KR101997952B1

KR101997952B1 - Conductive polymer composite and substrate

Info

Publication number: KR101997952B1
Application number: KR1020150124057A
Authority: KR
Inventors: 준 하타케야마; 고지 하세가와; 다카유키 나가사와
Original assignee: 신에쓰 가가꾸 고교 가부시끼가이샤
Priority date: 2014-09-05
Filing date: 2015-09-02
Publication date: 2019-07-08
Also published as: TWI670343B; JP2016056346A; JP6407107B2; KR20160029684A; TW201627421A

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 complex comprises a dopant polymer having a weight average molecular weight of 1,000 to 500,000, which comprises (A) a? 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, R ² is a fluorine atom or a trifluoromethyl group, Z is a single bond or -C (= O) -O-, m is an integer of 1 to 4, a is 0 < a &le; 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 polymers such as polyacetylene, polythiophene, polyselenophene, polytelulophene, polypyrrole, and polyaniline, and mixtures thereof, and the like are used as the π conjugated polymer. Examples of the anion molecule (dopant) Of the anion are the most frequently used. This is because the strong acid sulfonic acid interacts with the? -Conjugate-based polymer efficiently.

As sulfonic acid anion dopants, sulfonic acid polymers such as polyvinylsulfonic acid and polystyrenesulfonic acid (PSS) are widely used (Patent Document 1). The sulfonic acid polymer also includes vinyl perfluoroalkyl ether sulfonic acid typified by the registered trademark Nifion, which is used for fuel cell applications.

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

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

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

When polythiophene in which PSS is used as a dopant is absorbed in a blue region near a wavelength of 500 nm, when the material is applied on a transparent substrate such as a transparent electrode and used, There is a problem in that the transmittance as a member is influenced by the concentration or the film thickness.

Patent Document 2 discloses a π conjugated polymer formed by a repeating unit selected from thiophene, selenophene, telulophene, pyrrole, aniline, and polycyclic aromatic compound, and an organic solvent, A conductive polymer composition comprising a conductive polymer containing a fluorinated polymer polymer neutralized with water, a precursor monomer of a π-conjugated polymer, a fluorinated polymer polymer and an oxidizing agent in any order, It turns out to be a body.

However, in such a conventional conductive polymer, particles aggregate in the dispersion immediately after the synthesis, and addition of an organic solvent which is a high-grade dialysis agent as a coating material promotes further 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, resulting in a problem that coating failure is caused.

The polythiophene in which PSS is used as a dopant may be used as a hole injection layer. In this case, a hole injection layer is formed between the transparent electrode such as ITO and the light emitting layer. Since the conductivity is ensured by the lower transparent electrode, high conductivity is not required for the hole injection layer. In the hole injection layer, there is no occurrence of dark spots, and a high hole transporting ability is required.

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

As described above, the polythiophene-based conductive polymer using PSS as a dopant, such as PEDOT-PSS, which is highly versatile, has a high conductivity but is poor in transparency because it is absorbed in visible light and has high cohesiveness in aqueous dispersion. And there is a problem that the film-forming property by spin coating and the surface roughness of the film-forming portion are poor.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a conductive polymer composite having good filtration property and good film forming property by spin coating and capable of forming 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 formula (1) and having a weight average molecular weight of 1,000 to 500,000

And a conductive polymer.

With such a conductive polymer composite, a conductive film having good transparency and good flatness can be formed when the film is formed with good filterability, good spin-coating property to an inorganic or organic substrate, and formed.

It is also preferable that the repeating unit a in the component (B) includes at least one repeating unit selected from the repeating units a1 and a2 represented by the following formulas (1-1) and (1-2).

(Wherein R ^1-1 and R ^1-2 are each independently a hydrogen atom or a methyl group, R ^2-1 and R ^2-2 are each independently a fluorine atom or a trifluoromethyl group, m ₁ and m ₂ 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 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.

In this case, it is preferable that the component (B) further comprises a repeating unit b represented by the following formula (2).

(In the formula, 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 polymerized with 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) Thus, when the film is formed by spin coating, the stability by light or heat is improved. Therefore, it is possible to form a conductive film having high durability and excellent transparency, flatness and conductivity. 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.

In addition, 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 material for forming a conductive film which can form a conductive film having good transparency and good flatness when film formation is good with good filterability and good film-forming property by spin coating has been demanded.

