a hydrogen atom or a methyl group.

R ² is a fluorine atom or a trifluoromethyl group.

Z series single bond or -C(=O)-O-.

m is an integer from 1 to 4.

a is 0 < a ≦ 1.0, preferably 0.2 ≦ a ≦ 1.0.

As a single system to which the repeating unit a is given, the following may be specifically listed.

(In the formula, R ¹ is the same as defined above, and an X-based hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or a ruthenium compound).

In addition, it is preferable that the repeating unit a represented by the general formula (1) contains one or more kinds of the repeating units a1 and a2 selected from the following general formulas (1-1) and (1-2).

(wherein R ^1-1 and R ^1-2 each independently represent a hydrogen atom or a methyl group, and R ^2-1 and R ^2-2 each independently represent a fluorine atom or a trifluoromethyl group, and m ₁ and m ₂ are each Each independently represents an integer from 1 to 4, a1 and a2 are 0≦a1≦1.0, 0≦a2≦1.0, 0<a1+a2≦1.0),

If the component (B) is used, the filterability and film formability of the material are improved, and the affinity for the organic solvent or the substrate is improved, and the transmittance after film formation is also improved. In particular, as the component (B), the effects of the present invention can be more reliably obtained by including both of the above-described repeating units a1 and a2.

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

(wherein b is 0 < b < 1.0).

As a single system that assigns the repeating unit b, it can be specifically listed The following.

(wherein X ₂ is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or an anthracene compound).

In the case of the X, X ₂ -based amine compound, (P1a-3) described in paragraph [0048] of JP-A-2013-228447.

Here, as described above, a is 0 < a ≦ 1.0, preferably 0.2 ≦ a ≦ 1.0. If 0 < a ≦ 1.0 (that is, if the repeating unit a is contained), the effect of the present invention can be obtained, and if 0.2 ≦ a ≦ 1.0, a better effect can be obtained. Further, when the repeating unit a contains one or more selected from the group consisting of the repeating units a1 and a2, 0≦a1≦1.0, 0≦a2≦1.0, and 0<a1+a2≦1.0 is preferable, preferably 0≦. A1≦0.9,0≦a2≦0.9, and 0.1≦a1+a2≦0.9, more preferably 0≦a1≦0.8, 0≦a2≦0.8, and 0.2≦a1+a2≦0.8.

Further, from the viewpoint of improving the conductivity when the repeating unit b is contained, 0.3 ≦ b < 1.0 is preferable, and 0.3 ≦ b ≦ 0.8 is more preferable.

Further, the ratio of the repeating unit a to the repeating unit b is preferably 0.2 ≦ a ≦ 0.7 and 0.3 ≦ b ≦ 0.8, and 0.3 ≦ a ≦ 0.6 and 0.4 ≦ b ≦ 0.7 is more preferable.

Further, the dopant polymer of the component (B) may have a repeating unit c other than the repeating unit a and the repeating unit b, and examples of the repeating unit c include a styrene type, a vinyl naphthalene type, and a vinyl decane type. , hydrazine, hydrazine, vinyl carbazole, etc.

As a single system to which the repeating unit c is given, the following may be specifically listed.

The method of synthesizing the dopant polymer of the component (B) is, for example, heating polymerization by adding a radical polymerization initiator to the monomer selected in the monomer of the repeating unit a to c in an organic solvent. And a method of obtaining a (co)polymer dopant 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.

As a radical polymerization initiator, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2 can be listed. , 2'-azobis(2-methylpropionate), benzammonium peroxide, lauric acid peroxide, and the like.

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

In the dopant polymer of the component (B), the single system to which the repeating unit a is added may be one type or two or more types, and it is preferable to combine the monomer of the methacryl type and the styrene type in order to improve the polymerizability.

Further, when two or more types of monomers to which the repeating unit a is added are used, each monomer may be randomly copolymerized or may be block copolymerized. When a block copolymer (block copolymer) is obtained, a repeating portion formed by two or more kinds of repeating units a is aggregated to form an island structure, and a specific structure is formed around the dopant polymer, and conductivity can be expected to be improved. advantage.

Further, the single system to which the repeating units a to c are added may be randomly copolymerized, or each may be block copolymerized. At this time, the block copolymer is also produced in the same manner as in the case of repeating the unit a, and the advantage of the conductivity improvement can be expected.

When random copolymerization is carried out by radical polymerization, polymerization is carried out by mixing a monomer or a radical polymerization initiator which is copolymerized and heating. The first monomer is initially polymerized in the presence of a radical polymerization initiator, and then, when the second monomer is added, one side of the polymer molecule is a structure in which the first monomer has been polymerized, and the other side is The second monomer has been subjected to polymerization. However, at this time, the monomer of the first part in the middle portion and the repeating unit of the second monomer are mixed, and the block copolymer has a different form. When a block copolymer is formed by radical polymerization, living radical polymerization is preferably used.

