JP6474358B2 - Conductive polymer composite and substrate - Google Patents

Description

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

  Although a polymer having a conjugated double bond (π-conjugated polymer) does not exhibit conductivity, the polymer itself exhibits conductivity by doping with an appropriate anion molecule, and a conductive polymer material (conductivity). Polymer composition). As the π-conjugated polymer, (hetero) aromatic polymers such as polyacetylene, polythiophene, polyselenophene, polytellurophene, polypyrrole, polyaniline, and mixtures thereof are used, and as anion molecules (dopants), Sulfonic anions are most often used. This is because sulfonic acid, which is a strong acid, efficiently interacts with the π-conjugated polymer.

  As the sulfonic acid-based anion dopant, sulfonic acid polymers such as polyvinyl sulfonic acid and polystyrene sulfonic acid (PSS) are widely used (Patent Document 1). In addition, sulfonic acid polymers include vinyl perfluoroalkyl ether sulfonic acids represented by registered trademark Nafion, which are used for fuel cell applications.

  Polystyrene sulfonic acid (PSS), which is a sulfonic acid homopolymer, is highly efficient in doping to π-conjugated polymers because sulfonic acid is continuously present in monomer units with respect to the polymer main chain, and π-conjugated after doping. The dispersibility of the water-based polymer in water can also be improved. This is because hydrophilicity is maintained by the presence of an excessive sulfo group in PSS, and the dispersibility in water is greatly improved.

  Since polythiophene using PSS as a dopant is highly conductive and can be handled as an aqueous dispersion, it is expected as a coating-type conductive film material replacing ITO (indium-tin oxide). However, as described above, PSS is a water-soluble resin and hardly dissolves in an organic solvent. Therefore, polythiophene using PSS as a dopant also has high hydrophilicity, but has low affinity for an organic solvent or an organic substrate, and it is difficult to disperse in an organic solvent and form a film on the organic substrate.

  In addition, when polythiophene using PSS as a dopant is used for a conductive film for organic EL lighting, for example, the hydrophilicity of polythiophene using PSS as a dopant is very high as described above, so that a large amount of moisture remains in the conductive film. The formed conductive film is easy to take in moisture from the external atmosphere. As a result, there is a problem in that the light emitting ability of the organic EL light emitting element is chemically changed to reduce the light emitting ability, the water aggregates over time and becomes a defect, and the lifetime of the entire organic EL device is shortened. In addition, polythiophene using PSS as a dopant has large particles in the aqueous dispersion, large irregularities on the surface of the film after film formation, and a problem that non-light-emitting parts called dark spots occur when applied to organic EL lighting There is.

  In addition, since polythiophene with PSS as a dopant has absorption in a blue region near a wavelength of 500 nm, when the material is applied on a transparent substrate such as a transparent electrode, the conductivity necessary for the device to function is used. Supplementing with solid content concentration and film thickness also has a problem of affecting the transmittance as a member.

  In Patent Document 2, a π-conjugated polymer formed by a repeating unit selected from thiophene, selenophene, tellurophene, pyrrole, aniline, and a polycyclic aromatic compound, and an organic solvent can be wetted, and more than 50% A conductive polymer composition formed by a conductive polymer containing a fluorinated acid polymer neutralized with a cation has been proposed, water, a precursor monomer of a π-conjugated polymer, a fluorinated acid polymer, And an oxidizing agent in any order has been shown to provide an aqueous dispersion of conductive polymer.

  However, such conventional conductive polymers have aggregated particles in the dispersion immediately after synthesis, and when an organic solvent that becomes a highly conductive agent is added as a coating material, the aggregation is further promoted and the filterability is deteriorated. To do. When spin coating is performed without filtration, there is a problem that a flat film cannot be obtained due to the influence of particle aggregates, resulting in poor coating.

  Polythiophene using PSS as a dopant can also be used as a hole injection layer. In this case, a hole injection layer is provided between the transparent electrode such as ITO and the light emitting layer. Since conductivity is ensured by the lower transparent electrode, the hole injection layer does not require high conductivity. The hole injection layer must be free of dark spots and have a high hole transport capability.

JP 2008-146913 A Japanese Patent No. 5264723

  As mentioned above, polythiophene-based conductive polymers using PSS such as PEDOT-PSS, which are highly versatile, have poor conductivity due to absorption of visible light, although they are highly conductive. Because of its high properties, filtration purification is difficult, and there is a problem that the film formability by spin coating and the surface roughness of the film forming portion are poor.

