JP2022068178A - Conductive polymer composite and substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive polymer composite and a composition thereof, which improve water volatilization efficiency during film formation by incorporating a novel non-doping fluorinated unit into a dopant polymer; also reduce H⁺ generation by using the non-doping fluorinated unit in place of an acid unit generating extra acids; exhibit good filterability and film formability; and are capable of forming a film having high transparency and good flatness when the film is formed.

SOLUTION: A conductive polymer composite is a composite including: (A) a π-conjugated polymer and (B) a dopant polymer that is composed of a copolymer having a polymer unit having a hexafluoro carbinol group and a polymer unit having a fluoroalkyl sulfonic acid group.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a conductive polymer composite, a conductive polymer composition, and a substrate on which an electrode layer or a hole injection layer in an organic EL device is formed by the conductive polymer composite or the conductive polymer composition.

Polymers with conjugated double bonds (π-conjugated polymers) do not exhibit conductivity by themselves, but by doping with appropriate anionic molecules, electron or hole transfer is manifested, and the conductive polymer. It becomes a material. As the π-conjugated polymer, (hetero) aromatic polymers such as polythiophene, polyselenophene, polyterlophen, polypyrrole, and polyaniline, and mixtures thereof are used, and the anion molecule (dopant) is a sulfonic acid. System anions are most often used. This is because sulfonic acid, which is a strong acid, interacts efficiently with the above-mentioned π-conjugated polymer.

As the sulfonic acid-based anionic dopant, sulfonic acid polymers such as polyvinyl sulfonic acid and polystyrene sulfonic acid (PSS) are widely used (Patent Document 1). Further, the sulfonic acid polymer also includes vinyl perfluoroalkyl ether sulfonic acid represented by the registered trademark Nafion, which is used for fuel cell applications.

Polystyrene sulfonic acid (PSS), which is a sulfonic acid homopolymer, has high efficiency in doping a π-conjugated polymer because sulfonic acid is continuously present in a monomer unit with respect to the polymer main chain, and π-conjugated after doping. The dispersibility of the polymer in water can also be improved. This is because the hydrophilicity is maintained by the presence of the sulfo group which is present in the PSS in excess of the doping site, and the dispersibility in water is dramatically improved.

Polythiophene using PSS as a dopant is highly conductive and can be treated as an aqueous dispersion, so it is a coating type that replaces ITO (indium-tin oxide) used as a transparent electrode for organic EL and solar cells. It is expected as a transparent electrode film material. In addition, polythiophene does not require high conductivity at the stage when thin film devices such as organic EL and solar cells are shifting to the full-layer coating type material mechanism, but it reduces the carrier transfer load from the electrode to the carrier transfer layer. It is expected to be applied as a coating material that functions as an injection layer.

Since PSS is a water-soluble resin having a very high affinity for water, when a composite with a π-conjugated polymer is formed, the polymer having hydrophobic properties can be dispersed as particles in water. .. This dispersion can be handled as a liquid, and by adding a surfactant or the like, it is possible to apply and form a film on an organic / inorganic substrate that is difficult to apply, and the substrate can also be applied in the above-mentioned applications. A top film can be formed. As a method for forming a film, for example, coating with a spin coater or the like, bar coater, dipping, comma coating, spray coating, roll coating, screen printing, flexographic printing, gravure printing, inkjet printing, and then a hot air circulation furnace, A conductive film can be formed by heat treatment with a hot plate or the like, IR, UV irradiation, or the like.

However, on the other hand, due to the high hydrophilicity of PSS, the composite with the π-conjugated polymer using PSS as a dopant is applied on the substrate, and then heat film formation by a hot air circulation furnace, a hot plate, etc., IR, and UV irradiation. A large amount of water remains in the film after film formation due to such factors, and the water content may volatilize and fill the inside of the device after the device is formed and sealed, which may significantly reduce the device performance. For example, when the material is used for the constituent film (thin film) of the organic EL, the residual moisture in the film and the moisture absorbed from the external atmosphere in the manufacturing process up to sealing cause the moisture after laminating and sealing the constituent layers. Volatilization or permeation into the adjacent layer occurs, causing defects due to moisture aggregation inside the sealing element or inside the film, deterioration of the function of the light emitting layer, and increase of the element drive voltage due to moisture in the film, resulting in deterioration of the element function. Problems such as shortened element life occur.

Further, when a composite with a π-conjugated polymer using PSS as a dopant is used as a transparent electrode material in an organic thin film element such as an organic EL or a solar cell or a material for a hole injection layer, the residual moisture after the film formation is used. In addition to the problem, poor affinity for organic solvents and poor coatability on hydrophobic substrates are also problems, and it is difficult to form a thin film by spin coating or various printing devices. Further, in PEDOT-PSS, which is being widely studied, light absorption is in the visible light region and the transmittance is low, which hinders the application to a light-transmitting light-emitting element, and the particles of the complex tend to aggregate. Due to such characteristics, it is difficult to filter and purify even after making it into a liquid composition material. If coating is performed without filtration, coating defects may occur due to the influence of particle agglomerates, or even if a uniform film is obtained, the surface roughness is poor, and the organic EL has a laminated structure due to severe surface irregularities and pinholes. When applied to solar cells and the like, there are problems such as carrier movement obstacles and short circuits.

In Patent Documents 2 and 3, a dopant polymer incorporating a fluorinated acid unit is used for forming a π-conjugated polymer formed by a repeating unit selected from thiophene, pyrrole, aniline, and a polycyclic aromatic compound. The conductive polymer composition to be used has been proposed. It has been shown that water, a precursor monomer of a π-conjugated polymer, a fluorinated acid polymer, and an oxidizing agent can be combined in any order to form an aqueous dispersion of a conductive polymer composite.
By introducing the fluorinated acid unit, the organic solvent affinity of the fluorine atom is imparted to the dopant polymer, and as a result, the affinity of the entire composite with the π-conjugated polymer to the organic solvent and the surface of the hydrophobic substrate is increased. The dispersibility of the composite in an organic solvent and the applicability to a hydrophobic substrate are improved.

Japanese Unexamined Patent Publication No. 2008-146913 Japanese Patent Publication No. 2008-546899 Japanese Unexamined Patent Publication No. 2016-188350

However, on the other hand, there is no effect of reducing the residual water content in the film after film formation, and the dopant is composed of a fluorinated acid unit and an acid unit such as styrene sulfonic acid which is a constituent monomer of PSS, and is π-conjugated. The amount of H ⁺ generated from the excess sulfonic acid terminal other than the sulfonic acid terminal doped in the system polymer is not controlled. That is, when the repeating unit of the dopant polymer is a unit having all sulfonic acid terminals, the repeating unit constituting the π-conjugated polymer is not doped 1: 1 and therefore the repeating unit of the non-doped state dopant polymer. The sulfonic acid terminal exists as a free acid, and the acidity of the material in the liquid state before film formation becomes very high. Due to the influence of this high acidity, there is a problem that corrosion of the peripheral base material progresses in the coating process, and as a component of the thin film element, even after film formation and drying, H ⁺ is added to the element structure via the adjacent layer or from the side surface of the laminated structure. Diffuses, causing chemical deterioration and functional deterioration of each constituent layer, deteriorating the performance of the entire element, and deteriorating durability.

The present invention has been made in view of the above circumstances, and by incorporating a novel non-doped fluorinated unit into a dopant polymer, the volatilization efficiency of water during film formation is improved, and an acid unit that generates excess acid is not said to be present. By replacing it with a dope-type fluorination unit, it is possible to reduce the generation of H ⁺ , to form a film with good filterability and good film formation, and when a film is formed, it is possible to form a film with high transparency and good flatness. It is an object of the present invention to provide a possible conductive polymer composite and a composition thereof.

（式中、Ｒ^１は水素原子又はメチル基、Ｚはフェニレン基、ナフチレン基、エステル基のいずれかであり、Ｚがフェニレン基、ナフチレン基であればＲ^２は単結合、エステル基、あるいはエーテル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかであり、Ｚがエステル基であればＲ^２は単結合、あるいはエーテル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかである。ｍは１～３である。Ｒ^３、Ｒ^５、Ｒ^７、Ｒ^１０、Ｒ^１２、Ｒ^１３及びＲ^１５は、それぞれ独立に水素原子又はメチル基であり、Ｒ^４、Ｒ^６、Ｒ^８、Ｒ^１１、及びＲ^１４は、それぞれ独立に単結合、エーテル基、あるいはエステル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかである。Ｒ^９は、炭素数１～４の直鎖状、分岐状のアルキレン基であり、Ｒ^９中の水素原子のうち、１個又は２個がフッ素原子で置換されていてもよい。Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４、Ｘ_６、及びＸ_７は、それぞれ独立に単結合、フェニレン基、ナフチレン基、エーテル基、エステル基、アミド基のいずれかであり、Ｘ_５は、単結合、エーテル基、エステル基のいずれかである。Ｙはエーテル基、エステル基、アミノ基、あるいはアミド基のいずれかを示し、アミノ基およびアミド基は水素原子、あるいはヘテロ原子を含んでもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかを含んでもよい。Ｒｆ_１はフッ素原子又はトリフルオロメチル基であり、Ｒｆ_２とＲｆ_３は少なくとも１つ以上のフッ素原子を有する炭素数１～４の直鎖状、分岐状のアルキル基、又はフッ素原子若しくはトリフルオロメチル基で置換されたフェニル基であり、ｎは１～４の整数である。ａ、ｂ１、ｂ２、ｂ３、ｂ４、ｂ５、ｂ６、及びｂ７は、０＜ａ＜１．０、０≦ｂ１＜１．０、０≦ｂ２＜１．０、０≦ｂ３＜１．０、０≦ｂ４＜１．０、０≦ｂ５＜１．０、０≦ｂ６＜１．０、０≦ｂ７＜１．０であり、０＜ｂ１＋ｂ２＋ｂ３＋ｂ４＋ｂ５＋ｂ６＋ｂ７＜１．０である。） In order to solve the above problems, the present invention
(A) π-conjugated polymer, (B) repeating unit a represented by the following general formula (1), and 1 selected from the repeating units represented by the following general formulas (2-1) to (2-7). Provided is a conductive polymer composite comprising a dopant polymer composed of a seed or a copolymer containing two or more repeating units b.