As a result of intensive studies on the above problems, the present inventors have found that, in place of polystyrenesulfonic acid (PSS) widely used as a dopant of a conductive polymer material, a dopant polymer having a repeating unit having a benzenesulfonic acid substituted with a fluorine atom or a trifluoromethyl group The dopant polymer of the super strong acid strongly interacts with the pi conjugated polymer and the visible light absorption region of the pi conjugated polymer shifts to improve the transparency and the pi conjugated polymer and the dopant polymer are strongly ion bonded, The stability by heat is improved. Further, the present inventors have 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.

That is,

(A) a π-conjugated polymer and

&Lt; / RTI >

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 a polymer obtained by polymerization of a precursor monomer (organic monomer molecule) forming a π conjugated system chain (a structure in which single bonds and double bonds are alternately continuous).

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

Of these monomers, pyrrole, thiophene, selenophene, telulophen, aniline, polycyclic aromatic compounds and derivatives thereof are preferable from the viewpoints of ease of polymerization and stability in the air, and pyrrole, thiophene, Are particularly preferred, but are not limited thereto.

When the conductive polymer composite of the present invention contains the polythiophene as the component (A), it has high conductivity and high transparency in visible light. Therefore, the conductive polymer composite can be used for a touch panel, an organic EL display, As shown in Fig. On the other hand, in the case where the conductive polymer composite of the present invention contains polyaniline as the component (A), it is difficult to apply in the display relation because it absorbs a large amount of visible light and has low conductivity compared with the case of containing polythiophene, The use of a top coat of a resist upper layer film for preventing electrons from being charged in EB lithography is conceivable because it is easy to carry out road spin coating.

Further, the component (A) can obtain sufficient conductivity even when the monomers constituting the π conjugated polymer are unsubstituted. However, in order to further increase the conductivity, it is preferable to use an alkyl group, a carboxyl group, a sulfo group, an alkoxy group, a hydroxy group, 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-ethylenedithiophene, 3,4-ethylenedithiothiophene, 3,4-ethylenedithiophene, 3,4-ethylenedioxythiophene, 3,4- Methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3- 3-methyl-4-carboxyethylthiophene, 3,4- (2,2-dimethylpropylene dioxy) thiophene, 3, 4- (2,2-diethylpropylene dioxy) thiophene, (2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-yl) methanol; Aniline, 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2-propylaniline, 3-propylaniline, Isobutyl aniline, 2-methoxy aniline, 2-ethoxy aniline, 2-aniline sulfonic acid, 3-aniline sulfonic acid and the like.

Among them, (co) polymers comprising one or two selected from the group consisting of pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene and 3,4- 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 having a repeating unit a represented by the following formula (1) and having a benzenesulfonic acid substituted with a fluorine atom or a trifluoromethyl group.

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

R ² is a fluorine atom or a trifluoromethyl group.

Z is a single bond or -C (= O) -O-.

m is an integer of 1 to 4;

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

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

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

The repeating unit a represented by the formula (1) preferably includes at least one repeating unit selected from the repeating units a1 and a2 represented by the following formulas (1-1) and (1-2).

With such component (B), the filterability of the material, the film forming property, the affinity for the organic solvent and the substrate are improved, and the transmittance after the film formation is improved. The effect of the present invention can be more certainly obtained by including both of the repeating units a1 and a2 as the component (B).

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

(In the formula, b is 0 < b < 1.0)

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)

In the case where X and X ₂ are amine compounds, (P1a-3) described in paragraph [0048] of JP-A-2013-228447 is exemplified.

Here, as described above, a is 0 < a &le; 1.0, and preferably 0.2 a &le; 1.0. When 0 < a &le; 1.0 (i.e., when the repeating unit a is included), the effect of the present invention is obtained. When the repeating unit a contains at least one repeating unit selected from the repeating units a1 and a2, 0? A1? 1.0, 0? A2? 1.0, and 0 <a1 + a2? 1.0 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.

When the repeating unit b is included, 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, vinyl silane type, Tylene, 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, Quot;) < / RTI > polymer.

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

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis 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 in order to improve the polymerizability, it is preferable to combine methacryl type and styrene type monomers.

When two or more kinds of monomers providing the repeating unit a are used, the respective monomers may be randomly copolymerized or may be copolymerized in a block. When a block copolymerization polymer (block copolymer) is used, it is advantageous that a specific structure is generated around the dopant polymer by forming a structure even when the repeating portions including two or more kinds of the repeating units a are aggregated, thereby improving the conductivity do.