A method of polymerizing an active radical called RAFS (Reversible addition Fragmentation Chain Transfer Polymerization) is to start the polymerization by using the monomer of the first monomer by the radical of the polymer terminal, which is added at the stage of consumption. The second monomer can form a diblock copolymer of a block of a repeating unit of the first monomer and a repeating unit of the second monomer. Further, the first monomer may be used for the initial polymerization, and the second monomer may be added at the stage of consumption, and then the third monomer may be formed by adding the third monomer.

When the RAFT polymerization is carried out, it is characterized in that a narrowly dispersed polymer having a narrow molecular weight distribution (dispersion degree) is formed, and in particular, a polymer having a narrow molecular weight distribution can be formed when the monomer is added once for RAFT polymerization.

Further, in the dopant polymer of the component (B), the molecular weight distribution (Mw/Mn) is preferably 1.0 to 2.0, and the narrow dispersion of 1.0 to 1.5 is particularly preferable. If it is narrowly dispersed, the transmittance of the conductive film formed by using the conductive polymer composite using it can be prevented from becoming low.

Chain transfer agent is required for RAFT polymerization, specifically Listed 2-cyano-2-propylbenzothiophenebenzoic acid, 4-cyano-4-(phenylcarbono thioylthio)pentanoate (HPP), 2-cyano 2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecyl-pyrimidinylthiocarbonyl)sulfanyl]pentanoic acid, 2-(dodecylthiosulfuric acid Carbonyl)-2-methylpropionic acid, cyanomethyldodecylthiocarbonate, cyanomethylmethyl(phenyl)carbonate, bis(thiobenzhydrazide) disulfide , bis(dodecyl-thiocarbonylpyrimidine) disulfide. Among these, 2-cyano-2-propylbenzothiophenebenzoic acid is particularly preferred.

When the dopant polymer of the component (B) contains the above repeating unit c, the ratio of the repeating units a to c is 0 < a ≦ 1.0, 0 ≦ b < 1.0, 0 < c < 1.0, preferably 0.1. ≦a≦0.9, 0.1≦b≦0.9, 0<c≦0.8, more preferably 0.2≦a≦0.8, 0.2≦b≦0.8, 0<c≦0.5.

In addition, a+b+c=1 is preferable.

The dopant polymer of the component (B) has a weight average molecular weight of 1,000 to 500,000, preferably in the range of 2,000 to 200,000. When the weight average molecular weight is less than 1,000, the heat resistance is deteriorated, and the uniformity of the complex solution with the component (A) is deteriorated. On the other hand, when the weight average molecular weight exceeds 500,000, in addition to deterioration in conductivity, the viscosity-enhancing workability is also deteriorated, and the dispersibility to water or an organic solvent is lowered.

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

Further, as the monomer constituting the dopant polymer of the component (B), a monomer having a sulfonic acid group may be used, and a lithium salt, a sodium salt, a potassium salt, an ammonium salt or a phosphonium salt of a sulfonic acid group may be used. The polymerization reaction is carried out using a monomer, and is converted into a sulfonic acid group by using an ion exchange resin after the polymerization.

[conductive polymer composite]

The conductive polymer composite of the present invention contains the π-conjugated polymer of the above (A) component and the dopant polymer of the component (B), and the dopant polymer of the component (B) is located at (A) The π-conjugated polymer of the component forms a complex.

The conductive polymer composite system of the present invention preferably has dispersibility in water or an organic solvent, and spin-coating film-forming property or film flatness on an inorganic or organic substrate (a substrate on which an inorganic film or an organic film is formed on a substrate surface) good.

(Manufacturing method of conductive polymer composite)

A composite system of the component (A) and the component (B), for example, a monomer which is a raw material of the component (A) in an aqueous solution of the component (B) or a mixed solution of the component (B) in water or an organic solvent (preferably pyrrole or thiophene) An oxidizing agent may be obtained by adding an oxidizing agent, an oxidizing agent, or an oxidizing agent as the case may be, and performing oxidative polymerization.

As the oxidizing agent and the oxidation catalyst, peroxodisulfate (persulfate) such as ammonium peroxodisulfate (ammonium persulfate), sodium persulfate (sodium persulfate), potassium peroxydisulfate (potassium persulfate), and chlorination can be used. Iron, sulfuric acid Transition metal compounds such as iron and copper chloride, metal oxides such as silver oxide and cerium oxide, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzamidine peroxide, and oxygen.