(In the formula, R ¹ is a hydrogen atom or a methyl group, Z is a phenylene group, a naphthylene group, or an ester group, and if Z is a phenylene group or a naphthylene group, R ² is a single bond, an ester group, or an ether. It is any of a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either or both of these groups, and if Z is an ester group, R ² is simple. It is any of a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either or both of a bonded or ether group. M is 1 to 3. R ³ , R ⁵ , R ⁷ , R ¹⁰ , R ¹² , R ¹³ and R ¹⁵ are independently hydrogen atoms or methyl groups, respectively, and R ⁴ , R ⁶ , R ⁸ , R ¹¹ and R ¹⁴ are. , A linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms, each of which may independently have a single bond, an ether group, an ester group, or both. R ⁹ is a linear or branched alkylene group having 1 to 4 carbon atoms, and one or two of the hydrogen atoms in R ⁹ may be substituted with a fluorine atom. X ₁ , X ₂ , X ₃ , X ₄ , X ₆ and X ₇ are each independently single-bonded, phenylene group, naphthylene group, ether group, ester group or amide group, and X ₅ is single-bonded. , Ether group, or ester group. Y indicates any of an ether group, an ester group, an amino group, or an amide group, and the amino group and the amide group have the number of carbon atoms which may contain a hydrogen atom or a hetero atom. It may contain any of 1-12 linear, branched or cyclic hydrocarbon groups. Rf ₁ is a fluorine atom or a trifluoromethyl group and Rf ₂ and Rf ₃ are at least one fluorine atom. It is a linear or branched alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with a fluorine atom or a trifluoromethyl group, and n is an integer of 1 to 4 a, b1, b2. , B3, b4, b5, b6, and b7 are 0 <a <1.0, 0 ≦ b1 <1.0, 0 ≦ b2 <1.0, 0 ≦ b3 <1.0, 0 ≦ b4 <1. .0, 0 ≦ b5 <1.0, 0 ≦ b6 <1.0, 0 ≦ b7 <1.0, and 0 <b1 + b2 + b3 + b4 + b5 + b6 + b7 <1.0)

Such a conductive polymer complex has good filterability and good film forming property on an organic / inorganic substrate having high hydrophobicity, and when a film is formed, the residual water content in the film can be reduced in the film forming process. It is possible to form a conductive film having good transparency and flatness.

（式中、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９およびＲ^２０は、それぞれ独立に水素原子又はメチル基であり、Ｒは単結合、メチレン基、エチリデン基、イソプロピリデン基であり、Ｙとｍは前記と同じである。） The repeating unit a in the (B) dopant polymer preferably contains one or more selected from the repeating units a1 to a5 represented by the following general formulas (4-1) to (4-5). ..

(In the formula, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom or a methyl group, R is a single bond, a methylene group, an ethylidene group, an isopropylidene group, and Y m is the same as above.)

（式中、Ｒ²¹、Ｒ²²、Ｒ²³およびＲ²⁴は、それぞれ独立に水素原子又はメチル基であり、ｂ‘１、ｂ’２、ｂ‘３、ｂ’４は、０≦ｂ‘１＜１．０、０≦ｂ’２＜１．０、０≦ｂ‘３＜１．０、０≦ｂ’４＜１．０、０＜ｂ‘１＋ｂ’２＋ｂ‘３＋ｂ’４＜１．０である。） Further, the repeating unit b in the (B) dopant polymer is one or more selected from the repeating units b'1 to b'4 represented by the following general formulas (5-1) to (5-4). It is preferable that it contains.

(In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ are independently hydrogen atoms or methyl groups, respectively, and b'1, b'2, b'3 and b'4 are 0≤b'1. <1.0, 0≤b'2 <1.0, 0≤b'3 <1.0, 0≤b'4 <1.0, 0 <b'1 + b'2 + b'3 + b'4 <1.0 Is.)

(B) If the repeating units a and b in the dopant polymer are the above-mentioned specific ones, the filterability and film-forming property of the conductive polymer composite, the coatability to an organic / inorganic substrate, and the transmittance after film formation are high. It is improved and further effective in reducing the residual water content in the film after film formation.

（ｃは０＜ｃ＜１．０である。） Further, the dopant polymer (B) may further contain the repeating unit c represented by the following general formula (6).

(C is 0 <c <1.0.)

(B) When the dopant polymer contains such a repeating unit c, the conductivity of the film can be adjusted to an appropriate one for application and efficient function development when the element constituent layer is formed.

(B) The weight average molecular weight of the dopant polymer is preferably 1,000 to 500,000.

(B) When the weight average molecular weight of the dopant polymer is in the above range, the heat resistance of the polymer composite, the uniformity of the solution of the polymer composite, and the dispersibility of the polymer composite in water and an organic solvent are improved.

(B) The copolymerization ratio of the repeating unit a in the dopant polymer with respect to all the repeating units is preferably 10% to 60%.

(B) When the copolymerization ratio of the repeating unit a in the dopant polymer to all the repeating units is in the above range, the effect of the present invention is more fully exhibited.

(B) The dopant polymer is preferably a block copolymer.
In this case, the conductivity of the conductive polymer composite is improved.

(A) The π-conjugated polymer is polymerized with one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurophenes, aniline, polycyclic aromatic compounds, and derivatives thereof. It is preferable that it is a thing.

If the precursor monomer is the specific monomer, the polymerization is easy and the stability in air is good, so that the (A) π-conjugated polymer can be easily synthesized.

The conductive polymer complex is preferably used for forming a transparent electrode layer or a hole injection layer of an organic EL element.
The conductive film formed from the conductive polymer composite is excellent in conductivity, hole injection property, and transparency, and therefore functions suitably as a transparent electrode layer or a hole injection layer of an organic EL element.

（式中、Ｒ^２０１及びＲ^２０２はそれぞれ独立にヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の１価炭化水素基、水素原子、ヘテロ原子のいずれかを示す。Ｒ^２０３及びＲ^２０４はそれぞれ独立に、ヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の１価炭化水素基、水素原子のいずれかを示す。Ｒ^２０１とＲ^２０３、あるいはＲ^２０１とＲ^２０４は互いに結合して環を形成してもよい。Ｌはヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の４価の有機基を示す。Ｌがヘテロ原子を有する場合、該ヘテロ原子はイオンであってもよい。） The present invention also provides a conductive polymer composition containing the above-mentioned conductive polymer composite, water or an organic solvent as a solvent, and the compound (C) represented by the following general formula (3).

(In the formula, R ²⁰¹ and R ²⁰² may each independently have a hetero atom. Either a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a hetero atom. R ²⁰³ and R ²⁰⁴ independently indicate either a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a heteroatom, or a hydrogen atom. R ²⁰¹ and R ²⁰³ , or R ²⁰¹ and R ²⁰⁴ may be bonded to each other to form a ring. L may have a heteroatom. Linear, branched or cyclic with 1 to 20 carbon atoms. It represents a tetravalent organic group. If L has a heteroatom, the heteroatom may be an ion.)

When such a conductive polymer composition is used as an electrode or a hole injection layer of a thin film laminated element such as an organic EL or a solar cell to form a film, the acid to the adjacent layer of the laminated structure and other constituent layers can be obtained. Diffusion is suppressed and the effect of acid can be mitigated.

In this case, the content of the compound (C) is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the conductive polymer composite.

When the content of the compound (C) is within the above-mentioned specific range, the effect of reducing acid diffusion from the antistatic film formed by the conductive polymer composition to other layers is further improved.

The pH of the conductive polymer composition is preferably 4.0 to 9.0.
When the pH of the conductive polymer composition is in the above range, the effect of the present invention is more fully exhibited.

The conductive polymer composition preferably further contains a nonionic surfactant.
The conductive polymer composition containing a nonionic surfactant further improves the applicability to a work piece such as a base material.

In this case, the content of the nonionic surfactant is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the conductive polymer composite.

When the content of the nonionic surfactant is in the above range, the applicability to the workpiece such as the base material becomes better, and the surface flatness of the formed film becomes better.

The conductive polymer composition is preferably used for forming a transparent electrode layer or a hole injection layer of an organic EL device.
The conductive film formed from the conductive polymer composition is excellent in conductivity, hole injection property, and transparency, and therefore functions suitably as a transparent electrode layer or a hole injection layer of an organic EL element.

Further, the present invention provides a substrate in which an electrode layer or a hole injection layer in an organic EL device is formed by a conductive polymer composite or the above-mentioned conductive polymer composition.

Such a substrate includes an electrode layer or a hole injection layer in an organic EL element formed of a conductive film having excellent conductivity, hole injection property, and transparency.

As described above, each of the conductive polymer composite of the present invention and its composition has low viscosity and good filterability, and has good coating film forming property by spin coating or the like. Due to the influence of fluorine atoms existing in each repeating unit of a and b, the removal of residual water in the film during film formation is efficient, and the transparency, flatness, conductivity, and hole injection efficiency are good. It is possible to form a film. Further, in the (B) dopant polymer, a repeating unit b containing a sulfo group and a non-doped fluorination unit a having no sulfonic acid terminal are copolymerized, and the polymer is used as a dopant to form a composite with the (A) π-conjugated polymer. By forming the excess sulfonic acid terminal in the non-doped state, the generation rate of H ⁺ is reduced as a result, and the conductive polymer composite of the present invention and its composition are each of the thin film laminated element. When applied as a constituent film, it is possible to suppress the influence of H ⁺ on other constituent layers. Further, such a conductive polymer composite and its composition have a good affinity for an organic / inorganic substrate having high hydrophobicity, and have a good film forming property for both an organic substrate and an inorganic substrate. It is a thing.
Further, the conductive film formed by such a conductive polymer composite or a composition thereof is excellent in conductivity, hole injection efficiency, transparency and the like, and even when applied as a constituent film of a thin film laminated element. Since volatilization and aggregation of water from the membrane can be reduced, it can effectively function as a transparent electrode layer or a hole injection layer of the thin film laminated element.

