KR101759388B1 - Conductive polymer composite and substrate - Google Patents

Abstract

Disclosed is a conductive polymer composite which has good filtration property, good film forming property by spin coating, and can form a conductive film having high transparency and good flatness when a film is formed. Wherein the conductive polymer composite comprises a dopant polymer having a weight average molecular weight in the range of 1,000 to 500,000, which comprises (A) a π conjugated polymer and (B) a repeating unit a represented by the following formula (1) .

(Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group or an ester group, A cyclic hydrocarbon group, Z is any one of a phenylene group, a naphthylene group and an ester group, and a is 0 < a? 1.0)

Description

[0001] CONDUCTIVE POLYMER COMPOSITE AND SUBSTRATE [0002]

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

The polymer having a conjugated double bond (π-conjugated system polymer) does not exhibit conductivity, but conductivity is exhibited by doping a suitable anion molecule to form a conductive polymer material (conductive polymer composition). (hetero) aromatic polymer such as polythiophene, polycelophenol, polythiourethane, polythiophene, polythiophene, polythiophene, polythiophene, polythiophene and polyaniline, and mixtures thereof. It is most often used. This is because the strong acid sulfonic acid interacts with the? -Conjugated polymer effectively.

As sulfonic acid anion dopants, sulfonic acid polymers such as polyvinylsulfonic acid and polystyrenesulfonic acid (PSS) are widely used (Patent Document 1). Also, sulfonic acid polymers include vinyl perfluoroalkyl ether sulfonic acid typified by a registered trademark and Fion, which is used for fuel cell applications.

Polystyrene sulfonic acid (PSS), which is a sulfonic acid homopolymer, has a high efficiency of doping with respect to a pi conjugated polymer since sulfonic acid is present continuously in a monomer unit with respect to the main chain of the polymer, and the dispersibility Can be improved. This is because hydrophilicity is maintained by the presence of an excess of sulfo group present in the PSS, and the dispersibility to water is remarkably improved.

The polythiophene having PSS as a dopant is expected to be a coating type conductive film material to replace ITO (indium-tin oxide) because it is highly conductive and can be handled as an aqueous dispersion. As described above, PSS is a water-soluble resin and hardly soluble in an organic solvent. Therefore, even though the polythiophene using PSS as a dopant has a high hydrophilicity, it has low affinity for an organic solvent and an organic substrate, and it is difficult to disperse the organic solvent or form an organic substrate.

In addition, when the polythiophene in which PSS is used as a dopant is used for a conductive film for organic EL lighting, for example, polythiophene having PSS as a dopant is very high in hydrophilicity as described above, Moisture is liable to remain, and the formed conductive film is liable to introduce moisture from the external atmosphere. As a result, there is a problem that the luminous efficiency of the organic EL light-emitting element is chemically changed and the moisture is aggregated with time, resulting in defects and shortening the lifetime of the entire organic EL device.

In addition, since the polythiophene in which PSS is used as a dopant has absorption in the visible region, 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 supplemented with the solid concentration or film thickness , There is also a problem that it affects the transmittance as a member.

Patent Document 2 discloses a conductive polymer composition comprising a π conjugated polymer formed from a repeating unit selected from thiophene, pyrrole, aniline and a polycyclic aromatic compound, and a conductive polymer formed from a conductive polymer containing a fluorocarbon polymer capable of being wetted with an organic solvent Polymer compositions have been proposed, and water, a precursor monomer of a π conjugated polymer, a fluorinated polymer, and an oxidizing agent are combined in an arbitrary order to form an aqueous dispersion of a conductive 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 agglomeration and deteriorates the filterability. When spin coating is performed without filtration, a flat film can not be obtained due to the influence of the particle agglomerates, which results in a problem of coating failure.

Japanese Patent Application Laid-Open No. 2008-146913 Japanese Patent Publication No. 2008-546899

As described above, the polythiophene-based conductive polymer using PSS as a dopant such as PEDOT-PSS, which has high versatility, has high transparency due to absorption in visible light and high flocculation property in the aqueous dispersion state There is a problem that filtration and purification are accompanied by difficulties and the film formation by spin coating and the surface roughness of the film formation portion are bad.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and aims to provide a conductive polymer composite which has good filtration property and good film forming property by spin coating and which can form a conductive film having high transparency and good flatness when a film is formed .

In order to solve the above problems, in the present invention,

(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 in the range of 1,000 to 500,000

And a conductive polymer.

(Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group or an ester group, A cyclic hydrocarbon group, Z is any one of a phenylene group, a naphthylene group and an ester group, and a is 0 < a? 1.0)

When such a conductive polymer composite is used, it is possible to form a conductive film having good filterability, good spin-coating property to inorganic and organic substrates, and high transparency and good flatness when formed.

It is also preferable that the repeating unit a in the component (B) includes at least one kind selected from the repeating units a1 to a6 represented by the following general formulas (1-1) to (1-6).

(Wherein, R ¹ is the same as above, a1, a2, a3, a4 , a5 and a6 are each 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0 A5? 1.0, 0? A6? 1.0, and 0 <a1 + a2 + a3 + a4 + a5 + a6?

As described above, the component (B) is preferably as described above, and the filterability of the material and the film forming property and the affinity to the organic solvent and the substrate are improved, and the transmittance after the film formation is improved.