As the reaction solvent used in the oxidative polymerization, water or a mixed solvent of water and a solvent can be used. The solvent used herein may be mixed with water, and is preferably a solvent which can dissolve or disperse the component (A) and the component (B). For example, N-methyl-2-pyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethylammonium, hexamethylenephosphonium Polar solvents such as triamine; alcohols such as methanol, ethanol, propanol, and butanol; ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, D-glucose, D - aliphatic polyols such as sorbitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl glycol; a carbonate compound such as ethyl ester or propyl carbonate; a cyclic ether compound such as dioxane or tetrahydrofuran; a dialkyl ether, an ethylene glycol monoalkyl ether, a ethylene glycol dialkyl ether, a propylene glycol monoalkyl ether , propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, and polypropylene glycol dialkyl ether and other chain ethers; 3-methyl-2-oxazolinone and other heterocyclic compounds; acetonitrile, glutaronitrile And nitrile compounds such as methoxyacetonitrile, propionitrile, and benzonitrile. These solvents may be used singly or as a mixture of two or more types. The mixing ratio of the solvent which can be mixed with water with respect to water is preferably 50% by mass or less of the entire reaction solvent.

Further, in addition to the dopant polymer of the component (B), an anion which can be doped with the π-conjugated polymer of the component (A) may be used in combination. As such an anion, it is derived from the dedoping property of the π-conjugated polymer, the dispersibility of the conductive polymer composite, heat resistance, and adjustment of environmental resistance. From the viewpoint, an organic acid is preferred. Examples of the organic acid include organic carboxylic acids, phenols, and organic sulfonic acids.

The organic carboxylic acid can be used for one or two or more carboxyl groups in an aliphatic, aromatic, cyclic aliphatic or the like. For example, 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, trichloroacetic acid , trifluoroacetic acid, nitroacetic acid, triphenylacetic acid, and the like.

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

As the organic sulfonic acid, one or two or more sulfonic acid groups may be used in an aliphatic, aromatic, or cyclic aliphatic group. As the organic sulfonic acid containing one sulfonic acid group, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethane Sulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, colistin methanesulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amine 2-naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 3-aminopropanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonate Acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzene Sulfonic acid, nonylbenzenesulfonic acid, nonylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, cetylbenzenesulfonic acid, 2,4 -dimethylbenzenesulfonic acid, two Propylbenzenesulfonic 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-acetamido-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid , p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, 4-amino-1-naphthalene A sulfonic acid group containing a sulfonic acid group, such as a sulfonic acid, 8-chloronaphthalene-1-sulfonic acid, a naphthalenesulfonic acid formalin polycondensate, a melaminesulfonic acid formalin polycondensate, or the like.

Examples of the organic sulfonic acid containing two or more sulfonic acid groups include ethane disulfonic acid, butane disulfonic acid, pentane disulfonic acid, decane disulfonic acid, isophthalic disulfonic acid, and phthalic acid. Sulfonic acid, terephthalic acid, toluene disulfonic acid, xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonate Acid, diethylbenzenedisulfonic acid, dibutylbenzenedisulfonic acid, naphthalene disulfonic acid, methylnaphthalene disulfonic acid, ethylnaphthalene disulfonic acid, dodecyl naphthalene disulfonic acid, pentadecyl Naphthalene disulfonic acid, butyl naphthalene disulfonic acid, 2-amino-1,4-benzene disulfonic acid, 1-amino-3,8-naphthalene disulfonic acid, 3-amino-1,5-naphthalene Disulfonic acid, 8-amino-1-naphthalene-3,6-disulfonic acid, sulfonium disulfonic acid, butyl sulfonium disulfonic acid, 4-acetamide-4'-isothiocyanate-2 , 2'-disulfonic acid, 4-acetamimidin-4'-guanidinium isothiocyanate-2,2'-disulfonic acid, 4-acetamidine-4'-maleimide oxime-2, 2'-diacetamide-4'-maleimidyl stilbene-2,2'-disulfonate, 1-acetoxypurine-3,6,8-trisulphonic acid, 7-amino-1, 3,6-naphthalenetrisulfonic acid, 8-aminenaphthalene-1,3,6-trisulphonic acid, 3-amino-1,5,7-naphthalenetrisulfonic acid and the like.

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

The composite of the component (A) and the component (B) thus obtained may be used after being refined by a crystallizer such as a homogenizer or a ball mill.

It is preferred to use a mixing dispersing machine which imparts high shearing force to the grain refining. Examples of the mixing and dispersing machine include a homogenizer, a high pressure homogenizer, a bead mill, and the like, and among these, a high pressure homogenizer is preferred.

Specific examples of the high-pressure homogenizer include Nanomizer manufactured by Yoshida Machinery Co., Ltd., micro-fluidizer manufactured by Powrex Corporation, and ULTIMAIZER manufactured by Sugino Machinery Co., Ltd., and the like.