As described above, the conductive film has good filterability and good film forming property by spin coating or the like, can efficiently remove residual water in the film in the film forming process, and has high film transparency and flatness. There has been a demand for the development of a material for forming a conductive film capable of forming a conductive film.

As a result of diligent studies on the above problems, the present inventors have replaced the polystyrene sulfonic acid homopolymer (PSS), which is widely used as a dopant for conductive polymer materials, with the non-doped fluorination unit a and the α-position. By using a dopant polymer copolymerized with a repeating unit b having a repeating unit having a fluorinated sulfo group, the filterability is good, the film formation property in a spin coat is good, and the acidity of the material is relaxed from the molecular structure. We have found a conductive polymer composite and a composition thereof that can form a conductive polymer having a small amount of residual water when a film is formed and can form a conductive film having high transparency and high flatness, and further, a configuration of an organic EL element. The present invention was completed by mounting it as a layer and obtaining good results in its performance evaluation.

（式中、Ｒ^１は水素原子又はメチル基、Ｚはフェニレン基、ナフチレン基、エステル基のいずれかであり、Ｚがフェニレン基、ナフチレン基であればＲ^２は単結合、エステル基、あるいはエーテル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかであり、Ｚがエステル基であればＲ^２は単結合、あるいはエーテル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかである。ｍは１～３である。Ｒ^３、Ｒ^５、Ｒ^７、Ｒ^１０、Ｒ^１２、Ｒ^１３及びＲ^１５は、それぞれ独立に水素原子又はメチル基であり、Ｒ^４、Ｒ^６、Ｒ^８、Ｒ^１１、及びＲ^１４は、それぞれ独立に単結合、エーテル基、あるいはエステル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかである。Ｒ^９は、炭素数１～４の直鎖状、分岐状のアルキレン基であり、Ｒ^９中の水素原子のうち、１個又は２個がフッ素原子で置換されていてもよい。Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４、Ｘ_６、及びＸ_７は、それぞれ独立に単結合、フェニレン基、ナフチレン基、エーテル基、エステル基、アミド基のいずれかであり、Ｘ_５は、単結合、エーテル基、エステル基のいずれかである。Ｙはエーテル基、エステル基、アミノ基、あるいはアミド基のいずれかを示し、アミノ基およびアミド基は水素原子、あるいはヘテロ原子を含んでもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかを含んでもよい。Ｒｆ_１はフッ素原子又はトリフルオロメチル基であり、Ｒｆ_２とＲｆ_３は少なくとも１つ以上のフッ素原子を有する炭素数１～４の直鎖状、分岐状のアルキル基、又はフッ素原子若しくはトリフルオロメチル基で置換されたフェニル基であり、ｎは１～４の整数である。ａ、ｂ１、ｂ２、ｂ３、ｂ４、ｂ５、ｂ６、及びｂ７は、０＜ａ＜１．０、０≦ｂ１＜１．０、０≦ｂ２＜１．０、０≦ｂ３＜１．０、０≦ｂ４＜１．０、０≦ｂ５＜１．０、０≦ｂ６＜１．０、０≦ｂ７＜１．０であり、０＜ｂ１＋ｂ２＋ｂ３＋ｂ４＋ｂ５＋ｂ６＋ｂ７＜１．０である。） That is, the present invention comprises (A) a π-conjugated polymer, (B) a repeating unit a represented by the following general formula (1), and a repeating unit represented by the following general formulas (2-1) to (2-7). It is a conductive polymer composite which is a composite containing a dopant polymer composed of a copolymer containing one kind or two or more kinds of repeating units b selected from units.

(In the formula, R ¹ is a hydrogen atom or a methyl group, Z is a phenylene group, a naphthylene group, or an ester group, and if Z is a phenylene group or a naphthylene group, R ² is a single bond, an ester group, or an ether. It is any of a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either or both of these groups, and if Z is an ester group, R ² is simple. It is any of a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either or both of a bonded or ether group. M is 1 to 3. R ³ , R ⁵ , R ⁷ , R ¹⁰ , R ¹² , R ¹³ and R ¹⁵ are independently hydrogen atoms or methyl groups, respectively, and R ⁴ , R ⁶ , R ⁸ , R ¹¹ and R ¹⁴ are. , A linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms, each of which may independently have a single bond, an ether group, an ester group, or both. R ⁹ is a linear or branched alkylene group having 1 to 4 carbon atoms, and one or two of the hydrogen atoms in R ⁹ may be substituted with a fluorine atom. X ₁ , X ₂ , X ₃ , X ₄ , X ₆ and X ₇ are each independently single-bonded, phenylene group, naphthylene group, ether group, ester group or amide group, and X ₅ is single-bonded. , Ether group, or ester group. Y indicates any of an ether group, an ester group, an amino group, or an amide group, and the amino group and the amide group have the number of carbon atoms which may contain a hydrogen atom or a hetero atom. It may contain any of 1-12 linear, branched or cyclic hydrocarbon groups. Rf ₁ is a fluorine atom or a trifluoromethyl group and Rf ₂ and Rf ₃ are at least one fluorine atom. It is a linear or branched alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with a fluorine atom or a trifluoromethyl group, and n is an integer of 1 to 4 a, b1, b2. , B3, b4, b5, b6, and b7 are 0 <a <1.0, 0 ≦ b1 <1.0, 0 ≦ b2 <1.0, 0 ≦ b3 <1.0, 0 ≦ b4 <1. .0, 0 ≦ b5 <1.0, 0 ≦ b6 <1.0, 0 ≦ b7 <1.0, and 0 <b1 + b2 + b3 + b4 + b5 + b6 + b7 <1.0)

（式中、Ｒ^２０１及びＲ^２０２はそれぞれ独立にヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の１価炭化水素基、水素原子、ヘテロ原子のいずれかを示す。Ｒ^２０３及びＲ^２０４はそれぞれ独立に、ヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の１価炭化水素基、水素原子のいずれかを示す。Ｒ^２０１とＲ^２０３、あるいはＲ^２０１とＲ^２０４は互いに結合して環を形成してもよい。Ｌはヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の４価の有機基を示す。Ｌがヘテロ原子を有する場合、該ヘテロ原子はイオンであってもよい。） Further, the present invention is a conductive polymer composition containing the above-mentioned conductive polymer composite, water or an organic solvent as a solvent, and the compound (C) represented by the following general formula (3).

(In the formula, R ²⁰¹ and R ²⁰² may each independently have a hetero atom. Either a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a hetero atom. R ²⁰³ and R ²⁰⁴ independently indicate either a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a heteroatom, or a hydrogen atom. R ²⁰¹ and R ²⁰³ , or R ²⁰¹ and R ²⁰⁴ may be bonded to each other to form a ring. L may have a heteroatom. Linear, branched or cyclic with 1 to 20 carbon atoms. It represents a tetravalent organic group. If L has a heteroatom, the heteroatom may be an ion.)

Further, the present invention is a substrate on which an electrode layer or a hole injection layer in an organic EL device is formed by the conductive polymer composite or the conductive polymer composition.

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

[(A) π-conjugated polymer]
The conductive polymer complex of the present invention contains (A) a π-conjugated polymer. The (A) π-conjugated polymer may be a polymer of a precursor monomer (organic monomer molecule) forming a π-conjugated chain (a structure in which a single bond and a double bond are alternately continuous).
Examples of such precursor monomers include monocyclic aromatics such as pyrroles, thiophenes, thiophenebinylenes, selenophenes, tellrophens, phenylenes, phenylenebinylenes, and aniline; Cyclic aromatics; acetylenes and the like can be mentioned, and monopolymers or copolymers of these monomers can be used as the (A) π-conjugated polymer.
Among the above monomers, pyrrole, thiophene, selenophene, tellurophenes, aniline, polycyclic aromatic compounds, and derivatives thereof are preferable from the viewpoint of ease of polymerization and stability in air, and pyrrole, thiophene, aniline, And these derivatives are particularly preferred.

Further, even if the monomer constituting the (A) π-conjugated polymer remains unchanged, the (A) π-conjugated polymer can obtain sufficient conductivity, but in order to further enhance the conductivity, an alkyl group, A monomer substituted with a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, a cyano group, a halogen atom or the like may be used.

Specific examples of monomers of pyrrols, thiophenes and anilins include pyrrol, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole and 3-octylpyrrole. 3-decylpyrrole, 3-dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl-4-carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3- Methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene , 3-Ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene , 3-Chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-Butoxythiophene, 3-Hexyloxythiophene, 3-Heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3, 4-Dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4- Dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3 -Methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene , Aniline, 2-Methylaniline, 3-Isobuchi Examples thereof include luaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-aniline sulfonic acid, 3-aniline sulfonic acid and the like.

Among them, one or more (co) polymers selected from pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, and 3,4-ethylenedioxythiophene have resistance values and reactions. It is preferably used from the viewpoint of sex. Furthermore, a monopolymer made of pyrrole and 3,4-ethylenedioxythiophene has high conductivity and is more preferable.

[(B) Dopant polymer]
The conductive polymer complex of the present invention contains (B) a dopant polymer. The dopant polymer (B) is one or two selected from the repeating unit a represented by the following general formula (1) and the repeating unit represented by the following general formulas (2-1) to (2-7). It is a strongly acidic polyanion composed of a copolymer containing the above repeating unit b.