The monomers providing the repeating units a to c may be randomly copolymerized or may be copolymerized with each other in 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 a 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 the second monomer is added at a later stage, 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, since the repeating units of the first monomer and the second monomer are mixed in the middle portion, the shape is different from that of the block copolymer. In order to form a block copolymer by radical polymerization, living radical polymerization is preferably used.

In the living radical polymerization method called RAFT polymerization (reversible addition fragmentation chain transfer polymerization), since the radical at the end of the polymer is always maintained, the polymerization is initiated with the first monomer, By adding the second monomer, 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 copolymer may also be formed when the polymerization is initiated with the first monomer, the second monomer is added at the stage where the polymerization 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 the RAFT polymerization is carried out by adding 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, and more preferably 1.0 to 1.5. 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.

When the dopant polymer of the component (B) contains the repeating unit c described above, the proportion of the repeating units a to c is preferably 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, and 0 <c? 0.5.

It is also preferable that a + b + c = 1.

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, not only the conductivity is deteriorated but also the viscosity increases and the workability deteriorates, and the dispersibility into water and organic solvents decreases.

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

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

[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 Thereby forming a complex.

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

(Method for producing conductive polymer composite)

The complex of the component (A) and the component (B) can be obtained, for example, by reacting the monomer (B) or the monomer (B) , 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 oxidizing catalyst include peroxo 2 sulfate (persulfate) such as ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate) and potassium peroxodisulfate (persulfate) Transition metal compounds such as iron, ferric sulfate and cupric chloride, metal oxides such as silver oxide and cesium oxide, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen and the like.

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 component (A) and the component (B), which is miscible with water. For example, a polar solvent such as N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, or hexamethylphosphoric triamide, 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 and the like, 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 heterocyclic compounds such as 3-methyl-2-oxazolidinone, and nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, and the like. These solvents may be used alone or in a mixture of two or more. The blending amount of these water-miscible solvents is preferably 50 mass% or less of the total reaction solvent.

Further, in addition to the dopant polymer of the component (B), a dopable anion to the π conjugated polymer of the component (A) may be used in combination. As such an anion, an organic acid is preferable from the viewpoints of adjusting the dedoping property from the π conjugated polymer, the dispersibility of the conductive 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-amino-2-chlorotoluene-sulfonic acid, 4-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, Sulfonic acid, 4-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene sulfonic acid, 2-methylbenzene-1-sulfonic acid, 4-acetamido-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid 1-naphthalene sulfonic acid, 8-chloronaphthalene-1-sulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate And sulfonic acid compounds containing sulfonic acid groups such as sulfonic acid groups.

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

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 oxidation polymerization catalyst before the polymerization of the component (A) May be added to the conductive polymer composite (solution) containing the component (A) and the component (B).

The composite of the component (A) and the component (B) obtained as described above can be used in a finely divided form 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, a bead mill, and the like. Among them, a high-pressure homogenizer is preferable.

Specific examples of the high-pressure homogenizer include a nano-beater manufactured by Yoshida and a teacher, a microfluidizer manufactured by Paurex, and an atomizer manufactured by Suginomachin Co.,

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

The impurities may be removed by filtration, ultrafiltration, dialysis or the like before or after atomization, and then 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 . 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 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 water solution or in which the monomer can be diluted include alcohols such as methanol, ethanol, propanol and butanol, alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, 1,2-butanediol, 1,3-butanediol, Butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol, Chain ethers such as ethylene glycol monomethyl ether, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, dioxane, tetrahydrofuran , Cyclic ether compounds such as cyclohexanone, methyl Propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t- Butyl ether acetate,? -Butyrolactone, N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide and hexamethylenephosphoramide A polar solvent, a carbonate compound such as ethylene carbonate or propylene carbonate, a carbonate compound such as 3-methyl-2- Sasol may be a heterocyclic compound, acetonitrile, gluconic Taro nitrile, methoxy acetonitrile, propionitrile, compounds and mixtures, such as benzonitrile, etc., such as non-piperidinyl.

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. When the amount of the organic solvent used is less than 1,000 mL, the reaction vessel is not over-sized, which is economical.

[Other components]

(Surfactants)

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

(Advanced telephone system)

In the present invention, for the purpose of improving the conductivity of the conductive polymer composite, an organic solvent may be added separately from the main agent. Specific examples of such additives include polar solvents such as ethylene glycol, polyethylene glycol, dimethylsulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) And mixtures thereof. The addition amount is preferably 1.0 to 30.0 mass%, particularly preferably 3.0 to 10.0 mass%.