  The present invention has been made in view of the above circumstances, and it is possible to form a conductive film with good filterability and good film formation by spin coating and having high transparency and good flatness when the film is formed. It is an object to provide a conductive polymer composite.

（式中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は単結合、エステル基、あるいはエーテル基、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。Ｚは単結合、フェニレン基、ナフチレン基、エーテル基、エステル基のいずれかである。ａは、０＜ａ≦１．０である。） In order to achieve the above object, the present invention comprises (A) a π-conjugated polymer, and (B) a repeating unit a represented by the following general formula (1), and having a weight average molecular weight of 1,000 to 500,000. Dopant polymers that are in a range,
A conductive polymer composite is provided.

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² has a single bond, an ester group, an ether group, an ester group, or both of which may have 1 to 12 carbon atoms. A straight-chain, branched, or cyclic hydrocarbon group, Z is a single bond, a phenylene group, a naphthylene group, an ether group, or an ester group, and a is 0 <a ≦ 1.0. .)

  With such a conductive polymer composite, filterability is good, spin coat film formation on inorganic and organic substrates is good, and when forming a film, a conductive film with high transparency and good flatness is obtained. Can be formed.

（式中、Ｒ^１は前記と同様である。ａ１、ａ２、ａ３、及びａ４は、０≦ａ１≦１．０、０≦ａ２≦１．０、０≦ａ３≦１．０、０≦ａ４≦１．０、かつ０＜ａ１＋ａ２＋ａ３＋ａ４≦１．０である。） Moreover, it is preferable at this time that the repeating unit a in the said (B) component contains 1 or more types chosen from the repeating units a1-a4 shown by the following general formula (1-1)-(1-4). .

(Wherein R ¹ is the same as above. A1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4. ≦ 1.0 and 0 <a1 + a2 + a3 + a4 ≦ 1.0.)

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

（式中、ｂは、０＜ｂ＜１．０である。） At this time, the component (B) preferably further contains a repeating unit b represented by the following general formula (2).

(Wherein b is 0 <b <1.0)

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

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

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

  Also, at this time, the component (A) is obtained by polymerizing one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurophene, aniline, polycyclic aromatic compounds, and derivatives thereof. It is preferable that

  Such a monomer is easy to polymerize and has good stability in air, so that the component (A) can be easily synthesized.

  At this time, the conductive polymer composite is preferably dispersible in water or an organic solvent.

The present invention also provides a substrate having a conductive film formed of the conductive polymer composite.
Thus, the conductive polymer composite of the present invention can be formed into a conductive film by coating and forming a film on a substrate or the like.

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

As described above, in the conductive polymer composite of the present invention, the (B) component dopant polymer containing a super strong acid sulfo group forms a composite with the (A) component π-conjugated polymer. With low viscosity, good filterability, good film formability with spin coating, and when the film is formed, stability against light and heat is improved, so durability is high, transparency, A conductive film with good flatness and conductivity can be formed. In addition, such a conductive polymer composite has good affinity for an organic solvent and an organic substrate, and good film formability for both organic and inorganic substrates.
Moreover, since the electrically conductive film formed with such a conductive polymer composite is excellent in electroconductivity, transparency, etc., it can function as a transparent electrode layer.

  As described above, development of a conductive film forming material that has good filterability, good film formation by spin coating, and can form a conductive film with high transparency and good flatness when the film is formed. Was demanded.

  As a result of intensive studies on the above problems, the present inventors include a sulfo group having a trifluoromethyl group at the β-position instead of polystyrene sulfonic acid (PSS) widely used as a dopant for conductive polymer materials. By using a dopant polymer having a repeating unit, the super strong acid dopant polymer interacts strongly with the π-conjugated polymer, and the visible light absorption region of the π-conjugated polymer is shifted, thereby improving the transparency and the π-conjugated system. It has been found that the stability of light and heat is improved by strong ionic bonding between the polymer and the dopant polymer. Further, the present inventors have found that the filterability is improved, the film forming property by spin coating is improved, and the flatness during film formation is also improved, and the present invention has been completed.

（式中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は単結合、エステル基、あるいはエーテル基、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。Ｚは単結合、フェニレン基、ナフチレン基、エーテル基、エステル基のいずれかである。ａは、０＜ａ≦１．０である。） That is, the present invention
(A) a π-conjugated polymer, and (B) a dopant polymer containing a repeating unit a represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000,
Is a conductive polymer composite.