（式中、Ｒ^１は水素原子又はメチル基、Ｚはフェニレン基、ナフチレン基、エステル基のいずれかであり、Ｚがフェニレン基、ナフチレン基であればＲ^２は単結合、エステル基、あるいはエーテル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかであり、Ｚがエステル基であればＲ^２は単結合、あるいはエーテル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかである。ｍは１～３である。Ｒ^３、Ｒ^５、Ｒ^７、Ｒ^１０、Ｒ^１２、Ｒ^１３及びＲ^１５は、それぞれ独立に水素原子又はメチル基であり、Ｒ^４、Ｒ^６、Ｒ^８、Ｒ^１１、及びＲ^１４は、それぞれ独立に単結合、エーテル基、あるいはエステル基のいずれか又はこれらの両方を有していてもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかである。Ｒ^９は、炭素数１～４の直鎖状、分岐状のアルキレン基であり、Ｒ^９中の水素原子のうち、１個又は２個がフッ素原子で置換されていてもよい。Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４、Ｘ_６、及びＸ_７は、それぞれ独立に単結合、フェニレン基、ナフチレン基、エーテル基、エステル基、アミド基のいずれかであり、Ｘ_５は、単結合、エーテル基、エステル基のいずれかである。Ｙはエーテル基、エステル基、アミノ基、あるいはアミド基のいずれかを示し、アミノ基およびアミド基は水素原子、あるいはヘテロ原子を含んでもよい炭素数１～１２の直鎖状、分岐状、環状の炭化水素基のいずれかを含んでもよい。Ｒｆ_１はフッ素原子又はトリフルオロメチル基であり、Ｒｆ_２とＲｆ_３は少なくとも１つ以上のフッ素原子を有する炭素数１～４の直鎖状、分岐状のアルキル基、又はフッ素原子若しくはトリフルオロメチル基で置換されたフェニル基であり、ｎは１～４の整数である。ａ、ｂ１、ｂ２、ｂ３、ｂ４、ｂ５、ｂ６、及びｂ７は、０＜ａ＜１．０、０≦ｂ１＜１．０、０≦ｂ２＜１．０、０≦ｂ３＜１．０、０≦ｂ４＜１．０、０≦ｂ５＜１．０、０≦ｂ６＜１．０、０≦ｂ７＜１．０であり、０＜ｂ１＋ｂ２＋ｂ３＋ｂ４＋ｂ５＋ｂ６＋ｂ７＜１．０である。）

(In the formula, R ¹ is a hydrogen atom or a methyl group, Z is a phenylene group, a naphthylene group, or an ester group, and if Z is a phenylene group or a naphthylene group, R ² is a single bond, an ester group, or an ether. It is any of a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either or both of these groups, and if Z is an ester group, R ² is simple. It is any of a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either or both of a bonded or ether group. M is 1 to 3. R ³ , R ⁵ , R ⁷ , R ¹⁰ , R ¹² , R ¹³ and R ¹⁵ are independently hydrogen atoms or methyl groups, respectively, and R ⁴ , R ⁶ , R ⁸ , R ¹¹ and R ¹⁴ are. , A linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms, each of which may independently have a single bond, an ether group, an ester group, or both. R ⁹ is a linear or branched alkylene group having 1 to 4 carbon atoms, and one or two of the hydrogen atoms in R ⁹ may be substituted with a fluorine atom. X ₁ , X ₂ , X ₃ , X ₄ , X ₆ and X ₇ are each independently single-bonded, phenylene group, naphthylene group, ether group, ester group or amide group, and X ₅ is single-bonded. , Ether group, or ester group. Y indicates any of an ether group, an ester group, an amino group, or an amide group, and the amino group and the amide group have the number of carbon atoms which may contain a hydrogen atom or a hetero atom. It may contain any of 1-12 linear, branched or cyclic hydrocarbon groups. Rf ₁ is a fluorine atom or a trifluoromethyl group and Rf ₂ and Rf ₃ are at least one fluorine atom. It is a linear or branched alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with a fluorine atom or a trifluoromethyl group, and n is an integer of 1 to 4 a, b1, b2. , B3, b4, b5, b6, and b7 are 0 <a <1.0, 0 ≦ b1 <1.0, 0 ≦ b2 <1.0, 0 ≦ b3 <1.0, 0 ≦ b4 <1. .0, 0 ≦ b5 <1.0, 0 ≦ b6 <1.0, 0 ≦ b7 <1.0, and 0 <b1 + b2 + b3 + b4 + b5 + b6 + b7 <1.0)

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

(B) The copolymerization ratio of the repeating unit a in the dopant polymer with respect to all the repeating units is preferably 10% to 60%. Further, from the viewpoint of the stability of the conductive polymer composite, the copolymerization ratio of the repeating unit a to all the repeating units is more preferably 10 to 40%. When the copolymerization ratio of the repeating unit a with respect to all the repeating units is in the above range, it becomes easy to develop conductivity that exhibits sufficient functions when the conductive polymer composite is applied as an electrode, and the conductivity is also increased. When the polymer composite is applied as a hole injection layer, it becomes easy to develop a hole injection efficiency that exhibits a sufficient function.

Specific examples of the monomer giving the repeating unit b1 include the following.

（式中、Ｒ^３は前述の通り。）

(In the formula, R ³ is as described above.)

Specific examples of the monomer for obtaining the repeating unit b2 can be exemplified below.

（式中、Ｒ^５は前述の通り。）

( ^In the formula, R5 is as described above.)

Specific examples of the monomer giving the repeating unit b3 include the following.

（式中、Ｒ^７は前記と同様である。）

(In the formula, R ⁷ is the same as above.)

Specific examples of the monomer giving the repeating unit b4 include the following.

（式中、Ｒ^１０は前記と同様である。）

(In the formula, R ¹⁰ is the same as described above.)

（式中、Ｒ^１２は前記と同様である。） Specific examples of the monomer giving the repeating unit b5 include the following.

(In the formula, R ¹² is the same as described above.)

Specific examples of the monomer giving the repeating unit b6 include the following.

（式中、Ｒ^１３は前記と同様である。）

(In the formula, R ¹³ is the same as described above.)

Specific examples of the monomer giving the repeating unit b7 include the following.

（式中、Ｒ^１５は前記と同様である。）

(In the formula, ^R15 is the same as above.)

The component (B) can further include a repeating unit c represented by the following general formula (6).

上記導電性ポリマー複合体を電極として適用した場合に十分な機能を発現する導電率を発現しやすくし、また上記導電性ポリマー複合体を正孔注入層として適用した場合に十分な機能を発現する正孔注入効率を発現しやすくする観点から、上記繰り返し単位ｂの全繰り返し単位に対する共重合割合は６０～９０％であることが好ましく、上記繰り返し単位ｃを含有する場合は、６０％≦ｂ＋ｃ≦９０％であり、その時上記繰り返し単位ｃの全繰り返し単位に対する共重合割合は４０％以下であることが好ましい。 Specific examples of the monomer giving the repeating unit c include the following.

When the above-mentioned conductive polymer composite is applied as an electrode, it easily develops a conductivity that exhibits a sufficient function, and when the above-mentioned conductive polymer composite is applied as a hole injection layer, it exhibits a sufficient function. From the viewpoint of facilitating the development of hole injection efficiency, the copolymerization ratio of the repeating unit b with respect to all the repeating units is preferably 60 to 90%, and when the repeating unit c is contained, 60% ≦ b + c ≦. It is 90%, and at that time, the copolymerization ratio of the repeating unit c with respect to all the repeating units is preferably 40% or less.

Further, the dopant polymer (B) may have a repeating unit d other than the repeating unit b and the repeating unit c, and the repeating unit d may be, for example, styrene-based, vinylnaphthylene-based, vinylsilane-based, acenaphthylene, or indene. , Vinylcarbazole and the like.

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

(B) As a method for synthesizing the dopant polymer, for example, a desired monomer among the monomers giving the above-mentioned repeating units a to d is heat-polymerized by adding a radical polymerization initiator in an organic solvent, and (co) weighted. A coalesced 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, γ-butyrolactone and the like.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis (2-methylpro). Pionate), benzoyl peroxide, lauroyl peroxide and the like can be exemplified.

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

(B) In the dopant polymer, the monomer that gives the repeating unit a may be one kind or two or more kinds, but it is preferable to combine a methacrylic type and a styrene type monomer that enhance the polymerizable property.
Further, when two or more kinds of monomers giving the repeating unit a are used, each monomer may be copolymerized at random or may be copolymerized in a block. In the case of a block copolymer (block copolymer), a peculiar structure is generated around the dopant polymer by agglomerating the repeating portions composed of two or more kinds of repeating units a to form a sea-island structure, and the conductivity is increased. The merit of improvement is expected.

Further, the monomers giving the repeating units a to c may be copolymerized at random, or each may be copolymerized in a block. In this case as well, as in the case of the repeating unit a described above, it is expected that the block copolymer has the merit of improving the conductivity.

When random copolymerization is carried out by radical polymerization, a method of mixing a monomer to be copolymerized and a radical polymerization initiator and carrying out the polymerization by heating is common. When the polymerization is started in the presence of the first monomer and the radical polymerization initiator, and then the second monomer is added, one side of the polymer molecule has a structure in which the first monomer is polymerized, and the other is the second. The structure is such that the monomers are polymerized. However, in this case, the repeating unit of the first monomer and the second monomer is mixed in the intermediate portion, and the form is different from that of the block copolymer. Living radical polymerization is preferably used to form block copolymers by radical polymerization.

In the method of polymerizing living radicals called RAFT polymerization (Reversible Addition Fragmentation chain Transfer polymerization), since the radical at the end of the polymer is always alive, polymerization is started with the first monomer, and when it is consumed, the second monomer is used. It is possible to form a diblock polymer with a block of repeating units of the first monomer and a block of repeating units of the second monomer. It is also possible to initiate polymerization with the first monomer, add the second monomer when it is consumed, and then add the third monomer to form a triblock polymer.

When RAFT polymerization is performed, a narrow dispersion polymer with a narrow molecular weight distribution (dispersity) is formed, and especially when a monomer is added at once and RAFT polymerization is performed, a polymer with a narrower molecular weight distribution is formed. can do.
In the dopant polymer (B), the molecular weight distribution (Mw / Mn) is preferably 1.0 to 2.0, particularly preferably 1.0 to 1.5, which is a narrow dispersion. If the dispersion is narrow, the effect of preventing the transmittance of the conductive film formed by the conductive polymer composite using the dispersion from being lowered tends to be improved.