Examples of the dispersion treatment using a high-pressure homogenizer include a treatment for colliding the composite solution prior to the application of the dispersion treatment by high pressure, a treatment using a high-pressure passage hole or a slit, and the like.

The impurities may be removed by filtration, ultrafiltration, dialysis or the like before or after the granulation, and may be purified by a cation exchange resin, an anion exchange resin, a chelating resin or the like.

Further, the total content of the component (A) and the component (B) in the conductive polymer composite 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% by mass or more, sufficient conductivity can be obtained, and when it is 5.0% by mass or less, a uniform conductive coating film can be easily obtained.

The content of the component (B) is preferably in the range of 0.1 to 10 moles of the sulfonic acid group in the component (B), and preferably in the range of 1 to 7 moles. . When the sulfonic acid 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 ensured. Further, when the sulfonic acid group in the component (B) is 10 mol or less, the content of the component (A) is moderate, and sufficient conductivity can be obtained.

Examples of the organic solvent which can be added to the aqueous solution of the polymerization reaction or the monomer which can be diluted include alcohols such as methanol, ethanol, propanol and butanol, ethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, and 1,3-. Butylene glycol, 1,4-butanediol, D-glucose, D-glucitol, isoprene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,9-nonanediol, neopentane Aliphatic polyols such as diols, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, polyethylene glycol dialkyl ethers , chain ethers such as polypropylene glycol dialkyl ether, cyclic ether compounds such as dioxane and tetrahydrofuran, cyclohexanone, methyl amyl ketone, ethyl acetate, butanediol monomethyl ether, propylene glycol monomethyl Ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, ethyl pyruvate, butyl acetate, 3-methoxy Methyl propionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono-tert-butyl ether acetate, γ-butyrolactone, N-methyl a polar solvent such as -2-pyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl hydrazine, hexamethylenephosphonium triamine, ethylene carbonate And C a carbonate compound such as an olefin carbonate or a heterocyclic compound such as 3-methyl-2-oxazolidinone; a nitrile compound such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile or benzonitrile; and the like.

Further, the amount of the organic solvent used is preferably from 0 to 1,000 mL, particularly preferably from 0 to 500 mL, per mole of the monomer. When the amount of the organic solvent used is 1,000 mL or less, it is economical because the reaction container is not excessively large.

[other ingredients] (surfactant)

In the present invention, in order to improve the wettability to a workpiece such as a substrate, a surfactant may be added. Examples of such a surfactant include nonionic, cationic, and anionic surfactants. Specific examples thereof include nonionic surfactants such as oxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylate, sorbitan ester, and polyoxyethylene sorbitan ester, and alkyl group III. Cationic surfactants such as methyl ammonium chloride, alkyl benzyl ammonium chloride, alkyl or alkyl allyl sulfate, alkyl or alkyl allyl sulfonate, dialkyl sulfosuccinic acid Anionic surfactant such as salt, amphoteric surfactant such as amino acid type or betaine type, acetylene alcohol surfactant, acetylene alcohol surfactant which is oxidized by polyethylene or oxidized by polypropylene, etc. .

(high conductivity agent)

In the present invention, as a purpose of improving the electrical conductivity of the conductive polymer composite It is also possible to add an additional organic solvent with the main agent. Examples of the solvent to be added include polar solvents, and specific examples thereof include ethylene glycol, polyethylene glycol, dimethyl hydrazine (DMSO), dimethylformamide (DMF), and N-methyl-2-pyrrolidone ( NMP), cyclobutyl hydrazine and these mixtures. The addition amount is preferably 1.0 to 30.0% by mass, particularly preferably 3.0 to 10.0% by mass.

(neutralizer)

In the aqueous solution of the conductive polymer composite of the present invention, the pH is acidic. For the purpose of neutralization, the nitrogen-containing aromatic cyclic compound described in paragraphs [0033] to [0045] of JP-A-2006-96975 may be added, and the paragraph [0127] described in Japanese Patent No. 5264723 may be added. The cations control the pH to neutral. The rust is prevented by controlling the pH of the solution to be near neutral and suitable for use in a printing press.

As described above, in the conductive polymer composite of the present invention, the filterability and the film formability by spin coating are good, and the transparency is high, and a conductive film having a low surface roughness can be formed.

[conductive film]

The conductive polymer composite (solution) obtained as described above can be formed into a conductive film by being applied to a workpiece such as a substrate. Examples of the coating method of the conductive polymer composite (solution) include coating by spin coating, bar coating, dip coating, spot coating, spray coating, roll coating, screen printing, flexographic printing, and gravure printing. Printing, inkjet printing, etc. After coating, it can be formed by heat treatment such as hot air circulation furnace or hot plate, and can be formed by IR or UV irradiation. Electric film.