It is also preferable that the component (B) further comprises 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, 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, telulophene, aniline, polycyclic aromatic compounds and derivatives thereof.

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

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

In addition, the present invention provides a substrate on which a conductive film is formed by the conductive polymer composite.

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

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

As described above, in the conductive polymer composite of the present invention, the dopant polymer of the component (B) containing the sulfo group of the super strong acid forms a complex with the? -Conjugate polymer of the component (A) And it is possible to form a conductive film having good transparency, flatness, durability and conductivity when a film is formed by spin coating. In addition, such a conductive polymer composite has good affinity for an organic solvent and an organic substrate, and good film-forming properties for both an organic substrate and an inorganic substrate.

Further, since the conductive film formed by such a conductive polymer composite has excellent conductivity, transparency, and the like, it can function as a transparent electrode layer.

As described above, development of a conductive film-forming material capable of forming a conductive film having good transparency and good flatness when a film is formed with good filterability and good film-forming property by spin coating has been required.

As a result of intensive studies on the above problems, the present inventors have found that by using a dopant polymer having a repeating unit having a sulfo group fluorinated at the? -Position instead of polystyrenesulfonic acid (PSS) widely used as a dopant of a conductive polymer material, It has been found that the dopant polymer strongly interacts with the pi conjugated polymer, and the visible light absorption region of the pi conjugated polymer shifts to improve the transparency. Further, it has been found that the film-forming property by spin coating is improved and the flatness at the time of film formation is also improved because the filterability is improved, and the present invention has been accomplished.

That is,

(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 in the range of 1,000 to 500,000

&Lt; / RTI &gt;

(Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group or an ester group, A cyclic hydrocarbon group, Z is any one of a phenylene group, a naphthylene group and an ester group, 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)? Conjugated polymer]

The conductive polymer composite of the present invention includes a π conjugated polymer as the component (A). The component (A) may be one 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 the air, and pyrrole, thiophene, Are particularly preferred, but are not limited thereto.

In addition, the component (A) can obtain sufficient conductivity even when the monomer constituting the π conjugated polymer is in an unsubstituted form. However, in order to further increase the conductivity, the component (A) may be an alkyl group, a carboxyl group, a sulfo group, an alkoxy group, a hydroxy group, Atoms or the like may be used.

Specific examples of the monomers of the pyrrole, thiophene and aniline are pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, Carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3- But are not limited to, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3- Roll; 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-butenedioxyphenol, 3,4-butenedioxyphenol, 3,4-butenedioxyphenol, 3,4-dipentyloxythiophene, 3,4- Thiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-carthoxythiophene, 3-methyl-4-carboxybutyl thiophene; Aniline, 2-methylaniline, 3-isobutyl aniline, 2-methoxy aniline, 2-ethoxy aniline, 2-aniline sulfonic acid and 3-aniline sulfonic acid.

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 high conductivity.

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 polymer composite of the present invention comprises a dopant polymer as the component (B). The dopant polymer of the component (B) is a super strong acid anion containing a sulfonic acid fluorinated at the? -Position containing the repeating unit a represented by the following general formula (1).

(Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group or an ester group, A cyclic hydrocarbon group, Z is any one of a phenylene group, a naphthylene group and an ester group, and a is 0 < a? 1.0)

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

R ² is any of a single bond, an ester group, a straight, branched or cyclic hydrocarbon group of 1 to 12 carbon atoms which may have either or both of an ether group and an ester group, For example, an alkylene group, an arylene group, and an alkenylene group.

Z is any one of a phenylene group, a naphthylene group and an ester group.

a is 0 < a &amp;le; 1.0, preferably 0.2 a &amp;le; 1.0.

It is preferable that the repeating unit a includes at least one kind selected from the repeating units a1 to a6 represented by the following general formulas (1-1) to (1-6).

(Wherein, R ¹ is the same as above, a1, a2, a3, a4 , a5 and a6 are each 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0 A5? 1.0, 0? A6? 1.0, and 0 <a1 + a2 + a3 + a4 + a5 + a6?

When such a component (B) is used, a dispersion of the component (A) when formed into a complex can form a conductive film having good filterability, good film forming property by spin coating, and high transparency and excellent flatness when formed.

Specific examples of the monomer providing the repeating unit a include the following.

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

The component (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.

Specific examples of the monomer providing 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 compound or a sulfonium compound)

When X ₁ and X ₂ are amine compounds, (P1a-3) described in paragraph [0048] of JP-A-2013-228447 can be cited as an example.

Here, as described above, a satisfies 0 < a &amp;le; 1.0, and preferably 0.2 a &amp;le; 1.0. When 0 &lt; a &amp;le; 1.0 (i.e., when the repeating unit a is included), the effect of the present invention 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 a to the repeating unit b is preferably 0.2? A? 0.7 and 0.3? B? 0.8, more preferably 0.3? A? 0.6 and 0.4? B? 0.7.

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 styrene type, vinyl naphthalene type, vinylsilane type, Naphthylene, indene, vinylcarbazole, and the like.

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

As a method for synthesizing the dopant polymer of the component (B), for example, a desired monomer among the monomers providing the above-mentioned repeating units a to c is subjected to heat polymerization by adding a radical polymerization initiator in an organic solvent, A polymer dopant polymer can be obtained.

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 Propionate), benzoyl peroxide, and lauroyl peroxide.