(corrector)

In the present invention, the pH of the conductive polymer complex in an aqueous solution shows acidity. For the purpose of neutralizing this, the nitrogen-containing aromatic cyclic compound described in paragraphs [0033] to [0045] of Japanese Patent Application Laid-Open No. 2006-96975, the cation described in paragraph [0127] You can also control. It is possible to prevent the occurrence of rust in the case of applying the solution to a printing machine by bringing the pH of the solution close to neutrality.

As described above, the conductive polymer composite of the present invention can form a conductive film having good film-forming property by 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 and a hole injection 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 to a photoresist film and use it as an antistatic topcoat.

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) Thus, it is possible to form a conductive film having good transparency, flatness, durability and conductivity when a film is formed by spin coating with good film formation. 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.

[Synthesis of dopant polymer]

(Synthesis Examples 1 to 5)

A solution of dimethyl 2,2'-azobis (isobutyrate) in methanol was added dropwise to the solution obtained by dissolving the monomer stirred at 64 ° C in methanol under nitrogen atmosphere over 4 hours, and the mixture was stirred for 4 hours. After cooling to room temperature, the solution was added dropwise with vigorous stirring to ethyl acetate, and the resulting solid was filtered and vacuum dried at 50 ° C for 15 hours. The obtained white polymer was dissolved in methanol, and the cation of the monomer was dissolved in methanol And converted into a sulfo group.

In this way, the following dopant polymers 1 to 5 were obtained.

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)

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

In a nitrogen atmosphere, 2-cyano-2-propylbenzodithioate and 2,2'-azobisisobutyronitrile were dissolved in methanol, and the solution was stirred at 64 ° C for 3 hours under a nitrogen atmosphere. A solution prepared by dissolving benzyltrimethylammonium 2,3,5,6-tetrafluorostyrene-4-sulfonate as a first monomer in methanol was added dropwise to the solution for 2 hours, and then, as a second monomer, A solution prepared by dissolving benzyltrimethylammonium 4-styrenesulfonate equivalent to the above-mentioned first monomer in methanol was added dropwise over 2 hours, and after completion of the dropwise addition, the mixture was stirred at 64 占 폚 for 4 hours. After cooling to room temperature, the mixture was added dropwise with vigorous stirring to ethyl acetate, and the resulting solid was collected by filtration and vacuum-dried at 50 占 폚 for 15 hours to obtain a red polymer.

The obtained red polymer was dissolved in methanol, and the benzyltrimethylammonium salt was converted into a sulfo 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

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

(Production Example 1)

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

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

1,000 mL of ultrapure water was added to the obtained reaction solution, and about 1,000 mL of the solution was removed by ultrafiltration. This operation was repeated three times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the filtrate thus treated, and about 2,000 mL of the treatment solution was removed using 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.

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 five times to obtain 1.3 wt% of the conductive polymer composite dispersion 1 of blue color.

Ultrafiltration conditions were as follows.

Differentiation molecular weight of ultrafiltration membrane: 30K

Cross flow type

Feed flow rate: 3,000 mL / min

Membrane partial pressure: 0.12 Pa

Ultrafiltration was carried out under the same conditions in other production examples.

(Production 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, the amount of sodium persulfate was changed to 5.31 g, and the amount of ferric sulfate was changed to 1.50 g , A conductive polymer composite dispersion 2 was obtained in the same manner as in Production Example 1. [

(Production 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, the amount of sodium persulfate was changed to 6.00 g, and the amount of ferric sulfate was changed to 1.60 g , A conductive polymer composite dispersion 3 was obtained in the same manner as in Production Example 1. [

(Production Example 4)

12.5 g of the dopant polymer 1 was changed to 10.8 g of the dopant polymer 4, 8.40 g of sodium persulfate was changed to 4.50 g of ammonium persulfate, 2.04 g of 3,4-ethylenedioxythiophene was added, Production was carried out in the same manner as in Production Example 1 except that the blending amount was changed to 1.23 g to obtain Conductive Polymer Complex Dispersion 4.

(Production Example 5)

12.5 g of the dopant polymer 1 was changed to 10.5 g of the dopant polymer 5, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, the amount of 3,4-ethylenedioxythiophene was 2.41 g, Production was carried out in the same manner as in Production Example 1 except that the blending amount was changed to 1.50 g to obtain a conductive polymer composite dispersion 5.