Thus, the conductive polymer composite system of the present invention can be coated or formed into a film by a substrate or the like to obtain a conductive film. Moreover, the conductive film formed in this way has a function as a transparent electrode layer and a hole injection layer because it is excellent in electrical conductivity and transparency.

[substrate]

The present invention also provides a substrate of a conductive film formed by the above-described conductive polymer composite of the present invention.

Examples of the substrate include a compound semiconductor wafer such as a glass substrate, a quartz substrate, a mask base substrate, a resin substrate, a tantalum wafer, a gallium arsenide wafer, and an indium phosphide wafer, and a flexible substrate. Further, it may be applied to a photoresist film to be used as an antistatic top coat.

As described above, in the conductive polymer composite of the present invention, the dopant polymer of the (B) component containing a sulfonic acid group of a super acid is formed by complexing with the π-conjugated polymer of the component (A). In the low-viscosity state, the filterability is good, and the film formation property by spin coating is good, and when the film is formed, a conductive film having excellent transparency, flatness, durability, and conductivity can be formed. In addition, when the conductive polymer composite is used, the affinity for the organic solvent and the organic substrate is good, and the film formation property of either the organic substrate or the inorganic substrate is good.

Moreover, the conductive film formed by such a conductive polymer composite is excellent in conductivity, transparency, and the like, and has a function as a transparent electrode layer.

[Examples]

Hereinafter, the present invention will be specifically described using a synthesis example, a preparation example, a comparative preparation example, an example, and a comparative example, but the present invention is not limited thereto.

[Synthesis of dopant polymer] (Synthesis Examples 1 to 5)

A solution of dimethyl 2,2'-azobis(isobutyric acid) dissolved in methanol was taken for 4 hours under a nitrogen atmosphere in a solution of the stirred monomer which had been dissolved in the solution at 60 ° C in methanol. Stir for 4 hours. After cooling to room temperature, ethyl acetate was added dropwise with vigorous stirring, and the resulting solid component was filtered and dried under vacuum at 50 ° C for 15 hours. Then, the obtained white polymer was dissolved in methanol, and the ion exchange resin was used. The cation of the body is converted into a hydrogen atom and converted into a sulfonic acid group.

The dopant polymers 1 to 5 shown below were obtained by such a method.

Dopant polymer 1

Weight average molecular weight (Mw) = 43,000

Molecular weight distribution (Mw/Mn) = 1.77

Dopant polymer 2

Weight average molecular weight (Mw) = 42,000

Molecular weight distribution (Mw/Mn)=1.79

Dopant polymer 3

Weight average molecular weight (Mw) = 35,000

Molecular weight distribution (Mw/Mn)=1.69

Dopant polymer 4

Weight average molecular weight (Mw) = 33,000

Molecular weight distribution (Mw/Mn)=1.69

Dopant polymer 5

Weight average molecular weight (Mw) = 41,000

Molecular weight distribution (Mw/Mn)=1.92

(Synthesis Example 6)

The diblock dopant polymer was synthesized by the following RAFT polymerization.

2-Cyano-2-propylbenzodisulfide salt and 2,2'-azobisisobutyronitrile were dissolved in methanol under a nitrogen atmosphere, and the solution was stirred at 64 ° C for 3 hours under a nitrogen atmosphere. A solution of benzyltrimethylammonium 2,3,5,6-tetrafluorostyrene-4-sulfonate dissolved in methanol as a monomer of the first monomer was dropped for 2 hours in the solution, and then The solution takes 2 hours to drip as the second monomer, which has been dissolved in methanol, and the above-mentioned first monomer, etc., benzyltrimethylammonium 4-benzene The solution of the ethylene sulfonate was stirred at 64 ° C for 4 hours after the completion of the dropwise addition. After cooling to room temperature, ethyl acetate was added dropwise with vigorous stirring, and the resulting solid component was filtered, and dried under vacuum at 50 ° C for 15 hours to obtain a red polymer.

The obtained red polymer was dissolved in methanol, and the benzyltrimethylammonium salt was converted into a sulfonic acid group using an ion exchange resin to obtain a diblock dopant polymer 6.

Dopant polymer 6

Weight average molecular weight (Mw) = 21,000

Molecular weight distribution (Mw/Mn) = 1.30

[Preparation of a conductive polymer composite dispersion containing a polythiophene as a π-conjugated polymer] (Modulation example 1)

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

The mixed solution thus obtained was kept at 30 ° C, and 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water was slowly added while stirring. 2.3 g of an oxidizing catalyst solution of iron sulfate was stirred for 4 hours to cause a reaction.