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), the monomers providing the repeating unit a may be one kind or two or more kinds, but it is preferable to combine methacryl type and styrene type monomers which improve the polymerizability.

When two or more kinds of monomers providing the repeating unit a are used, each of the monomers may be randomly copolymerized or may be copolymerized with a block. In the case of a block copolymerization polymer (block copolymer), it is advantageous that a specific structure is generated around the dopant polymer by forming a sea-island structure even when the repeating portions including two or more kinds of the repeating units a are aggregated Is expected.

Further, the monomers providing the repeating units a to c may be randomly copolymerized, or each may be copolymerized with a block. Also in this case, as in the case of the repeating unit a described above, it is expected that the conductivity is improved by using a block copolymer.

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

A living radical polymerization method called RAFT polymerization (Reversible Addition Fragmentation chain transfer polymerization) is a method in which a radical is always present at the end of a polymer, and therefore polymerization is initiated with the first monomer, By adding the two monomers, it is possible to form a diblock copolymer with a block of the repeating unit of the first monomer and a block of the repeating unit of the second monomer. The triblock polymer may also be formed when the polymerization is initiated with the first monomer, the second monomer is added in the step where it is consumed, and the third monomer is subsequently added.

When the RAFT polymerization is carried out, a narrow-dispersion polymer having a narrow molecular weight distribution (dispersion degree) is formed. In particular, when RAFT polymerization is carried out by adding the monomers at one time, 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, particularly 1.0 to 1.5, narrowly dispersed. If it is narrowly dispersed, the transmittance of the conductive film formed by the conductive polymer composite 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 dopant polymer of the component (B) has a weight average molecular weight of 1,000 to 500,000, preferably 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, the conductivity is deteriorated, and the viscosity is increased to deteriorate the workability and the dispersibility into water and organic solvent decreases.

The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) using water, dimethylformamide (DMF) or tetrahydrofuran (THF) as a solvent and measuring the values of polyethylene oxide, polyethylene glycol or polystyrene to be.

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, sodium salt, potassium salt, ammonium salt or sulfonium salt of a sulfo group as a monomer , And after the polymerization, it may be converted into a sulfo group using an ion exchange resin.

[Conductive polymer complex]

The conductive polymer composite of the present invention comprises the π conjugated polymer as the component (A) and the dopant polymer as the component (B), wherein the dopant polymer of the component (B) is a π conjugated polymer To form a complex.

The conductive polymer composite of the present invention preferably has dispersibility in water or an organic solvent and preferably has good spin coating film formability 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) .

(Method for producing conductive polymer composite)

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 performing oxidation polymerization.

Examples of the oxidizing agent and the oxidation catalyst include peroxosulfuric acid (persulfate) such as ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate) and potassium peroxodisulfate (persulfate), ferric chloride, Transition metal compounds such as iron 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 can be used.

Water or a mixed solvent of water and a solvent may be used as the reaction solvent used in the oxidation polymerization. The solvent used here is preferably a solvent capable of dissolving or dispersing the components (A) and (B), which is miscible with water. For example, polar solvents such as N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide and hexamethylenephosphoramide, Propanol and butanol; and alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, Polyhydric alcohols such as 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol, carbonate compounds such as ethylene carbonate and propylene carbonate, Cyclic ether compounds such as tetrahydrofuran, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, polyethylene glycol dialkyl ethers, polypropylene glycol dialkyl ethers, And the like nitrile compounds, such as LE, such as chain ethers, 3-methyl-2-oxazolidinone, such as heterocyclic compounds, acetonitrile, gluconic Taro nitrile, methoxy acetonitrile, propionitrile, benzonitrile. 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 component (B), a dopable anion to the π conjugated polymer of component (A) may also 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 polymer composite, 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, an aliphatic, aromatic, cyclic aliphatic or the like containing one or two or more carboxyl groups can be used. For example, there may be mentioned inorganic acids such as 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, And phenylacetic acid.

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

As the organic sulfonic acid, aliphatic, aromatic, cyclic aliphatic or the like containing 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-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, Amino-5-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 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, Naphthalene-1-sulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate and the like. And sulfonic acid compounds containing a sulfonic acid group.

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, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, dibutylbenzene disulfonic acid , 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- Naphthalene disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, anthracene di Sulfonic acid, butyl anthracene disulfonic acid, 4-acetamide-4'-isothio-cyanato stilbene-2,2'-disulfone , 4-acetamido-4'-isothiocyanato-2,2'-disulfonic acid, 4-acetamido-4'-maleimidylstilbene-2,2'-disulfonic acid, 1- Trisulfonic acid, 7-amino-1,3,6-naphthalenetrisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, 3- Naphthalene trisulfonic 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 a 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 may 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 mixing and dispersing machine include a homogenizer, a high-pressure homogenizer, and a bead mill, among which a high pressure homogenizer is preferable.

Specific examples of the high-pressure homogenizer include a nanoverter manufactured by Yoshida Kikai Kogyo Co., a microfluidizer manufactured by Powrex Corporation, and an atomizer manufactured by Suginomachine.

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

The impurities may be removed by a method such as filtration, ultrafiltration, or dialysis 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 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 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 Do. 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 and sufficient conductivity can be ensured. 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.