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² has a single bond, an ester group, an ether group, an ester group, or both of which may have 1 to 12 carbon atoms. A straight-chain, branched, or cyclic hydrocarbon group, Z is a single bond, a phenylene group, a naphthylene group, an ether group, or an ester group, and a is 0 <a ≦ 1.0. .)

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

[(A) π-conjugated polymer]
The conductive polymer composite of the present invention contains a π-conjugated polymer as the component (A). This (A) component should just be what polymerized the precursor monomer (organic monomer molecule | numerator) which forms (pi) conjugated system chain (structure in which the single bond and the double bond continued alternately).
Examples of such precursor monomers include monocyclic aromatics such as pyrroles, thiophenes, thiophene vinylenes, selenophenes, tellurophenes, phenylenes, phenylene vinylenes, and anilines; Cyclic aromatics; acetylenes and the like, and a single polymer or copolymer of these monomers can be used as the component (A).
Among the above monomers, pyrrole, thiophene, selenophene, tellurophene, aniline, polycyclic aromatic compounds, and derivatives thereof are preferable from the viewpoint of ease of polymerization and stability in air, pyrrole, thiophene, aniline, And derivatives thereof are particularly preferred, but not limited thereto.

  When the conductive polymer composite of the present invention contains polythiophene as the component (A) in particular, it has high conductivity and high transparency with visible light, so that a touch panel, an organic EL display, organic EL lighting, etc. Development to the use of can be considered. On the other hand, when the conductive polymer composite of the present invention contains polyaniline as the component (A), it is difficult to apply it for display because it absorbs more visible light and has lower conductivity than polythiophene. However, since it is easy to spin-coat with low viscosity, the use of the top coat for preventing the resist upper layer film from being charged by electrons in EB lithography can be considered.

  In addition, the component (A) can obtain sufficient conductivity even when the monomer constituting the π-conjugated polymer remains unsubstituted. However, in order to further increase the conductivity, an alkyl group, a carboxy group, a sulfo group, an alkoxy group can be obtained. A monomer substituted with a group, a hydroxy group, a cyano group, a halogen atom or the like may be used.

  Specific examples of monomers of pyrroles, thiophenes, and anilines include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 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-propyl Offene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodo Thiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxy Thiophene, 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-dioctyloxy Thiophene, 3,4-didecyloxythiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-ethylenedithiothiophene, 3,4-propylenedioxythiophene, 3,4- Butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxymethylthiophene, 3-methyl -4-carboxyethylthiophene, 3-methyl Ru-4-carboxybutylthiophene, 3,4- (2,2-dimethylpropylenedioxy) thiophene, 3,4- (2,2-diethylpropylenedioxy) thiophene, (2,3-dihydrothieno [3,4] -B] [1,4] dioxin-2-yl) methanol; aniline, 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2-propylaniline, 3-propylaniline, 2- Examples include butylaniline, 3-butylaniline, 2-isobutylaniline, 3-isobutylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-anilinesulfonic acid, and 3-anilinesulfonic acid.

  Among them, a (co) polymer composed of one or two kinds selected from pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, and 3,4-ethylenedioxythiophene has resistance and reactivity. From the point of view, it is preferably used. Furthermore, a single polymer of pyrrole or 3,4-ethylenedioxythiophene is more preferable because of its high conductivity.

For practical reasons, the number of repeating units (precursor monomers) in component (A) is preferably in the range of 2-20, more preferably in the range of 6-15.
Further, the molecular weight of the component (A) is preferably about 130 to 5,000.

（式中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は単結合、エステル基、あるいはエーテル基、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。Ｚは単結合、フェニレン基、ナフチレン基、エーテル基、エステル基のいずれかである。ａは、０＜ａ≦１．０である。） [(B) Dopant polymer]
The conductive polymer composite of the present invention contains a dopant polymer as the component (B). This (B) component dopant polymer is a super strong acidic polymer containing a sulfonic acid having a trifluoromethyl group at the β-position containing the repeating unit a represented by the following general formula (1).

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² has a single bond, an ester group, an ether group, an ester group, or both of which may have 1 to 12 carbon atoms. A straight-chain, branched, or cyclic hydrocarbon group, Z is a single bond, a phenylene group, a naphthylene group, an ether group, or an ester group, and a is 0 <a ≦ 1.0. .)