(Production Example 6)

12.5 g of the dopant polymer 1 was changed to 11.0 g of the dopant polymer 6, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, the amount of 3,4-ethylenedioxythiophene was changed to 2.41 g, A conductive polymer composite dispersion 6 was obtained in the same manner as in Production Example 1 except that the compounding amount was changed to 1.50 g.

(Production Example 7)

3.87 g of 3,4-dimethoxythiophene and 11.0 g of the dopant polymer 2 dissolved in 1,000 mL of ultrapure water were mixed at 30 占 폚.

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 five times to obtain 1.3 mass% of the conductive polymer composite dispersion 7 of blue color.

(Preparation Example 8)

A solution obtained by dissolving 4.62 g of (2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-yl) methanol and 11.0 g of the dopant polymer 2 in 1,000 mL of ultrapure water was charged with 30 Lt; 0 > C.

The mixed solution thus obtained was maintained at 30 캜 and, while stirring, 8.40 g of sodium persulfate and 2.3 g of ferric sulfate ferrous oxide solution dissolved in 100 mL of ultrapure water were added slowly and reacted for 4 hours with stirring.

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 five times to obtain a dispersion liquid 8 of a conductive polymer complex having a blue color of 1.3% by mass.

(Preparation Example 9)

4.16 g of 3,4-propylene dioxythiophene and 11.0 g of the dopant polymer 2 dissolved in 1,000 mL of ultrapure water were mixed at 30 占 폚.

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 five times to obtain 1.3 mass% of the conductive polymer composite dispersion 9 of blue color.

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

(Preparation Example 10)

27.3 g of 2-methoxyaniline and 45.4 g of the dopant polymer 1 dissolved in 1,000 mL of ultrapure water were mixed at 25 占 폚.

45.8 g of ammonium persulfate dissolved in 200 mL of ultrapure water was added slowly while stirring at 0 째 C, and the mixture was stirred and reacted.

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 then added dropwise to 4,000 mL of acetone to purify and finely grind the green powder. This operation was repeated three times. 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.

(Preparation Example 11)

Production was carried out in the same manner as in Production Example 10 except that 45.4 g of the dopant polymer 1 was changed to 38.2 g of the dopant polymer 2 to obtain the conductive polymer composite dispersion 11.

(Production Example 12)

Production was carried out in the same manner as in Production Example 10 except that 45.4 g of the dopant polymer 1 was changed to 36.5 g of the dopant polymer 3 and the blending amount of 2-methoxyaniline was changed to 27.5 g to obtain the conductive polymer composite dispersion 12 .

(Preparation Example 13)

Production was carried out in the same manner as in Production Example 10 except that 45.4 g of the dopant polymer 1 was changed to 41.4 g of the dopant polymer 4 and the blending amount of 2-methoxyaniline was changed to 27.5 g to prepare the conductive polymer composite dispersion 13 .

(Preparation Example 14)

Production was carried out in the same manner as in Production Example 10 except that 45.4 g of the dopant polymer 1 was changed to 43.4 g of the dopant polymer 5 and the blending amount of 2-methoxyaniline was changed to 27.5 g to obtain the conductive polymer composite dispersion 14 .

[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 polystyrene sulfonic acid aqueous solution (18.0% by mass, manufactured by Aldrich) were diluted with 250 mL of ion-exchanged water and mixed at 30 캜. Other than this, the same procedure as in Production Example 1 was carried out to obtain 1.3 wt% of a conductive polymer composite dispersion 15 of blue (PEDOT-PSS dispersion).

(Comparative Production Example 2)

27.3 g of 2-methoxyaniline and 226 g of polystyrene sulfonic acid aqueous solution (18.0% by mass produced by Aldrich) were dissolved in 400 mL of ion-exchanged water and mixed at 0 占 폚. Other than that, the production was conducted in the same manner as in Production Example 10 to obtain a conductive polymer composite dispersion (16).

[Example]

20 g of the 1.3 wt% conductive polymer composite dispersion 1 to 14 obtained in Production Examples 1 to 14, 5 g of dimethyl sulfoxide and 0.5 g of Surfynol 465 as a surfactant and a defoaming agent were mixed, And then filtered using a cellulose filter (manufactured by ADVANTEC CO., LTD.) To prepare conductive polymer compositions, respectively, as Examples 1 to 14.

[Comparative Example]

Conductive polymer compositions 15 and 16 obtained in Comparative Preparation Examples 1 and 2 were used instead of the conductive polymer composition dispersions 15 and 16 obtained in Comparative Preparation Examples 1 and 2. Comparative Examples 1 and 2 were respectively prepared.