Examples of the organic solvent which can be added to the polymerization reaction aqueous solution or in which the monomer can be diluted include alcohols such as methanol, ethanol, propanol and butanol, alcohols such as methanol, ethylene glycol, propylene glycol, 1,3-propanediol, Butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, 1,2-butanediol, 3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, , 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,3-cyclohexanetriol, 1,3,5-cyclohexanetriol and neopentyl glycol. Alcohols, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, polyethylene glycol dialkyl ethers, polypropylene Cyclohexanone, methyl amyl ketone, ethyl acetate, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether; Butylene glycol 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, Propyl methacrylate, methyl methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate,? -Butyrolactone, '-Dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylenephosphine A polar solvent such as trimethylolpropane, tridolamide, etc., a carbonate compound such as ethylene carbonate and propylene carbonate, a heterocyclic compound such as 3-methyl-2-oxazolidinone and the like, acetonitrile, glutaronitrile, methoxyacetonitrile , Nitrile compounds such as propionitrile and benzonitrile, and mixtures thereof.

The amount of the organic solvent to be used is preferably 0 to 1,000 mL, more preferably 0 to 500 mL, per 1 mol of the monomer. If the amount of the organic solvent is 1,000 mL or less, the reaction vessel is not excessively large, which is economical.

[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 Anionic surfactants such as alkyl or alkylallylsulfates, alkyl or alkylallylsulfonates and dialkylsulfosuccinates; amphoteric surfactants such as amino acid and betaine; and the like, .

(High conductivity agent)

In the present invention, an organic solvent may be contained separately from the main solvent for the purpose of improving conductivity of the conductive polymer composite and improving coating and film forming properties on a substrate. Specific examples include alcohols such as methanol, ethanol, propanol and butanol, alcohols such as methanol, ethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, 1,3-butylene glycol, , D-glucose, D-glucitol, isoprene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, Diol, 1,2-hexanediol, 1,6-hexanediol, 1,9-nonanediol, 1,3,5-adamantanetriol, 1,2,3-butanetriol, 1,2,4 Cyclohexanetriol, 1,3,5-cyclohexanetriol, neopentyl glycol, and polyethylene glycol, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol monoalkyl ethers, Chain ethers such as ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, Cyclic ether compounds such as 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 Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propyleneglycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, acetic acid N, N'-dimethylformamide, dimethylsulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, N-methylpyrrolidone, '-Dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylenephosphoric triamide and other polar solvents Carbonate compounds such as ethylene carbonate, propylene carbonate and the like, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzo Nitrile compounds such as nitrile, and mixtures thereof. The content is preferably 1.0 to 50.0 mass%, particularly 3.0 to 40.0 mass%. These solvents may be added before or after the polymerization of the conductive polymer complex.

INDUSTRIAL APPLICABILITY As described above, the conductive polymer composite of the present invention can form a conductive film having good film formability through filtration and spin coating, high transparency, and low surface roughness.

[Conductive film]

The conductive polymer composite (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 polymer composite (solution) include coating with a spin coater, bar coater, immersion, comma coating, spray coating, roll coating, screen printing, flexo printing, gravure printing, have. After the application, the conductive film can be formed by heat treatment with hot air circulation, hot plate or the like, IR, UV irradiation, or the like.

As described above, the conductive polymer composite of the present invention can be applied to a substrate or the like to form a conductive film. Further, since the conductive film thus formed is excellent in conductivity and transparency, it can function as a transparent electrode layer.

[Board]

Further, the present invention provides a substrate on which a conductive film is formed by the above-described conductive polymer composite 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 on a photoresist film and use it as an antistatic top coat.

As described above, in the conductive polymer composite of the present invention, the dopant polymer of the component (B) containing the sulfo group of the super strong acid forms a complex with the? -Conjugate polymer of the component (A) And it is possible to form a conductive film having good transparency, flatness, durability and conductivity when a film is formed by spin coating. In addition, such a conductive polymer composite has good affinity for an organic solvent and an organic substrate, and good film-forming properties for both an organic substrate and an inorganic substrate.

Further, since the conductive film formed by such a conductive polymer composite has excellent 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, Production Examples, Comparative Production Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

The monomers used in the synthesis examples are shown below.

Monomer 1: 1,1,3,3,3-pentafluoro-2- (methacryloyloxy) propane-1-sulfonate

Monomer 2: benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2- (methacryloyloxy) propane-1-sulfonate

Monomer 3: benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2- (3-methacryloyloxy-adamantane-1-carbonyloxy) -propane-1-sulfonate

Monomer 4: benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2- (3-methacryloyloxy-benzene-4-carbonyloxy) -propane-1-sulfonate

Monomer 5: tetrabutylammonium 1,1,3,3,3-pentafluoro-2- (acryloyloxy) propane-1-sulfonate

Monomer 6: benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2- (4-methacryloyloxy-4-methyladamantane-1-carbonyloxy) Nate

Monomer 7: benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2- (4-acryloyloxy-4-methylcyclohexane-1-carbonyloxy) -propane-1-sulfonate

[Synthesis of dopant polymer]

(Synthesis Example 1)

A solution obtained by dissolving 30.9 g of monomer 1, 19.1 g of styrene sulfonic acid, and 4.77 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C in a nitrogen atmosphere over 4 hours And added. The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration, and vacuum-dried at 50 DEG C for 15 hours to obtain 42.5 g of a white polymer.

The obtained polymer was analyzed by ¹⁹ F, ¹ H-NMR and GPC, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 1: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 29,900

Molecular weight distribution (Mw / Mn) = 1.91

This polymer compound is referred to as (dopant polymer 1).