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

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

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by an ultrafiltration method. This operation was repeated 5 times to obtain 1.3% by mass of the cyan conductive polymer composite dispersion 1 .

The ultrafiltration conditions are as follows.

Cut-off molecular weight of ultrafiltration membrane: 30K

Cross flow

Supply flow rate: 3,000 mL / min

Membrane partial pressure: 0.12Pa

In addition, other modulation examples were also subjected to ultrafiltration under the same conditions.

(Modulation example 2)

12.5 g of the dopant polymer 1 was changed to 11.0 g of the dopant polymer 2, the amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, and the amount of sodium persulfate was changed to 5.31 g. In the same manner as in Modification Example 1, the amount of iron sulfate was changed to 1.50 g, and a guide was obtained. Electropolymer composite dispersion 2.

(Modulation Example 3)

12.5 g of the dopant polymer 1 was changed to 10.5 g of the dopant polymer 3, the amount of 3,4-ethylenedioxythiophene was changed to 2.72 g, and the amount of sodium persulfate was changed to 6.00 g. In the same manner as in Preparation Example 1, except that the amount of the iron sulfate was changed to 1.60 g, the conductive polymer composite dispersion 3 was obtained.

(Modulation Example 4)

12.5 g of the dopant polymer 1 was changed to 10.8 g of the dopant polymer 4, and 8.40 g of sodium persulfate was changed to 4.50 g of ammonium persulfate, and the amount of 3,4-ethylenedioxythiophene was adjusted. The conductive polymer composite dispersion liquid 4 was obtained by the same method as that of the preparation example 1 except that the amount of the iron sulfate was changed to 1.23 g.

(Modulation Example 5)

12.5 g of the dopant polymer 1 was changed to 10.5 g of the dopant polymer 5, and 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, and the amount of 3,4-ethylenedioxythiophene was adjusted. The conductive polymer composite dispersion liquid 5 was obtained by the same method as that of the preparation example 1 except that the amount of the iron sulfate was changed to 1.50 g.

(Modulation Example 6)

12.5 g of the dopant polymer 1 was changed to 11.0 g of the dopant polymer 6, and 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, and the amount of 3,4-ethylenedioxythiophene was adjusted. The conductive polymer composite dispersion liquid 6 was obtained by the same method as that of the preparation example 1 except that the amount of the iron sulfate was changed to 1.50 g.

(Modulation Example 7)

A solution of 3.87 g of 3,4-ethylenedioxythiophene and 11.0 g of the dopant polymer 2 dissolved in 1,000 mL of ultrapure water was mixed at 30 °C.

The mixed solution thus obtained was kept at 30 ° C, and 8.00 g of sodium persulfate dissolved in 100 mL of ultrapure water and an oxidation catalyst solution of 2.3 g of ferric sulfate were slowly added while stirring, and stirred for 4 hours. Its reaction.

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

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

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by ultrafiltration. This operation was repeated 5 times to obtain a 1.3% by mass of cyan conductive polymer composite dispersion liquid 7.

(Modulation Example 8)

4.62 g of (2,3-Dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol and 11.0 g of dopant dissolved in 1,000 mL of ultrapure water at 30 ° C A solution of polymer 2.

The mixed solution thus obtained was kept at 30 ° C, and 8.00 g of sodium persulfate dissolved in 100 mL of ultrapure water and an oxidation catalyst solution of 2.3 g of ferric sulfate were slowly added while stirring, and stirred for 4 hours. Its reaction.

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

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

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by ultrafiltration. This operation was repeated 5 times to obtain a 1.3% by mass of cyan conductive polymer composite dispersion 8 .

(Modulation Example 9)

A solution of 4.16 g of 3,4-propylenedioxythiophene and 11.0 g of the dopant polymer 2 dissolved in 1,000 mL of ultrapure water was mixed at 30 °C.

The mixed solution thus obtained was kept at 30 ° C, and 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water was slowly added while stirring. 2.3 g of an oxidizing catalyst solution of iron sulfate was stirred for 4 hours to cause a reaction.

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

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

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by ultrafiltration. This operation was repeated 5 times to obtain a 1.3% by mass of cyan conductive polymer composite dispersion 9.

[Preparation of polyaniline-containing conductive polymer composite dispersion as π-conjugated polymer] (Modulation Example 10)

A solution of 27.3 g of 2-methoxyaniline and 45.4 g of the dopant polymer 1 dissolved in 1,000 mL of ultrapure water was mixed at 25 °C.

The mixed solution thus obtained was kept at 0 ° C, and 45.8 g of ammonium persulfate dissolved in 200 mL of ultrapure water was slowly added while stirring, and the mixture was stirred and reacted.