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, when the filter was regenerated by using a regenerated cellulose filter having a pore diameter of 0.45 mu m, it was found that the filter was able to be filtered, and that the filter could not be filtered due to clogging 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 using a 1H-360S SPINCOATER (manufactured by MIKASA) so as to have a film thickness of 100 ± 5 nm. Subsequently, baking was performed at 120 DEG C for 5 minutes in an accurate high-temperature machine, and the solvent was removed to obtain a conductive film. The refractive index (n, k) at a wavelength of 636 nm was determined for this conductive film by using a spectroscopic ellipsometer VASE (manufactured by J.A. Woollam) having an incident angle variable. The results are shown in Table 1 and Table 2, in which a uniform film could be formed, and the refractive index could be measured, but the defects originating from the particle and the partial occurrence of distortion occurred in the film.

(Transmittance)

From the refractive index (k) measured by a spectroscopic ellipsometer (VASE) having an incident angle variable, the transmittance for a light beam with a wavelength of 550 nm at FT = 200 nm was calculated. 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 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 an accurate high-temperature machine, and the solvent was removed to obtain a conductive film.

The conductivity (S / cm) of the obtained conductive film was measured using a surface resistivity (Ω / □) measured by using Hiresta-UP MCP-HT450, 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 the evaluation method of conductivity. RMS (root mean squareness) was measured by AFM NANO-IM-8 (manufactured by Image Metrology). 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 캜. 35 mL was measured in a dedicated measuring cell attached to a tuning-fork vibratory viscometer SV-10 (manufactured by A & D Co.), 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, Examples 1 to 9 including the polythiophene as the? -Conjugated polymer and the dopant polymer having the repeating unit a had satisfactory filterability and uniformity by application of the spin coater I could get one coat. In addition, the conductivity was high, the transmittance to visible light of? = 550 nm was also good, and the surface roughness was good.

On the other hand, Comparative Example 1 using polystyrenesulfonic acid having no repeating unit a as a dopant polymer has poor filtrability because of its high viscosity. As a result, in spin coating, there is produced a strain due to particles or bubbles on the film, A uniform 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 lower than those of Examples 1 to 9.

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

As shown in Table 2, in Examples 10 to 14 including a dopant polymer containing polyaniline as the? -Conjugate-based polymer and having the repeating unit a, it was confirmed that Examples 10 to 14 having good filtration properties and uniformity by coating with a spin coater And the surface roughness of the film surface after application was also good.

In addition, the conductivity was similar to that of Comparative Example 2, though it fell to the above Examples 1 to 9 including the polythiophene as the π conjugated polymer.

On the other hand, in Comparative Example 2 using polystyrenesulfonic acid having no repeating unit a as a dopant polymer, filtration was possible and coating was good, but surface roughness was lower than in Examples 10 to 14. [

As described above, the conductive polymer composite of the present invention is excellent in film forming properties by spin coating and has good low-viscosity and good filtration property. When the film is formed, a conductive film and a hole injection layer having good transparency, flatness, durability, It is clear that it can be formed.

The present invention is not limited to the above-described embodiments. The above-described embodiments are illustrative, and any of those having substantially the same constitution as the technical idea described in the claims of the present invention and exhibiting the same operation effect are included in the technical scope of the present invention.

Claims

(A) a π-conjugated polymer and
(B) a dopant polymer having a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (2) and having a weight average molecular weight of 1,000 to 500,000
Wherein the conductive polymer is a polyimide.

(Wherein R ^1-1 is independently a methyl group, R ^2-1 is independently a fluorine atom or a trifluoromethyl group, m ₁ is an integer of 1 to 4, and a 1 is 0 <a1? 1.0)

(In the formula, b is 0 < b < 1.0)

The conductive polymer composite according to claim 1, wherein the component (B) is a block copolymer.

The positive resist composition according to claim 1 or 2, wherein the component (A) is at least one precursor monomer selected from the group consisting of pyrrole, thiophene, selenophene, telulophene, aniline, polycyclic aromatic compound, Wherein the conductive polymer is a polymer obtained by polymerization.

The conductive polymer composite according to claim 1 or 2, wherein the conductive polymer composite has dispersibility in water or an organic solvent.

A substrate, characterized in that a conductive film is formed by the conductive polymer composite according to any one of claims 1 to 4.

The substrate according to claim 5, wherein the conductive film functions as a transparent electrode layer.

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