(Synthesis Example 2)

A solution obtained by dissolving 38.3 g of monomer 3, 11.7 g of lithium styrene sulfonate and 2.82 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C in a nitrogen atmosphere for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration, and vacuum-dried at 50 DEG C for 15 hours to obtain 46.8 g of a white polymer.

The obtained white polymer was dissolved in 421 g of methanol, and an ammonium salt and a lithium salt were converted into a sulfo group using an ion exchange resin. The obtained polymer was analyzed by ¹⁹ F, ¹ H-NMR and GPC, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 3: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 43,000

Molecular weight distribution (Mw / Mn) = 1.77

This polymer compound is referred to as (dopant polymer 2).

(Synthesis Example 3)

A solution obtained by dissolving 37.5 g of monomer 4, 12.5 g of lithium styrene sulfonate, and 3.04 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C in a nitrogen atmosphere for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration, and vacuum-dried at 50 DEG C for 15 hours to obtain 47.1 g of a white polymer.

The obtained white polymer was dissolved in 424 g of methanol, and an ammonium salt and a lithium salt were converted into a sulfo group using an ion exchange resin. The obtained polymer was analyzed by ¹⁹ F, ¹ H-NMR and GPC, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 4: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 39,000

Molecular weight distribution (Mw / Mn) = 1.81

This polymer compound (dopant polymer 3) is used.

(Synthesis Example 4)

A solution obtained by dissolving 54.5 g of monomer 4 and 4.19 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added dropwise to 37.5 g of methanol stirred at 64 占 폚 in a nitrogen atmosphere over 4 hours. The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration, and vacuum-dried at 50 DEG C for 15 hours to obtain 43.6 g of a white polymer.

The obtained white polymer was dissolved in 396 g of methanol, and an ammonium salt was converted into a sulfo group using an ion exchange resin. The obtained polymer was analyzed by ¹⁹ F, ¹ H-NMR and GPC, and the following analysis results were obtained.

Weight average molecular weight (Mw) = 24,400

Molecular weight distribution (Mw / Mn) = 1.94

This polymer compound is referred to as (dopant polymer 4).

(Synthesis Example 5)

To 37.5 g of methanol stirred at 64 占 폚 in a nitrogen atmosphere, 20.4 g of Monomer 2, 17.3 g of lithium styrene sulfonate, and 10 g of 4- (1,1,1,3,3,3-hexafluoro-2-propanol) styrene 12.3 g and 4.19 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added dropwise over 4 hours. The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration, and vacuum-dried at 50 DEG C for 15 hours to obtain 44.0 g of a white polymer.

The obtained white polymer was dissolved in 396 g of methanol, and an ammonium salt and a lithium salt were converted into a sulfo group using an ion exchange resin. The obtained polymer was analyzed by ¹⁹ F, ¹ H-NMR and GPC, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 2: styrene sulfonic acid: 4- (1,1,1,3,3,3-hexafluoro-2-propanol) styrene = 1: 2:

Weight average molecular weight (Mw) = 29,900

Molecular weight distribution (Mw / Mn) = 1.91

This polymer compound is referred to as (dopant polymer 5).

(Synthesis Example 6)

A solution of 25.3 g of Monomer 5, 19.1 g of lithium styrene sulfonate, and 3.34 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C in a nitrogen atmosphere for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration and vacuum dried at 50 DEG C for 15 hours to obtain 39.6 g of a white polymer.

The resulting white polymer was dissolved in 414 g of methanol, and the ammonium salt and lithium salt were converted into sulfo groups using an ion exchange resin. The obtained polymer was analyzed by ¹⁹ F, ¹ H-NMR and GPC, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 5: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 28,700

Molecular weight distribution (Mw / Mn) = 1.58

This polymer compound (dopant polymer 6) is used.

(Synthesis Example 7)

A solution obtained by dissolving 32.0 g of monomer 6, 19.1 g of lithium styrene sulfonate, and 3.34 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C in a nitrogen atmosphere for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration, and vacuum-dried at 50 DEG C for 15 hours to obtain 46.9 g of a white polymer.

The resulting white polymer was dissolved in 414 g of methanol, and the ammonium salt and lithium salt were converted into sulfo groups using an ion exchange resin. The obtained polymer was analyzed by ¹⁹ F, ¹ H-NMR and GPC, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 6: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 45,100

Molecular weight distribution (Mw / Mn) = 1.93

This polymer compound is referred to as (dopant polymer 7).

(Synthesis Example 8)

A solution obtained by dissolving 29.4 g of monomer 7, 19.1 g of styrene sulfonate, and 3.34 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C in a nitrogen atmosphere for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration, and vacuum-dried at 50 DEG C for 15 hours to obtain 44.1 g of a white polymer.

The resulting white polymer was dissolved in 414 g of methanol, and the ammonium salt and lithium salt were converted into sulfo groups using an ion exchange resin. The obtained polymer was analyzed by ¹⁹ F, ¹ H-NMR and GPC, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 7: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 48,300

Molecular weight distribution (Mw / Mn) = 1.98

This polymer compound (dopant polymer 8) is used.