A chain transfer agent is required to carry out RAFT polymerization, specifically 2-cyano-2-propylbenzothioate, 4-cyano-4-phenylcarbonotioilthiopentanoic acid, 2-cyano-2-propyl. Dodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, 2- (dodecylthiocarbonothio oilthio) -2-methylpropanoic acid, cyanomethyldodecylthiocarbonate, cyanomethyl Examples thereof include methyl (phenyl) carbamothioate, bis (thiobenzoyl) disulfide, and bis (dodecylsulfanylthiocarbonyl) disulfide. Of these, 2-cyano-2-propylbenzothioate is particularly preferable.

The dopant polymer (B) preferably has a weight average molecular weight in the range of 1,000 to 500,000, preferably 2,000 to 200,000 from the viewpoint of heat resistance and viscosity.
The weight average molecular weight (Mw) is a measured value in terms of polyethylene oxide, polyethylene glycol, or polystyrene by gel permeation chromatography (GPC) using water, dimethylformamide (DMF), or tetrahydrofuran (THF) as a solvent. ..

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

[Conductive polymer composite]
The conductive polymer composite of the present invention contains the above-mentioned (A) π-conjugated polymer and (B) dopant polymer, and the (B) dopant polymer is coordinated with (A) π-conjugated polymer. Form a complex with.

The conductive polymer composite of the present invention preferably has an affinity for both water and an organic solvent, and further provides spin-coat film forming property and film flatness to a strongly hydrophobic inorganic or organic substrate. Can be good.

[Manufacturing method of conductive polymer composite]
The conductive polymer composite containing (A) a π-conjugated polymer and (B) a dopant polymer is, for example, (A) in an aqueous solution of (B) a dopant polymer or a water / organic solvent mixed solution of (B) a dopant polymer. It can be obtained by adding a monomer (preferably pyrrole, thiophene, aniline, or a derivative monomer thereof) as a raw material of the π-conjugated polymer, adding an oxidizing agent and optionally an oxidation catalyst, and performing oxidative polymerization.

Examples of the oxidizing agent and the oxidation catalyst include peroxodisulfate (persulfate) such as ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate) and potassium peroxodisulfate (potassium persulfate), and quaternary chloride. 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, and oxygen. Etc. can be used.

As the reaction solvent used for oxidative polymerization, water or a mixed solvent of water and a solvent can be used. The solvent used here is miscible with water, and a solvent capable of dissolving or dispersing (A) a π-conjugated polymer and (B) a dopant polymer is preferable. For example, polar solvents such as N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylenephosphortriamide, alcohols such as methanol, ethanol, propanol and butanol. , Ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6- Polyvalent aliphatic alcohols such as hexanediol, 1,9-nonanediol and neopentyl glycol, carbonate compounds such as ethylene carbonate and propylene carbonate, cyclic ether compounds such as dioxane and tetrahydrofuran, dialkyl ethers and ethylene glycol monoalkyl ethers, Chain ethers such as ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, glutaronitrile , Nitrile compounds such as methoxy acetonitrile, propionitrile, benzonitrile and the like. These solvents may be used alone or as a mixture of two or more kinds. The mixing ratio of these solvents that are miscible with water is preferably 50% by mass or less of the total reaction solvent.

Further, in addition to the (B) dopant polymer, a dopeable anion to the (A) π-conjugated polymer may be used in combination. As such an anion, an organic acid is preferable from the viewpoint of adjusting the dedoping property from the π-conjugated polymer, the dispersibility of the conductive polymer composite, the heat resistance, and the environmental resistance property. Examples of the organic acid include organic carboxylic acids, phenols, and organic sulfonic acids.

As the organic carboxylic acid, an aliphatic, aromatic, cyclic aliphatic or the like containing one or more carboxy groups can be used. For example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, Examples thereof include triphenylacetic acid.
Examples of the phenols include phenols such as cresol, phenol and xylenol.

As the organic sulfonic acid, an aliphatic, aromatic, cyclic aliphatic or the like containing one or more sulfonic acid groups can be used. Examples of those containing one sulfonic acid group include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid and 1-octanesulfonic acid. , 1-nonan sulfonic acid, 1-decane sulfonic acid, 1-dodecane sulfonic acid, 1-tetradecane sulfonic acid, 1-pentadecane sulfonic acid, 2-bromoethane sulfonic acid, 3-chloro-2-hydroxypropane sulfonic acid, trifluo Lomethanesulfonic acid, Coristinmethanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, Aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-Amino-5-naphthol-7-sulfonic acid , 3-Amino Propane Sulfonic Acid, N-Cyclohexyl-3-Amino Propane Sulfonic Acid, benzene Sulfonic Acid, p-Toluene Sulfonic Acid, Xylene Sulfonic Acid, Ethylbenzene Sulfonic Acid, propylbenzene Sulfonic Acid, Butylbenzene Sulfonic Acid, Pentyl benzene Sulfonic Acid Acid, hexylbenzene sulfonic acid, heptylbenzene sulfonic acid, octylbenzene sulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecilbenzenesulfonic acid , 2,4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, butylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene -5-Sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4 -Amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-acetamide-3-chlorobenzenesulfonic acid , 4-Chloro-3-nitrobenzene sulfonic acid, p-chlorobenzene sulfonic acid, naphthalene sulfonic acid, methylnaphthalene sulfonic acid, propylnaphthalene sulfonic acid, butylnaphthalene sulfonic acid, pentylnaphthalene sulfonic acid, dimethylnaphthalene sulfonic acid, 4-amino- 1-naphthalene sulfonic acid, 8-chloronaphthalene- Examples thereof include sulfonic acid compounds containing a sulfonic acid group such as 1-sulfonic acid, naphthalene sulfonic acid formarin polycondensate, and melamine sulfonic acid formarin polycondensate.

Examples of those containing two or more sulfonic acid groups include ethandisulfonic acid, butanedisulfonic acid, pentandisulfonic acid, decandisulfonic acid, m-benzenedisulfonic acid, o-benzenedisulfonic acid, p-benzenedisulfonic acid and toluenedisulfonic acid. Acid, xylenedisulfonic acid, chlorobenzenedisulfonic acid, fluorobenzenedisulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, dimethylbenzenedisulfonic acid, diethylbenzenedisulfonic acid, dibutylbenzenedisulfonic acid, naphthalenedisulfonic acid , Methylnaphthalenedisulfonic acid, Ethylnaphthalenedisulfonic acid, Dodecylnaphthalenedisulfonic acid, Pentadecylnaphthalenedisulfonic acid, Butylnaphthalenedisulfonic acid, 2-Amino-1,4-benzenedisulfonic acid, 1-Amino-3,8-naphthalenedisulfonic acid , 3-Amino-1,5-naphthalenedisulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, anthracendisulfonic acid, butylanthrasendisulfone Acid, 4-acetamide-4'-isothio-cyanatostylben-2,2'-disulfonic acid, 4-acetamide-4'-isothiocyanatostilben-2,2'-disulfonic acid, 4-acetamide-4'- Maleimidirstilben-2,2'-disulfonic acid, 1-acetoxypyrene-3,6,8-trisulfonic acid, 7-amino-1,3,6-naphthalentrisulfonic acid, 8-aminonaphthalen-1, Examples thereof include 3,6-trisulfonic acid and 3-amino-1,5,7-naphthalene trisulfonic acid.

These anions other than the (B) dopant polymer include (A) the raw material monomer of the π-conjugated polymer, (B) the dopant polymer, the oxidizing agent and / or the oxidation polymerization catalyst before the polymerization of the (A) π-conjugated polymer. It may be added to the solution, or it may be added to the conductive polymer composite containing the (A) π-conjugated polymer and the (B) dopant polymer after the polymerization.

The conductive polymer complex containing the (A) π-conjugated polymer and the (B) dopant polymer thus obtained can be used after being atomized by a homogenizer, a ball mill or the like, if necessary.
For fine graining, it is preferable to use a mixing / dispersing machine capable of imparting a high shearing force. Examples of the mixing / dispersing machine include a homogenizer, a high-pressure homogenizer, a bead mill, and the like, and a high-pressure homogenizer is preferable.

Specific examples of the high-pressure homogenizer include NanoVeta manufactured by Yoshida Kikai Kogyo Co., Ltd., Microfluidizer manufactured by Paulek Co., Ltd., and Ultimateizer manufactured by Sugino Machine Limited.
Examples of the dispersion treatment using the high-pressure homogenizer include a treatment in which the complex solution before the dispersion treatment is subjected to a facing collision at a high pressure, a treatment in which the complex solution is passed through an orifice or a slit at a high pressure, and the like.

Before or after atomization, impurities may be removed by a method such as filtration, ultrafiltration, dialysis, etc., and purified with a cation exchange resin, anion exchange resin, chelate resin or the like.

Organic solvents that can be added to the polymerization reaction aqueous solution or that can dilute the monomer that is the raw material of (A) π-conjugated polymer include methanol, ethyl acetate, cyclohexanone, methylamylketone, butanediol monomethyl ether, and propylene. Glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate , Butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone and mixtures thereof. ..

The amount of the organic solvent used is preferably 0 to 1,000 mL, particularly preferably 0 to 500 mL per 1 mol of the above-mentioned monomer. If the amount of the organic solvent is 1,000 mL or less, the reaction vessel does not become excessive, which is economical.

[Conductive polymer composition]
The total content of the (A) π-conjugated polymer and the (B) dopant polymer in the conductive polymer composition is preferably 0.05 to 5.0% by mass. When the total content ratio of the (A) π-conjugated polymer and the (B) dopant polymer is within the above range, it becomes easy to obtain a sufficient conductive or hole injection function and a uniform conductive coating film.