In general formula (1), R ¹ is a hydrogen atom or a methyl group.
R ² is a single bond, an ester group, an ether group, an ester group or any one of these, a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms. Examples of the hydrocarbon group include an alkylene group, an arylene group (for example, a phenylene group, a naphthylene group, etc.), an alkenylene group, and the like.
Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group.
a is 0 <a ≦ 1.0, and preferably 0.2 ≦ a ≦ 1.0.

  Specific examples of the monomer that gives the repeating unit a include the following.

（式中、Ｒ^１は前記と同様であり、Ｘは水素原子、リチウム原子、ナトリウム原子、カリウム原子、アミン化合物、又はスルホニウム化合物である。）

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

（式中、Ｒ^１は前記と同様である。ａ１、ａ２、ａ３、及びａ４は、０≦ａ１≦１．０、０≦ａ２≦１．０、０≦ａ３≦１．０、０≦ａ４≦１．０、かつ０＜ａ１＋ａ２＋ａ３＋ａ４≦１．０である。） The repeating unit a represented by the general formula (1) preferably includes one or more selected from repeating units a1 to a4 represented by the following general formulas (1-1) to (1-4). . That is, among the monomers exemplified above, monomers for obtaining the repeating units a1 to a4 are particularly preferable.

(Wherein R ¹ is the same as above. A1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4. ≦ 1.0 and 0 <a1 + a2 + a3 + a4 ≦ 1.0.)

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

（式中、ｂは、０＜ｂ＜１．０である。） The component (B) preferably further contains a repeating unit b represented by the following general formula (2). By including such a repeating unit b, the conductivity can be further improved.

(Wherein b is 0 <b <1.0)

（式中、Ｘ_２は水素原子、リチウム原子、ナトリウム原子、カリウム原子、アミン化合物、又はスルホニウム化合物である。） Specific examples of the monomer that gives the repeating unit b include the following.

(In the formula, X ₂ is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or a sulfonium compound.)

When X and X ₂ are amine compounds, (P1a-3) described in paragraph [0048] of JP2013-228447A can be exemplified.

Here, as described above, a satisfies 0 <a ≦ 1.0, and preferably 0.2 ≦ a ≦ 1.0. If 0 <a ≦ 1.0 (that is, if the repeating unit a is included), the effect of the present invention is obtained, but if 0.2 ≦ a ≦ 1.0, a better effect is obtained. When the repeating unit a includes one or more selected from the repeating units a1 to a4 as described above, 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, Preferably 0 ≦ a4 ≦ 1.0 and 0 <a1 + a2 + a3 + a4 ≦ 1.0, more preferably 0 ≦ a1 ≦ 0.9, 0 ≦ a2 ≦ 0.9, 0 ≦ a3 ≦ 0.9, 0 ≦ a4 ≦ 0.9 and 0.1 ≦ a1 + a2 + a3 + a4 ≦ 0.9, more preferably 0 ≦ a1 ≦ 0.8, 0 ≦ a2 ≦ 0.8, 0 ≦ a3 ≦ 0.8, 0 ≦ a4 ≦ 0.8 and 0.2 ≦ a1 + a2 + a3 + a4 ≦ 0.8.
Moreover, when the repeating unit b is included, it is preferable that it is 0.2 <= b <1.0 from a viewpoint of electroconductivity improvement, and it is more preferable that it is 0.3 <= b <= 0.8.
Further, the ratio of the repeating unit a and the repeating unit b is preferably 0.2 ≦ a ≦ 0.8 and 0.2 ≦ b ≦ 0.8, and 0.3 ≦ a ≦ 0.6 and 0. It is more preferable that 4 ≦ b ≦ 0.7.

  Further, the dopant polymer of the component (B) may have a repeating unit c other than the repeating unit a and the repeating unit b. Examples of the repeating unit c include styrene, vinylnaphthalene, vinylsilane, and acenaphthylene. , Indene, benzofuran, benzothiophene, (meth) acryl, vinylcarbazole and the like.

  Specific examples of the monomer that gives the repeating unit c include the following.

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

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

  Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropyl). Pionate), benzoyl peroxide, lauroyl peroxide and the like.

  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.

In the dopant polymer of the component (B), the monomer that gives the repeating unit a may be one type or two or more types, but it is preferable to combine a methacryl type monomer and a styrene type monomer that increase the polymerizability.
Moreover, when using 2 or more types of monomers which give the repeating unit a, each monomer may be copolymerized at random and may be copolymerized by the block. In the case of a block copolymer (block copolymer), a repeating structure composed of two or more kinds of repeating units a aggregates to form a sea-island structure, thereby generating a unique structure around the dopant polymer, and the conductivity is reduced. Benefits are expected to improve.