[Production of Dispersion of Conductive Polymer Complex Containing Polythiophene as? -conjugated Polymer]

(Production Example 1)

3.82 g of 3,4-ethylenedioxythiophene and 15.0 g of the dopant polymer 1 dissolved in 1,000 mL of ultrapure water were mixed at 30 占 폚.

While the mixed solution thus obtained was maintained 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 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 filtrate thus treated, and about 2,000 mL of the treatment solution was removed by ultrafiltration, and 2,000 mL of Ion exchanged water was added, and about 2,000 mL of the solution was removed by ultrafiltration. This operation was repeated three times.

After the obtained treatment liquid was purified with a cation exchange resin and an anion exchange resin, 2,000 mL of ion exchange water was added, and about 2,000 mL of the treatment solution was removed by ultrafiltration. This operation was repeated five times to obtain 1.3 wt% of the conductive polymer composite dispersion 1 of blue color.

Ultrafiltration conditions were as follows.

Fractional molecular weight of ultrafiltration membrane: 30K

Cross flow type

Feed flow rate: 3,000 mL / min

Membrane partial pressure: 0.12 Pa

Further, ultrafiltration was carried out under the same conditions in other production examples.

(Production Example 2)

The dopant polymer 1 of Production Example 1 was changed to the dopant polymer 2, the amount of 3,4-ethylenedioxythiophene was changed to 2.73 g, the amount of sodium persulfate to 6.01 g and the amount of ferric sulfate to 1.64 g Except that the conductive polymer composite dispersion 2 was obtained in the same manner as in Production Example 1. [

(Production Example 3)

The dopant polymer 1 of Production Example 1 was changed to the dopant polymer 3, the amount of 3,4-ethylenedioxythiophene was changed to 3.38 g, the amount of sodium persulfate to 7.44 g and the amount of ferric sulfate to 2.03 g , A conductive polymer composite dispersion 3 was obtained in the same manner as in Production Example 1. [

(Production Example 4)

The dopant polymer 1 of Production Example 1 was changed to the dopant polymer 4, the amount of 3,4-ethylenedioxythiophene was changed to 2.56 g, the amount of sodium persulfate to 5.63 g and the amount of ferric sulfate to 1.53 g Production was carried out in the same manner as in Production Example 1 except for obtaining the conductive polymer composite dispersion 4.

(Production Example 5)

The dopant polymer 1 of Production Example 1 was changed to the dopant polymer 5, and the amount of 3,4-ethylenedioxythiophene was changed to 4.77 g, the amount of sodium persulfate to 10.49 g and the amount of ferric sulfate to 2.86 g Except that the conductive polymer composite dispersion 5 was obtained in the same manner as in Production Example 1. [

(Production Example 6)

The dopant polymer 1 of Production Example 1 was changed to the dopant polymer 6, the amount of 3,4-ethylenedioxythiophene was changed to 3.93 g, the amount of sodium persulfate was changed to 8.65 g, and the amount of ferric sulfate was changed to 2.36 g Production was carried out in the same manner as in Production Example 1 except for obtaining the conductive polymer composite dispersion 6.

(Production Example 7)

The dopant polymer 1 of Production Example 1 was changed to the dopant polymer 7, the amount of 3,4-ethylenedioxythiophene was changed to 2.73 g, the amount of sodium persulfate to 6.01 g and the amount of ferric sulfate to 1.64 g Except that the conductive polymer composite dispersion 7 was obtained in the same manner as in Production Example 1. [

(Preparation Example 8)

The dopant polymer 1 of Production Example 1 was changed to the dopant polymer 8, the amount of the 2.96 g of 3,4-ethylenedioxythiophene, the amount of sodium persulfate of 6.51 g and the amount of ferric sulfate to 1.78 g Production was carried out in the same manner as in Production Example 1 except for obtaining the conductive polymer composite dispersion 8.

[Production of a conductive polymer composite containing polyaniline as a? -conjugated polymer]

(Preparation Example 9)

27.3 g of 2-methoxyaniline and 53.4 g of the dopant polymer 1 dissolved in 1,000 mL of ultrapure water were mixed at 25 占 폚.

The mixed solution was maintained at 0 캜 and 45.8 g of ammonium persulfate dissolved in 200 mL of ultrapure water was slowly added with stirring to react.

The obtained reaction solution was concentrated and then added dropwise to 4,000 mL of acetone to obtain a green powder. The green powder was again dispersed in 1,000 mL of ultrapure water and added dropwise to 4,000 mL of acetone to refine the green powder. This operation was repeated three times. The obtained green powder was re-dispersed 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. This dispersion was dropped into 4,000 mL of acetone to obtain a purified green powder (conductive polymer composite 9).

(Preparation Example 10)

Production was carried out in the same manner as in Production Example 9, except that 74.7 g of the dopant polymer 2 of the dopant polymer 1 of Production Example 9 was used to obtain the conductive polymer composite 10.

(Preparation Example 11)

Production was conducted in the same manner as in Production Example 9 except that the dopant polymer 1 of Production Example 9 was changed to 60.3 g of the dopant polymer 3 to obtain a conductive polymer composite 11.

(Production Example 12)

Production was carried out in the same manner as in Production Example 9 except that the dopant polymer 1 of Production Example 9 was changed to 79.8 g of the dopant polymer 4 to obtain Conductive Polymer Complex 12.

(Preparation Example 13)

Production was carried out in the same manner as in Production Example 9 except that the dopant polymer 1 of Production Example 9 was changed to 42.8 g of the dopant polymer 5 to obtain a conductive polymer composite 13.