（式中、Ｒ^２０１及びＲ^２０２はそれぞれ独立にヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の１価炭化水素基、水素原子、ヘテロ原子のいずれかを示す。Ｒ^２０３及びＲ^２０４はそれぞれ独立に、ヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の１価炭化水素基、水素原子のいずれかを示す。Ｒ^２０１とＲ^２０３、あるいはＲ^２０１とＲ^２０４は互いに結合して環を形成してもよい。Ｌはヘテロ原子を有してもよい炭素数１～２０の直鎖状、分岐状又は環状の４価の有機基を示す。Ｌがヘテロ原子を有する場合、該ヘテロ原子はイオンであってもよい。） (Compound (C))
A composition obtained by adding the compound (C) represented by the following general formula (3) to a solution or dispersion of water or an organic solvent of a complex containing the (A) π-conjugated polymer and the (B) dopant polymer. Can be formed.

(In the formula, R ²⁰¹ and R ²⁰² may each independently have a hetero atom. Either a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a hetero atom. R ²⁰³ and R ²⁰⁴ independently indicate either a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a heteroatom, or a hydrogen atom. R ²⁰¹ and R ²⁰³ , or R ²⁰¹ and R ²⁰⁴ may be bonded to each other to form a ring. L may have a heteroatom. Linear, branched or cyclic with 1 to 20 carbon atoms. It represents a tetravalent organic group. If L has a heteroatom, the heteroatom may be an ion.)

Each of such a conductive polymer composite and its composition has good filterability and good film forming property on an organic / inorganic substrate having high hydrophobicity, and when a film is formed, it is in the film in the film forming process. Residual water content can be reduced, and a conductive film having good transparency can be formed.
In the present invention, the compound (C) represented by the general formula (3) may be used alone or in combination of two or more. Moreover, any known compound can be used.

Specific examples of the structure of the compound represented by the general formula (3) include the following.

Further, in the conductive polymer composition of the present invention, L in the general formula (3) may have a hetero atom in a linear, branched or cyclic tetravalent organic having 2 to 10 carbon atoms. It preferably contains the compound that is the group.

In addition to the structure represented by the general formula (3), the following are preferably used in the present invention.

Further, the contents of the compound represented by the general formula of [0120] and the compound represented by the general formula (3) in the conductive polymer composition in the present invention are the above-mentioned (A) π-conjugated polymer and (B). ) It is preferably 1 part by mass to 50 parts by mass, and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the conductive polymer containing the dopant polymer. If the content of the compound represented by the general formula (3), such as the compound represented by the general formula of [0120], is such, the antistatic agent formed by the conductive polymer composition of the present invention is used. Acid diffusion from the film to the resist layer is reduced.

(Surfactant)
In the present invention, a surfactant may be added in order to further improve the wettability to the workpiece such as the substrate. Examples of such a surfactant include various nonionic, cationic and anionic surfactants. Specifically, for example, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylic acid ester, sorbitan ester, polyoxyethylene sorbitan ester, alkyltrimethylammonium chloride, alkylbenzylammonium. Cationic surfactants such as chloride, anionic surfactants such as alkyl or alkylallyl sulfates, alkyl or alkylallyl sulfonates, dialkylsulfosuccinates, amphoteric ionic surfactants such as amino acid type and betaine type, etc. Can be mentioned.

As described above, each of the conductive polymer composite of the present invention and its composition can efficiently remove residual water in the film during film formation, and has good filterability and spin-coating property and flatness. Therefore, it is possible to form a conductive film having high transparency.

[Condensate]
Each of the conductive polymer composite and the composition thereof obtained as described above can form a conductive film by being applied to a workpiece such as a substrate. Examples of the method for applying the conductive polymer composite (solution) include coating with a spin coater, bar coater, dipping, comma coating, spray coating, roll coating, screen printing, flexographic printing, gravure printing, inkjet printing and the like. Will be printed. After coating, a conductive film can be formed by heat treatment with a hot air circulation furnace, a hot plate, etc., IR, UV irradiation, and the like.

As described above, each of the conductive polymer composite of the present invention and its composition can be made into a conductive film by being applied and formed on a substrate or the like. Further, since the conductive film thus formed is excellent in conductivity and transparency, it can function as a transparent electrode layer or a hole injection layer.

[substrate]
The present invention also provides a substrate on which a conductive film is formed by each of the above-mentioned conductive polymer composite of the present invention and a composition thereof. In particular, it is preferable to use a substrate on which a transparent electrode layer or a hole injection layer in an organic EL element is formed.
Examples of the substrate include a glass substrate, a quartz substrate, a photomask blank substrate, a resin substrate, a silicon wafer, a gallium arsenic wafer, a compound semiconductor wafer such as an indium phosphide wafer, and a flexible substrate. It can also be applied on a photoresist film and used as an antistatic top coat.

As described above, in each of the conductive polymer composite and the composition thereof of the present invention, the (B) dopant polymer containing the sulfo group of the super strong acid and the non-doped fluorination unit is the (A) π-conjugated polymer. By forming a composite with, it has low viscosity and good filterability, good film forming property by spin coating, and transparency, flatness, durability, and conductivity when forming a film. It is possible to form a good conductive film. Further, by adding the compound (C) represented by the above general formula (3) for the purpose of relaxing the diffusion of H ⁺ derived from the non-doped acid unit, the acidity appropriate for the composition is maintained and after film formation. H ⁺ diffusion to the outside of the membrane can also be suppressed. Each of such a conductive polymer composite and its composition has good film forming property on both an organic substrate and an inorganic substrate having strong hydrophobicity.
Further, the conductive film formed by each of the conductive polymer composite and the composition thereof has excellent conductivity, transparency and the like, and therefore functions as a transparent electrode layer or a hole injection layer in the organic EL element. Can be.

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

[Dopant polymer synthesis example]
The raw material monomers for polymerizing the (B) dopant polymer in the conductive polymer composite used in each example are shown below.

[Synthesis Example 1]
1.20 g of monomer a "1, 3.75 g of monomer b" 1 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. under a nitrogen atmosphere. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 21,000
Molecular weight distribution (Mw / Mn) = 1.90
This polymer compound is referred to as (polymer 1).

[Synthesis Example 2]
In a nitrogen atmosphere, 0.6 g of monomer a "1, 5.00 g of monomer b" 1 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 20,500
Molecular weight distribution (Mw / Mn) = 1.94
This polymer compound is referred to as (polymer 2).

[Synthesis Example 3]
1.20 g of monomer a "2, 3.75 g of monomer b" 1 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. under a nitrogen atmosphere. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 20,000
Molecular weight distribution (Mw / Mn) = 1.88
This polymer compound is referred to as (polymer 3).

[Synthesis Example 4]
In a nitrogen atmosphere, 1.51 g of monomer a "1", 2.55 g of monomer b "2 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 22,000
Molecular weight distribution (Mw / Mn) = 1.93
This polymer compound is referred to as (polymer 4).

[Synthesis Example 5]
In a nitrogen atmosphere, 0.60 g of monomer a "1", 4.07 g of monomer b "2 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 19,500
Molecular weight distribution (Mw / Mn) = 1.99
This polymer compound is referred to as (polymer 5).

[Synthesis Example 6]
In a nitrogen atmosphere, 3.75 g of monomer a "6, 1.08 g of monomer b" 1 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 21,500
Molecular weight distribution (Mw / Mn) = 2.07
This polymer compound is referred to as (polymer 6).

[Synthesis Example 7]
In a nitrogen atmosphere, 0.87 g of monomer a "7, 5.00 g of monomer b" 1 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 19,500
Molecular weight distribution (Mw / Mn) = 2.00
This polymer compound is referred to as (polymer 7).

[Synthesis Example 8]
In a nitrogen atmosphere, 1.00 g of monomer a "8, 5.00 g of monomer b" 1 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 20,000
Molecular weight distribution (Mw / Mn) = 1.85
This polymer compound is referred to as (polymer 8).

[Synthesis Example 9]
In a nitrogen atmosphere, 1.51 g of monomer a "1 and 1.97 g of monomer b" 3 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 19,000
Molecular weight distribution (Mw / Mn) = 1.61
This polymer compound is referred to as (polymer 9).

[Synthesis Example 10]
In a nitrogen atmosphere, 1.51 g of monomer a "1 and 1.97 g of monomer b" 4 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 18,000
Molecular weight distribution (Mw / Mn) = 1.68
This polymer compound is referred to as (polymer 10).

[Synthesis Example 11]
In a nitrogen atmosphere, 0.90 g of monomer a "1 and 4.60 g of monomer b" 5 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 26,000
Molecular weight distribution (Mw / Mn) = 2.04
This polymer compound is referred to as (polymer 11).

[Synthesis Example 12]
In a nitrogen atmosphere, 0.90 g of monomer a "1 and 2.35 g of monomer b" 6 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the sodium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 31,000
Molecular weight distribution (Mw / Mn) = 2.11.
This polymer compound is referred to as (polymer 12).

[Synthesis Example 13]
1.20 g of monomer a "1 and 1.93 g of monomer b" 7 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. under a nitrogen atmosphere. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the lithium salt was converted into a sulfonimide group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 23,000
Molecular weight distribution (Mw / Mn) = 1.88
This polymer compound is referred to as (polymer 13).

[Synthesis Example 14]
1.20 g of monomer a "1 and 2.60 g of monomer b" 8 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. under a nitrogen atmosphere. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the potassium salt was converted into an n-carbonylsulfonamide group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 29,000
Molecular weight distribution (Mw / Mn) = 1.66
This polymer compound is referred to as (polymer 14).

[Synthesis Example 15]
1.20 g of monomer a "1, 1.90 g of monomer b" 9 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl were dissolved in 3 g of methanol in 10 g of methanol stirred at 64 ° C. under a nitrogen atmosphere. The solution was added dropwise over 4 hours. Further, the mixture was stirred at 64 ° C. for 4 hours. After cooling to room temperature, the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to give a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the potassium salt was converted into an n-carbonylsulfonamide group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 27,000
Molecular weight distribution (Mw / Mn) = 1.61
This polymer compound is referred to as (polymer 15).