  Moreover, the monomer which gives the repeating units ac may be copolymerized at random, and each may be copolymerized by the block. In this case, as in the case of the above-mentioned repeating unit a, a merit that the conductivity is improved by using a block copolymer is expected.

  When random copolymerization is performed by radical polymerization, a method in which a monomer for copolymerization or a radical polymerization initiator is mixed and polymerization is performed by heating is common. When the polymerization is started in the presence of the first monomer and the radical polymerization initiator and the second monomer is added later, one side of the polymer molecule has a structure in which the first monomer is polymerized, and the other is the second monomer. Is a polymerized structure. However, in this case, repeating units of the first monomer and the second monomer are mixed in the intermediate portion, and the form is different from that of the block copolymer. Living radical polymerization is preferably used to form a block copolymer by radical polymerization.

  In the living radical polymerization method called RAFT polymerization (Reversible Addition Fragmentation Chain Polymerization), since the radical at the end of the polymer is always alive, the polymerization is started with the first monomer, and the second monomer is consumed when it is consumed. It is possible to form a diblock copolymer with a block of repeating units of the first monomer and a block of repeating units of the second monomer. In addition, when the polymerization is started with the first monomer, when the second monomer is added, and then the third monomer is added, a triblock polymer can be formed.

When RAFT polymerization is performed, a narrow dispersion polymer having a narrow molecular weight distribution (dispersion degree) is formed. Particularly, when RAFT polymerization is performed by adding a monomer at a time, a polymer having a narrower molecular weight distribution is formed. can do.
In addition, in the dopant polymer of (B) component, it is preferable that molecular weight distribution (Mw / Mn) is 1.0-2.0, and it is especially preferable that it is 1.0-1.5 and narrow dispersion. If it is narrow dispersion, it can prevent that the transmittance | permeability of the electrically conductive film formed with the conductive polymer composite using the same becomes low.

  In order to perform RAFT polymerization, a chain transfer agent is required. Specifically, 2-cyano-2-propylbenzothioate, 4-cyano-4-phenylcarbonothioylthiopentanoic acid, 2-cyano-2-propyl Dodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, 2- (dodecylthiocarbonothioylthio) -2-methylpropanoic acid, cyanomethyldodecylthiocarbonate, cyanomethyl Mention may be made of methyl (phenyl) carbamothioate, bis (thiobenzoyl) disulfide, bis (dodecylsulfanylthiocarbonyl) disulfide. Of these, 2-cyano-2-propylbenzothioate is particularly preferable.

When the dopant polymer of the component (B) includes the above-mentioned repeating unit c, the ratio of the repeating units a to c is 0 <a ≦ 1.0, 0 ≦ b <1.0, 0 <c <1.0. It is preferable that 0.1 ≦ a ≦ 0.9, 0.1 ≦ b ≦ 0.9, 0 <c ≦ 0.8, and more preferably 0.2 ≦ a ≦ 0. 8, 0.2 ≦ b ≦ 0.8, 0 <c ≦ 0.5.
It is preferable that a + b + c = 1.

  The dopant polymer as the component (B) has a weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 200,000. When the weight average molecular weight is less than 1,000, the heat resistance is inferior, and the uniformity of the complex solution with the component (A) is deteriorated. On the other hand, when the weight average molecular weight exceeds 500,000, in addition to deterioration of conductivity, viscosity increases and workability deteriorates, and dispersibility in water and organic solvents decreases.

  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. .

  In addition, as a monomer which comprises the dopant polymer of (B) component, although the monomer which has a sulfo group may be used, the lithium salt, sodium salt, potassium salt, ammonium salt, sulfonium salt of a sulfo group is used as a monomer. A polymerization reaction may be performed and converted to a sulfo group using an ion exchange resin after polymerization.

[Conductive polymer composite]
The conductive polymer composite of the present invention includes the above-mentioned (A) component π-conjugated polymer and (B) component dopant polymer, and (B) component dopant polymer is (A) component. A complex is formed by coordination with the π-conjugated polymer.

  The conductive polymer composite of the present invention is preferably dispersible in water or an organic solvent, and is spin-coated on an inorganic or organic substrate (an inorganic film or a substrate having an organic film formed on the substrate surface). And the flatness of the film can be improved.