(Preparation Example 14)

Production was carried out in the same manner as in Production Example 9 except that the dopant polymer 1 of Production Example 9 was changed to 51.9 g of the dopant polymer 6 to obtain a conductive polymer composite 14.

(Preparation Example 15)

Production was carried out in the same manner as in Production Example 9, except that 74.7 g of the dopant polymer 7 of Production Example 9 was used instead of the dopant polymer 1 to obtain Conductive Polymer Complex 15.

(Production Example 16)

Production was carried out in the same manner as in Production Example 9, except that 68.9 g of the dopant polymer 8 of the dopant polymer 1 of Production Example 9 was used to obtain Conductive Polymer Complex 16.

[Production of Dispersion of Conductive Polymer Complex Containing Polystyrene Sulfonic Acid as a Dopant Polymer]

(Comparative Production Example 1)

5.0 g of 3,4-ethylenedioxythiophene and 83.3 g of an aqueous solution of polystyrene sulfonic acid (18.0% by mass of Aldrich) were diluted with 250 mL of ion-exchanged water and mixed at 30 占 폚. Other than that, the production was conducted in the same manner as in Production Example 1 to obtain 1.3 wt% of a conductive polymer composite dispersion 17 of blue (PEDOT-PSS dispersion).

(Comparative Production Example 2)

27.3 g of 2-methoxyaniline and 226 g of polystyrene sulfonic acid aqueous solution (Aldrich 18.0% by mass) were dissolved in 400 ml of ion-exchanged water and mixed at 0 占 폚. The other components were produced in the same manner as in Production Example 9 to obtain conductive polymer composite 18.

[Example]

20 g of 1.3 wt% of the conductive polymer composite dispersion 1 to 8 obtained in Production Examples 1 to 8, 5 wt% of dimethyl sulfoxide and 0.3 wt% of a fluoroalkyl nonionic surfactant FS-31 (produced by DuPont) ) Were mixed and then filtered using a regenerated cellulose filter (manufactured by ADVANTEC CORPORATION) having a pore diameter of 0.45 mu m to prepare conductive polymer compositions, which were Examples 1 to 8, respectively. Further, conductive polymer composites (powders) 9 to 16 obtained in Production Examples 9 to 16 were used as a dispersion of 2.8% by mass, 0.3% by mass of a fluoroalkyl nonionic surfactant FS-31 did. Thereafter, a conductive polymer composition was produced by filtration using a regenerated cellulose filter (Advantech Co., Ltd.) having a pore diameter of 0.45 mu m, and these were referred to as Examples 9 to 16, respectively.

[Comparative Example]

The conductive polymer composite dispersion 17 obtained in Comparative Production Example 1 was the same as Examples 1 to 8, and the conductive polymer composite 18 obtained in Comparative Production Example 2 was the same as that in Examples 9 to 16, , And two.

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

(Filterability)

In the production of the conductive polymer compositions of the examples and comparative examples described above, those which were able to be filtered when filtration was performed using a regenerated cellulose filter having a pore diameter of 0.45 mu m were evaluated as &amp; cir &amp; Are shown in Table 1 and Table 2, respectively.

(Coating property)

First, the conductive polymer composition was spin-coated (spin-coated) on a Si wafer so as to have a film thickness of 100 ± 5 nm using a 1H-360S spin coater (SPINCOATER, manufactured by MIKASA). Subsequently, baking was performed at 120 DEG C for 5 minutes in a precision thermostat, and the solvent was removed to obtain a conductive film. For this conductive film, the refractive index (n, k) at a wavelength of 636 nm was determined by a spectroscopic ellipsometer VASE (J.A. A film in which a uniform film could be formed was evaluated as &amp; cir &amp;, and the refractive index could be measured.

(Transmittance)

(K value) measured by a spectroscopic ellipsometer (VASE) having a variable incident angle was calculated for a light beam having a wavelength of 550 nm at FT = 200 nm. The results are shown in Tables 1 and 2.

(Conductivity)

First, 1.0 mL of a conductive polymer composition 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 were adjusted so that the film thickness was 100 ± 5 nm. Baking was carried out at 120 DEG C for 5 minutes in a precision thermostat, and the solvent was removed to obtain a conductive film.

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

(Surface roughness)

A conductive film was obtained on a SiO ₂ wafer having a diameter of 4 inches (100 mm) in the same manner as in the evaluation of conductivity. The Ra value (average roughness) was measured by NX10 (manufactured by Parks Systems). The results are shown in Tables 1 and 2.

(Viscosity)

The solid content of the conductive polymer composition was adjusted to 1.3 wt% in Examples 1 to 8 and Comparative Example 1, 2.8 wt% in Examples 9 to 16 and Comparative Example 2, and the liquid temperature was adjusted to 25 占 폚. 35 mL was weighed in an exclusive measuring cell of a tuning-fork type viscometer SV-10 (manufactured by A &amp; D), and the viscosity immediately after the measurement was measured. The results are shown in Tables 1 and 2.