After concentrating the obtained reaction liquid, 4,000 mL of acetone was dropped to obtain a green powder. This green powder was again dispersed in 1,000 mL of ultrapure water, and recrystallized by purifying green powder by dropping 4,000 mL of acetone. Repeat this After three operations, the obtained green powder was redispersed in 2,000 mL of ultrapure water, and about 1,000 mL of water was removed by ultrafiltration. This operation was repeated 10 times to obtain a conductive polymer composite dispersion 10.

(Modulation Example 11)

The conductive polymer composite dispersion 11 was obtained in the same manner as in Preparation Example 10 except that 45.4 g of the dopant polymer 1 was changed to 38.2 g of the dopant polymer 2.

(Modulation Example 12)

45.4 g of the dopant polymer 1 was changed to 36.5 g of the dopant polymer 3, and the amount of 2-methoxyaniline was changed to 27.5 g, and modulation was carried out in the same manner as in Preparation Example 10 to obtain conductivity. Polymer composite dispersion 12.

(Modulation Example 13)

45.4 g of the dopant polymer 1 was changed to 41.4 g of the dopant polymer 4, and the amount of 2-methoxyaniline was changed to 27.5 g, and modulation was carried out in the same manner as in Preparation Example 10 to obtain conductivity. Polymer composite dispersion 13.

(Modulation Example 14)

45.4 g of the dopant polymer 1 was changed to 43.4 g of the dopant polymer 5, and the amount of 2-methoxyaniline was changed to 27.5 g. In the same manner as in the production example 10, the conductive polymer composite dispersion liquid 14 was obtained.

[Preparation of a conductive polymer composite dispersion containing polystyrenesulfonic acid as a dopant polymer] (Comparative modulation example 1)

A solution of 5.0 g of 3,4-ethylenedioxythiophene and 83.3 g of an aqueous solution of polystyrenesulfonic acid (18.0% by mass of Aldrich) diluted with 250 mL of ion-exchanged water was mixed at 30 °C. Otherwise, it was prepared in the same manner as in Preparation Example 1 to obtain a 1.3% by mass of cyan conductive polymer composite dispersion 15 (PEDOT-PSS dispersion).

(Comparative modulation example 2)

A solution of 27.3 g of 2-methoxyaniline and 226 g of an aqueous solution of polystyrenesulfonic acid (18.0% by mass of Aldrich) dissolved in 400 mL of ion-exchanged water was mixed at 0 °C. Otherwise, it was prepared in the same manner as in Modification Example 10 to obtain a conductive polymer composite dispersion liquid 16.

[Examples]

20 g of each of 1.3% by mass of the conductive polymer composite dispersion obtained in Preparation Examples 1 to 14 was mixed with 1 to 14, 5 g of dimethyl sulfoxide, and 0.5 g of surfactant and defoamer Surfynol 465 were separately mixed. Then, the conductive polymer composition was prepared by filtration using a regenerated cellulose filter (manufactured by ADVANTEC Co., Ltd.) having a pore size of 0.45 μm, and was designated as Example 1 ~14.

[Comparative Example]

The conductive polymer composition was prepared in the same manner as in the examples except that the conductive polymer composite dispersions 15 and 16 obtained in the preparation examples 1 and 2 were used, and Comparative Examples 1 and 2 were designated.

The conductive polymer compositions of the examples and comparative examples prepared as described above were evaluated as follows.

(filterability)

In the preparation of the conductive polymer composition of the above examples and comparative examples, when filtration was carried out using a regenerated cellulose filter having a pore size of 0.45 μm, the filter was set to ○, and the filter was clogged without being filtered. Shown in Table 1 and Table 2.

(coating property)

First, a conductive polymer composition was spin-coated (spin coating) on a Si wafer so that the film thickness of 1H-360S SPINCOATER (manufactured by MIKASA) was 100±5 nm. Then, it was baked at 120 ° C for 5 minutes using a precision high temperature machine, and a conductive film was obtained by removing a solvent. A refractive index (n, k) having a wavelength of 636 nm was obtained for this conductive film by using a spectroscopic ellipsometer VASE (manufactured by J.A. Woollam Co., Ltd.) whose incident angle was changeable. The one which can form a uniform film is evaluated as ○, and although the refractive index can be measured but the defect or partial streaks of the particles derived from the film are generated, it is evaluated as × and is shown in Tables 1 and 2.

(penetration rate)

The transmittance of FT = 200 nm for light having a wavelength of 550 nm was calculated by using the refractive index (k) measured by a spectroscopic ellipsometer (VASE) whose incident angle was changeable. The results are shown in Table 1.