[Synthesis Example 16]
A solution of 6.25 g of monomer b "1 and 0.12 g of 2,2'-azobis (isobutyric acid) dimethyl in 3 g of methanol was added dropwise to 10 g of methanol stirred at 64 ° C. under a nitrogen atmosphere over 4 hours. The mixture was further stirred at 64 ° C. for 4 hours, and then the obtained reaction solution was added dropwise to 10 g of ethyl acetate with vigorous stirring. The resulting solid substance was filtered off and vacuumed at 50 ° C. for 15 hours. Drying gave a white polymer.
The obtained white polymer was dissolved in 100 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. When the obtained polymer was measured by ¹⁹ F, ¹ H-NMR and GPC, the following analysis results were obtained.
Weight average molecular weight (Mw) = 22,500
Molecular weight distribution (Mw / Mn) = 1.90
This polymer compound is referred to as (polymer 16).

[Preparation of conductive polymer composite dispersion liquid containing polythiophene as a π-conjugated polymer]
(Preparation Example 1)
2.27 g of 3,4-ethylenedioxythiophene and a solution of 15.0 g of dopant polymer 1 in 1,000 mL of ultrapure water were mixed at 30 ° C.
The mixture solution thus obtained was kept at 30 ° C., and while stirring, 4.99 g of sodium persulfate dissolved in 100 mL of ultrapure water and 1.36 g of ferric sulfate oxidation catalyst solution were slowly added. The mixture was stirred for 4 hours and reacted.
1,000 mL of ultrapure water was added to the obtained reaction solution, and about 1,000 mL of the solution was removed by using an ultrafiltration method. This operation was repeated 3 times.
Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treated solution subjected to the above-mentioned filtration treatment, and about 2,000 mL of the treated solution was removed using an ultrafiltration method. To this, 2,000 mL of ion-exchanged water was added, and about 2,000 mL of the liquid was removed using an ultrafiltration method. This operation was repeated 3 times.
Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by an ultrafiltration method. This operation was repeated 5 times to obtain 1.3% by mass of a blue conductive polymer composite dispersion liquid 1.

The conditions for extrafiltration were as follows.
Molecular weight cut-off of ultrafiltration membrane: 30K
Cross-flow type supply liquid flow rate: 3,000 mL / membrane partial pressure: 0.12 Pa
In other preparation examples, extrafiltration was performed under the same conditions.

(Preparation Example 2)
15.0 g of dopant polymer 1 was changed to dopant polymer 2, the amount of 3,4-ethylenedioxythiophene was 2.09 g, the amount of sodium persulfate was 4.59 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the weight was changed to 1.25 g, to obtain a conductive polymer composite dispersion liquid 2.

(Preparation Example 3)
The 15.0 g dopant polymer 1 was changed to the dopant polymer 3, the compounding amount of 3,4-ethylenedioxythiophene was 2.27 g, the compounding amount of sodium persulfate was 4.99 g, and the compounding amount of ferric sulfate. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.36 g, to obtain a conductive polymer composite dispersion liquid 3.

(Preparation Example 4)
15.0 g of dopant polymer 1 was changed to dopant polymer 4, the amount of 3,4-ethylenedioxythiophene was 2.79 g, the amount of sodium persulfate was 6.13 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the weight was changed to 1.67 g, to obtain a conductive polymer composite dispersion liquid 4.

(Preparation Example 5)
15.0 g of dopant polymer 1 was changed to dopant polymer 5, the amount of 3,4-ethylenedioxythiophene was 2.64 g, the amount of sodium persulfate was 5.82 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.59 g, to obtain a conductive polymer composite dispersion liquid 5.

(Preparation Example 6)
15.0 g of dopant polymer 1 was changed to dopant polymer 6, the amount of 3,4-ethylenedioxythiophene was 2.34 g, the amount of sodium persulfate was 5.14 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.40 g, to obtain a conductive polymer composite dispersion liquid 6.

(Preparation Example 7)
15.0 g of dopant polymer 1 was changed to dopant polymer 7, the amount of 3,4-ethylenedioxythiophene was 1.97 g, the amount of sodium persulfate was 4.32 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.17 g, to obtain a conductive polymer composite dispersion liquid 7.

(Preparation Example 8)
15.0 g of dopant polymer 1 was changed to dopant polymer 8, the amount of 3,4-ethylenedioxythiophene was 1.91 g, the amount of sodium persulfate was 4.20 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.12 g, to obtain a conductive polymer composite dispersion liquid 8.

(Preparation Example 9)
15.0 g of dopant polymer 1 was changed to dopant polymer 9, the amount of 3,4-ethylenedioxythiophene was 3.11 g, the amount of sodium persulfate was 6.62 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.87 g, to obtain a conductive polymer composite dispersion liquid 9.

(Preparation Example 10)
15.0 g of dopant polymer 1 was changed to dopant polymer 10, the amount of 3,4-ethylenedioxythiophene was 3.11 g, the amount of sodium persulfate was 6.85 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the weight was changed to 1.87 g, to obtain a conductive polymer composite dispersion liquid 10.

(Preparation Example 11)
15.0 g of dopant polymer 1 was changed to dopant polymer 11, the amount of 3,4-ethylenedioxythiophene was 2.06 g, the amount of sodium persulfate was 4.54 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.24 g, to obtain a conductive polymer composite dispersion liquid 11.

(Preparation Example 12)
The 15.0 g dopant polymer 1 was changed to the dopant polymer 12, the compounding amount of 3,4-ethylenedioxythiophene was 2.97 g, the compounding amount of sodium persulfate was 6.53 g, and the compounding amount of ferric sulfate. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.78 g, to obtain a conductive polymer composite dispersion liquid 12.

(Preparation Example 13)
15.0 g of dopant polymer 1 was changed to dopant polymer 13, the amount of 3,4-ethylenedioxythiophene was 2.97 g, the amount of sodium persulfate was 6.55 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.79 g, to obtain a conductive polymer composite dispersion liquid 13.

(Preparation Example 14)
15.0 g of dopant polymer 1 was changed to dopant polymer 14, the amount of 3,4-ethylenedioxythiophene was 1.78 g, the amount of sodium persulfate was 5.67 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.55 g, to obtain a conductive polymer composite dispersion liquid 14.

(Preparation Example 15)
The 15.0 g dopant polymer 1 was changed to the dopant polymer 15, the blending amount of 3,4-ethylenedioxythiophene was 3.20 g, the blending amount of sodium persulfate was 7.04 g, and the blending amount of ferric sulfate. Preparation was carried out in the same manner as in Preparation Example 1 except that the weight was changed to 1.92 g, to obtain a conductive polymer composite dispersion liquid 15.

(Comparative Preparation Example 1)
15.0 g of dopant polymer 1 was changed to dopant polymer 16, the amount of 3,4-ethylenedioxythiophene was 1.93 g, the amount of sodium persulfate was 4.25 g, and the amount of ferric sulfate was. Preparation was carried out in the same manner as in Preparation Example 1 except that the amount was changed to 1.16 g, to obtain a conductive polymer composite dispersion liquid 16.

(Comparative Preparation Example 2)
5.0 g of 3,4-ethylenedioxythiophene and 83.3 g of an aqueous polystyrene sulfonic acid solution (18.0% by mass manufactured by Aldrich) diluted with 250 mL of ion-exchanged water were mixed at 30 ° C. Other than that, the preparation was carried out in the same manner as in Preparation Example 1 to obtain 1.3% by mass of a blue conductive polymer composite dispersion liquid 17 (PEDOT-PSS dispersion liquid).

[Evaluation of Conductive Polymer Composition Containing Polythiophene as π-Conjugated Polymer]
L- (+)-Lycine 0, which is one of the compounds (C) represented by the above general formula (3), is added to the 2.5% by mass conductive polymer composite dispersion obtained in Preparation Examples 1 to 15. .43% by mass and fluoroalkylnonionic surfactant FS-31 (manufactured by DuPont) are mixed, and then filtered using a cellulosic filter (manufactured by ADVANTEC) having a pore size of 3.00 to 0.45 μm. , Conductive polymer compositions were prepared and used as Examples 1 to 15, respectively.

[Comparison example]
Conductive polymer compositions were prepared in the same manner as in Examples except that the conductive polymer composite dispersions 16 and 17 obtained in Comparative Preparation Examples 1 and 2 were used, and used as Comparative Examples 1 and 2, respectively.

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

(Filtability)
In the preparation of the conductive polymer compositions of the above Examples and Comparative Examples, the filter limit pore diameters that could be filtered and passed through when filtration was performed using a regenerated cellulose filter having a pore size of 3.0 to 0.45 μm are shown in Table 1. Shown in.

(Applicability)
First, the conductive polymer composition was spin-coated on a Si wafer using 1H-360S SPINCOATER (manufactured by MIKASA) so that the film thickness was 100 ± 5 nm. Next, the film was baked at 120 ° C. for 5 minutes in a precision high temperature machine to remove the solvent 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 (manufactured by JA Woolham) with a variable incident angle. Table 1 shows those in which a uniform film can be formed as ◯, and those in which the refractive index can be measured but particles-derived defects or partial striations occur in the film as x.

(viscosity)
The solid content of the conductive polymer composition was set to 1.3% by mass, and the liquid temperature was adjusted to 25 ° C. 35 mL was measured in the attached dedicated measuring cell of the tuning fork type vibration viscometer SV-10 (manufactured by A & D Co., Ltd.), and the viscosity immediately after preparation was measured. The results are shown in Table 1.

(PH measurement)
The pH of the conductive polymer composition was measured using a pH meter D-52 (manufactured by HORIBA, Ltd.). The results are shown in Table 1.

(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 method for evaluating conductivity. RMS (root mean square roughness) was measured by AFM NANO-IM-8 (manufactured by Image Metrology). The results are shown in Table 1.

(Transmittance)
From the refractive index (n, k) at a wavelength of 636 nm measured by a spectroscopic ellipsometer (VASE) with a variable incident angle, the transmittance for a light beam having a wavelength of 550 nm at FT = 200 nm was calculated. The results are shown in Table 1.