[Evaluation of conductive polymer composition containing polythiophene as? -conjugated polymer]

As shown in Table 1, in Examples 1 to 8 including the polythiophene as the? -Conjugated polymer and the dopant polymer having the repeating unit a, the filterability was good, and the uniformity A coating film was obtained. Also, the conductivity was about the same as that of Comparative Example 1, the transmittance to visible light at? = 550 nm was good, and the surface roughness was good. Examples 1 to 8 and Comparative Example 1 including a polythiophene as a? -Conjugate-based polymer were superior to Examples 9 to 16 and Comparative Example 2, which will be described below, which include polyaniline as a? did.

On the other hand, Comparative Example 1 in which polystyrene sulfonic acid having no repeating unit a was used as a dopant polymer had a limit in lowering the viscosity even after repeated atomization treatment, and the filtration property was lowered. As a result, in spin coating, And a uniform and flat coating film could not be obtained. In addition, although the conductivity is high, the transmittance and surface roughness of visible light at? = 550 nm were different from those of Examples 1 to 8.

[Evaluation of conductive polymer composition containing polyaniline as? -conjugated polymer]

As shown in Table 2, in Examples 9 to 16 including a dopant polymer containing polyaniline as the? -Conjugate polymer and having the repeating unit a, the filterability was good, and a uniform coating film was formed by coating with a spin coater . In addition, the conductivity was similar to that of Comparative Example 2, although the conductivity was decreased in Examples 1 to 8, which contained polythiophene as the? -Conjugated polymer, and the transmittance to visible light of? = 550 nm was also good and the surface roughness was good did.

On the other hand, in Comparative Example 2 using polystyrene sulfonic acid having no repeating unit a as a dopant polymer, filtration was possible and coating was good, but the transmittance and surface roughness of visible light at? = 550 nm were higher than those of Examples 9 to 16 I was away.

As described above, the conductive polymer composite of the present invention can form a conductive film having good low-viscosity, good filtration property, good film-forming property by spin coating, and good transparency, flatness, durability and conductivity at the time of film formation It became clear.

The present invention is not limited to the above embodiments. The above embodiment is an example, and any structure 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 (20)

(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 in the range of 1,000 to 500,000
Wherein the conductive polymer is a polyimide.

(Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group or an ester group, Wherein Z is any one of a phenylene group, a naphthylene group and an ester group, and a represents a relative amount of a corresponding repeating unit thereof, and 0 < a? 1.0. The positive resist composition according to claim 1, wherein the repeating unit (a) in the component (B) comprises at least one kind selected from repeating units a1 to a6 represented by the following general formulas (1-1) Lt; / RTI &gt;

(Wherein, R ¹ is the same as above, a1, a2, a3, a4 , a5 and a6 are as 0≤a1≤1.0, 0≤a2≤1.0, 0≤ showing the relative amount of their corresponding repeat units that each a3? 1.0, 0? a4? 1.0, 0? a5? 1.0, 0? a6? 1.0 and 0 <a1 + a2 + a3 + a4 + a5 + The conductive polymer composite according to claim 1, wherein the component (B) further comprises a repeating unit (b) represented by the following general formula (2).

(Wherein b represents a relative amount of its corresponding repeating unit, and ranges from 0 < b < 1.0) The conductive polymer composite according to claim 2, wherein the component (B) further comprises a repeating unit (b) represented by the following general formula (2).

(Wherein b represents a relative amount of its corresponding repeating unit, and ranges from 0 < b < 1.0) The conductive polymer composite according to claim 1, wherein the component (B) is a block copolymer. The conductive polymer composite according to claim 2, wherein the component (B) is a block copolymer. The conductive polymer composite according to claim 3, wherein the component (B) is a block copolymer. The conductive polymer composite according to claim 4, wherein the component (B) is a block copolymer. The positive resist composition according to claim 1, wherein the component (A) is a polymer of at least one precursor monomer selected from the group consisting of pyrrole, thiophene, selenophene, telulophene, aniline, polycyclic aromatic compounds and derivatives thereof By weight of the conductive polymer. The method according to claim 2, wherein the component (A) is a polymerized product of at least one precursor monomer selected from the group consisting of pyrrole, thiophene, selenophene, telulophene, aniline, polycyclic aromatic compounds and derivatives thereof By weight of the conductive polymer. The positive resist composition according to claim 3, wherein the component (A) is a polymer of at least one precursor monomer selected from the group consisting of pyrrole, thiophene, selenophene, telulophene, aniline, polycyclic aromatic compounds and derivatives thereof By weight of the conductive polymer. The method according to claim 4, wherein the component (A) is a polymerization product of at least one precursor monomer selected from the group consisting of pyrrole, thiophene, selenophene, telulophene, aniline, polycyclic aromatic compounds and derivatives thereof By weight of the conductive polymer. The method according to claim 5, wherein the component (A) is a polymerization product of at least one precursor monomer selected from the group consisting of pyrrole, thiophene, selenophene, telulophene, aniline, polycyclic aromatic compounds and derivatives thereof By weight of the conductive polymer. The conductive polymer composite according to claim 1, wherein the conductive polymer composite has dispersibility in water or an organic solvent. Characterized in that a conductive film is formed by the conductive polymer composite according to any one of claims 1 to 6. Characterized in that a conductive film is formed by the conductive polymer composite according to claim 2. Wherein the conductive film is formed by the conductive polymer composite according to claim 3. Wherein the conductive film is formed by the conductive polymer composite according to any one of claims 1 to 4. Wherein the conductive film is formed by the conductive polymer composite according to claim 5. 16. The substrate according to claim 15, wherein the conductive film functions as a transparent electrode layer.