(Conductivity)

First, 1.0 mL of a conductive polymer composition was dropped on a SiO ₂ wafer having a diameter of 4 inches (100 mm), and after 10 seconds, the entire coating was spin-coated using a spin coater. The spin coating conditions were adjusted so that the film thickness became 100 ± 5 nm. The film was baked at 120 ° C for 5 minutes using a precision high temperature machine, and a conductive film was obtained by removing the solvent.

The conductivity (S/cm) of the obtained conductive film was measured by the surface resistivity (Ω/□) measured using Hiresta-Up MCP-HT450 and Loresta-GP MCP-T610 (manufactured by Mitsubishi Chemical Corporation). ) The measured value of the film thickness is obtained. The results are shown in Tables 1 and 2.

(Surface roughness)

A conductive film was obtained on a 4 inch (100 mm) diameter SiO ₂ wafer in the same manner as the conductivity evaluation method. RMS (root mean square roughness) was measured by AFM NANO-IM-8 (manufactured by Image Metrology Co., Ltd.). The results are shown in Tables 1 and 2.

(viscosity)

The solid content of the conductive polymer composition was adjusted to 1.3 wt%, and the liquid temperature was adjusted to 25 °C. The attached special measuring unit of the tuning fork vibrating viscometer SV-10 (manufactured by A&D Co., Ltd.) measures 35 mL, and the viscosity immediately after the preparation is measured. The results are shown in Tables 1 and 2.

[Assessment of Conductive Polymer Composition Containing Polythiophene as π Conjugated Polymer]

As shown in Table 1, Examples 1 to 9 containing a polythiophene as a π-conjugated polymer and having a dopant polymer having a repeating unit a were excellent in filterability and coated by a spin coater. A uniform coating film is obtained. Further, the conductivity is high, the transmittance to visible light rays of λ = 550 nm is also good, and the surface roughness is also good.

On the other hand, Comparative Example 1 in which polystyrenesulfonic acid having no repeating unit a was used as a dopant polymer was poor in filterability due to high viscosity, and as a result, spin coating was caused on the film due to particles or The stripes of the bubbles do not provide a uniform coating film. Further, although the conductivity was high, the transmittance and surface roughness of visible light rays of λ = 550 nm were inferior to those of Examples 1 to 9.

[Assessment of Conductive Polymer Composition Containing Polyaniline as π Conjugated Polymer]

As shown in Table 2, Examples 10 to 14 containing a polyaniline as a π-conjugated polymer and having a dopant polymer having a repeating unit a were excellent in filterability and coated by a spin coater. A uniform coating film can be obtained, and the surface roughness of the film after coating is also good.

In addition, the conductivity of Examples 1 to 9 described above as the π-conjugated polymer-containing polythiophene deteriorated, and the conductivity was the same as that of Comparative Example 2.

On the other hand, although there will be no polyphenylene with repeating unit a Comparative Example 2, which was used as a dopant polymer, was filterable and had good coatability, but the surface roughness of Examples 10 to 14 was deteriorated.

As described above, in the conductive polymer composite of the present invention, the filterability is good in a low-viscosity state, the film formability by spin coating is also good, and transparency, flatness, and durability can be formed when a film is formed. Conductive films and hole injection layers with good properties and electrical conductivity are well understood.

Further, the present invention is not limited to the above embodiment. The above-described embodiments are exemplified, and substantially the same as the technical idea described in the claims of the present invention, and exhibiting the same effects, even if any of them are included in the technical scope of the present invention.

Claims (7)

A conductive polymer composite comprising the following components: (A) a π-conjugated polymer, and (B) a repeating unit represented by the following general formula (1-1), having a weight average molecular weight of 1,000 a dopant polymer in the range of ~500,000, (wherein R ^1-1 each independently represents a hydrogen atom or a methyl group, and R ^2-1 each independently represents a fluorine atom or a trifluoromethyl group, and m ₁ each independently represents an integer of 1 to 4, and a1 is 0< A1≦1.0). The conductive polymer composite according to the first aspect of the invention, wherein the component (B) further comprises a repeating unit b represented by the following general formula (2), (wherein b is 0 < b < 1.0). The conductive polymer composite according to claim 1 or 2, wherein the component (B) is a block copolymer. The conductive polymer composite according to claim 1 or 2, wherein the component (A) is selected from the group consisting of pyrrole, thiophene, selenophene, porphin, aniline, polycyclic aromatic compound, and the like. One or more types of precursor monomers in the group formed are polymerized. The conductive polymer composite according to claim 1 or 2, wherein the conductive polymer composite system has dispersibility in water or an organic solvent. A substrate characterized by forming a conductive film by the conductive polymer composite according to any one of claims 1 to 5. The substrate of claim 6, wherein the conductive film has a function as a transparent electrode layer.