(conductivity)
1.0 mL of the conductive polymer composition was dropped onto a SiO ₂ wafer having a diameter of 4 inches (100 mm), and 10 seconds later, the whole was rotationally coated using a spinner. The rotary coating conditions were adjusted so that the film thickness was 100 ± 5 nm. A conductive film was obtained by baking at 120 ° C. for 5 minutes in a precision high temperature machine and removing the solvent.
The conductivity (S / cm) of the obtained conductive film is the surface resistivity (Ω / □) measured using Hiresta-UP MCP-HT450 and Loresta-GP MCP-T610 (both manufactured by Mitsubishi Chemical Corporation). It was obtained from the measured value of the film thickness. The results are shown in Table 1.

As shown in Table 1, Examples 1 to 15 containing polythiophene as a π-conjugated polymer and a dopant polymer having repeating units a and b have good filterability and are uniform when applied by a spin coater. A coating film could be obtained. In addition, the conductivity showed E-04 to E-05S / cm, which is suitable as a hole injection layer material, the transmittance to visible light at λ = 550 nm was good, and the surface roughness was also good.

On the other hand, Comparative Example 1 having no repeating unit a and Comparative Example 2 using polystyrene sulfonic acid having no repeating units a and b as a dopant polymer have a limit in the decrease in viscosity, and Comparative Example 1 has a limit in terms of filterability. Although the same as in Examples 1 to 15, the surface roughness of the film after film formation was inferior, and in Comparative Example 2, the filterability was further inferior, and the filtration limit filter pore diameter remained at 1.0 μm. Therefore, in Comparative Example 2, as a result, particles were observed on the film in the spin coating, and striations caused by particles and bubbles were generated. Further, in the mounted light emission test of an organic EL element having high conductivity, which will be described later, an electrode-like function is exhibited in a portion other than the vapor-filmed surface of ITO vapor-deposited on the substrate as a transparent electrode, and the electrode-like function is exhibited on the ITO electrode. Excessive light emission in the portion other than the light emission area of the stacked elements caused a decrease in the light emission efficiency of the original element portion. Further, the transmittance for visible light at λ = 550 nm was inferior to that of Examples 1 to 15.

The conductive compositions of Examples 1 to 15 and Comparative Examples 1 and 2 were mounted as a hole injection layer in an organic EL device, and the brightness reduction rate of each device was measured.

The compositions of Examples 1 to 15 and Comparative Examples 1 and 2 were spin-coated on the washed glass substrate with ITO so as to have a film thickness of 100 nm, and α-NPD (diphenylnaphthyldiamine) was applied as a hole transport layer at 80 nm. It was laminated by vapor deposition so as to have a film thickness of. Next, Alq ₃ (tris (8-hydroxyquinoline) aluminum complex) was deposited as a light emitting layer so as to have a film thickness of 35 nm, and 8-Liq (8-hydroxyquinolinolato-lithium) was deposited on the upper layer to a film thickness of 30 nm. It was vapor-deposited so as to be. An electrode having a film thickness of 100 nm was formed on the electrode with a mixture of magnesium and silver to obtain an organic EL device. This element was continuously emitted with a high load of a fixed current density of 200 mA / m ² , and the elapsed time until the brightness became 70% of the initial brightness was measured. Table 2 shows these results.

As shown in Table 2, it is a conductive polymer composition obtained by adding compound (C) to a conductive polymer composite containing (A) polythiophene as a π-conjugated polymer and (B) a dopant polymer having a repeating unit a. In Examples 1 to 15, the effect of reducing the residual water content during the film formation by the repeating unit a was remarkably exhibited, and the brightness reduction rate (device life) of the organic EL element in which these films were mounted as the hole injection layer became long.

On the other hand, in the composition (Comparative Examples 1 and 2) of the conductive polymer complex containing the dopant polymer having no repeating unit a and the compound (C), a remarkable decrease in brightness was observed, and the device life was short. ..

As described above, each of the conductive polymer composite of the present invention and its composition has low viscosity, good filterability, good coating film forming property by spin coating or the like, and among the components of (B) dopant polymer. Due to the influence of fluorine atoms existing in each repeating unit of a and b, the removal of residual water in the film during film formation is efficient, and the formed film is transparent, flat, conductive or hole-injected. It has been clarified that it is possible to form a conductive film with good efficiency. Further, in (B) a dopant polymer, a repeating unit b containing a sulfo group and a non-doped fluorination unit a having no sulfonic acid terminal are copolymerized, and the polymer is used as a dopant to form a composite with (A) a π-conjugated polymer. By forming the above, the excess sulfonic acid terminal in the non-doped state is reduced, and as a result, the generation rate of H ⁺ is reduced ^. It is possible to suppress the influence on the constituent layers of. Further, each of such a conductive polymer composite and its composition has a good affinity for an organic / inorganic substrate having high hydrophobicity, and has a film forming property for both an organic substrate and an inorganic substrate. It turned out to be good.

Further, the conductive film formed by each of such a conductive polymer composite and its composition is excellent in conductivity, hole injection efficiency, transparency and the like, and when applied as a constituent film of a thin film laminated element. Also, since volatilization and aggregation of water from the film can be reduced, it can effectively function as a transparent electrode layer or a hole injection layer of the thin film laminated element.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

Claims (10)

(A) π-conjugated polymer, (B) repeating unit a represented by the following general formula (1), and 1 selected from the repeating units represented by the following general formulas (2-1) to (2-7). A composite comprising a dopant polymer consisting of a seed or a copolymer comprising two or more repeating units b.
The complex is a complex in which the monomer giving the repeating unit a is any of the following formulas (G1) to (G3), or the monomer giving the repeating unit b is the following general formulas (G4) to (G4). A conductive polymer complex characterized by being a complex which is any one of G25).

(In the formula, R ¹ is a hydrogen atom or a methyl group, Z is a phenylene group, a naphthylene group, or an ester group, and if Z is a phenylene group or a naphthylene group, R ² is a single bond, an ester group, or an ether. It is any of a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either or both of these groups, and if Z is an ester group, R ² is simple. It is any of a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either or both of a bonded or ether group. M is 1 to 3. R ³ , R ⁵ , R ⁷ , R ¹⁰ , R ¹² , R ¹³ and R ¹⁵ are independently hydrogen atoms or methyl groups, respectively, and R ⁴ , R ⁶ , R ⁸ , R ¹¹ and R ¹⁴ are. , A linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms, each of which may independently have a single bond, an ether group, an ester group, or both. R ⁹ is a linear or branched alkylene group having 1 to 4 carbon atoms, and one or two of the hydrogen atoms in R ⁹ may be substituted with a fluorine atom. X ₁ , X ₂ , X ₃ , X ₄ , X ₆ and X ₇ are each independently single-bonded, phenylene group, naphthylene group, ether group, ester group or amide group, and X ₅ is single-bonded. , Ether group, or ester group. Y indicates any of an ether group, an ester group, an amino group, or an amide group, and the amino group and the amide group have the number of carbon atoms which may contain a hydrogen atom or a hetero atom. It may contain any of 1-12 linear, branched or cyclic hydrocarbon groups. Rf ₁ is a fluorine atom or a trifluoromethyl group and Rf ₂ and Rf ₃ are at least one fluorine atom. It is a linear or branched alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with a fluorine atom or a trifluoromethyl group, and n is an integer of 1 to 4 a, b1, b2. , B3, b4, b5, b6, and b7 are 0.1 ≦ a ≦ 0.6, 0 ≦ b1 ≦ 0.9, 0 ≦ b2 ≦ 0.9, 0 ≦ b3 ≦ 0.9, 0 ≦ b4. ≦ 0.9, 0 ≦ b5 ≦ 0.9, 0 ≦ b6 ≦ 0.9, 0 ≦ b7 ≦ 0.9, and 0 <b1 + b2 + b3 + b4 + b5 + b6 + b7 ≦ 0.9).

(In the formula, R ³ , R ⁵ , R ⁷ , R ¹⁰ , R ¹² , R ¹³ , and R ¹⁵ are the same as described above.) The repeating unit a in the (B) dopant polymer is characterized by containing one or more selected from the repeating units a1 to a5 represented by the following general formulas (4-1) to (4-5). The conductive polymer composite according to claim 1.

(In the formula, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom or a methyl group, R is a single bond, a methylene group, an ethylidene group, an isopropylidene group, and Y m is the same as above.) The repeating unit b in the (B) dopant polymer includes one or more selected from the repeating units b'1 to b'4 represented by the following general formulas (5-1) to (5-4). The conductive polymer complex according to claim 1 or 2, characterized in that it is a product.

(In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ are independently hydrogen atoms or methyl groups, respectively, and b'1, b'2, b'3 and b'4 are 0≤b'1. <1.0, 0≤b'2 <1.0, 0≤b'3 <1.0, 0≤b'4 <1.0, 0 <b'1 + b'2 + b'3 + b'4 <1.0 Is.) The conductive polymer complex according to any one of claims 1 to 3, wherein the dopant polymer (B) further contains a repeating unit c represented by the following general formula (6).

(C is 0 <c <1.0.) The conductive polymer complex according to any one of claims 1 to 4, wherein the dopant polymer (B) has a weight average molecular weight of 1,000 to 500,000. The conductive polymer complex according to any one of claims 1 to 5, wherein the copolymerization ratio of the repeating unit a in the dopant polymer (B) to all the repeating units is 10% to 60%. .. The conductive polymer composite according to any one of claims 1 to 6, wherein the dopant polymer (B) is a block copolymer. The (A) π-conjugated polymer polymerizes one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurophenes, aniline, polycyclic aromatic compounds, and derivatives thereof. The conductive polymer composite according to any one of claims 1 to 7, which is characterized by the above. The conductive polymer complex according to any one of claims 1 to 8, which is used for forming a transparent electrode layer or a hole injection layer of an organic EL device. A substrate characterized in that an electrode layer or a hole injection layer in an organic EL device is formed by the conductive polymer composite according to any one of claims 1 to 9.