(Method for producing conductive polymer composite)
The complex of the component (A) and the component (B) is, for example, a monomer (preferably, a raw material for the component (A) in an aqueous solution of the component (B) or a water / organic solvent mixed solution of the component (B). Pyrrole, thiophene, aniline, or a derivative monomer thereof) may be added, and an oxidant and optionally an oxidation catalyst may be added to perform oxidative polymerization.

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

  As a reaction solvent used when oxidative polymerization is performed, water or a mixed solvent of water and a solvent can be used. The solvent used here is miscible with water, and is preferably a solvent capable of dissolving or dispersing the component (A) and the component (B). For example, polar solvents such as N-methyl-2-pyrrolidone, N, N′-dimethylformamide, N, N′-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, and 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- Hexanediol, 1,9-nonanediol, polyvalent aliphatic alcohols such as neopentyl glycol, carbonate compounds such as ethylene carbonate and propylene carbonate, cyclic ethers such as dioxane and tetrahydrofuran Compounds, chain ethers such as dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, 3-methyl-2- Examples include heterocyclic compounds such as oxazolidinone, and nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile. These solvents may be used alone or as a mixture of two or more. The blending amount of these water-miscible solvents is preferably 50% by mass or less of the entire reaction solvent.

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

  As the organic carboxylic acid, aliphatic, aromatic, cycloaliphatic and 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, And triphenylacetic acid.

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

  As the organic sulfonic acid, those containing one or more sulfonic acid groups in aliphatic, aromatic, cycloaliphatic and the like 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-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoro Lomethanesulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid , 3-aminopropanesulfonic acid, N-cyclohexyl- -Aminopropanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octyl Benzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, dipropylbenzene Sulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid, 4 Amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene- 1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-acetamido-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methyl Naphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1-sulfonic acid, naphthalenesulfonic acid formalin polycondensation Melamine sulfonic acid Examples thereof include sulfonic acid compounds containing a sulfonic acid group such as formalin polycondensate.

  Examples of those containing two or more sulfonic acid groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, m-benzenedisulfonic acid, o-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfone. Acid, xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, diethylbenzene disulfonic acid, dibutylbenzene disulfonic acid, naphthalene disulfonic acid, methyl naphthalene disulfonic acid Ethyl naphthalene disulfonic acid, dodecyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, butyl naphthalene disulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino -3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, anthracene disulfonic acid, butylanthracene disulfonic acid, 4-acetamide-4 '-Isothio-cyanatostilbene-2,2'-disulfonic acid, 4-acetamido-4'-isothiocyanatostilbene-2,2'-disulfonic acid, 4-acetamido-4'-maleimidylstilbene-2, 2'-disulfonic acid, 1-acetoxypyrene-3,6,8-trisulfonic acid, 7-amino-1,3,6-naphthalene trisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid , 3-amino-1,5,7-naphthalene trisulfonic acid and the like.

  These anions other than the component (B) may be added to the solution containing the raw material monomer of the component (A), the component (B), the oxidizing agent and / or the oxidation polymerization catalyst before the polymerization of the component (A), Moreover, you may add to the conductive polymer composite (solution) containing (A) component and (B) component after superposition | polymerization.

The composite of component (A) and component (B) obtained in this way can be used after being finely divided by a homogenizer, a ball mill or the like, if necessary.
It is preferable to use a mixing and dispersing machine capable of applying a high shearing force for the fine graining. Examples of the mixing and dispersing machine include a homogenizer, a high-pressure homogenizer, and a bead mill. Among them, a high-pressure homogenizer is preferable.

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

  Before or after the fine granulation, impurities may be removed by a technique such as filtration, ultrafiltration, or dialysis, and the mixture may be purified with a cation exchange resin, an anion exchange resin, a chelate resin, or the like.

  The total content of the component (A) and the component (B) in the conductive polymer complex solution is preferably 0.05 to 5.0% by mass. If the total content of the component (A) and the component (B) is 0.05% by mass or more, sufficient conductivity is obtained, and if it is 5.0% by mass or less, a uniform conductive coating film is easy. Is obtained.

  The content of the component (B) is preferably such that the sulfo group in the component (B) is in the range of 0.1 to 10 mol with respect to 1 mol of the component (A). It is more preferable that the amount be in the range. When the sulfo group in the component (B) is 0.1 mol or more, the doping effect on the component (A) is high, and sufficient conductivity can be ensured. Moreover, if the sulfo group in (B) component is 10 mol or less, content of (A) component will also become moderate and sufficient electroconductivity will be obtained.

  Organic solvents that can be added to the polymerization reaction aqueous solution or that can dilute the monomer include methanol, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and 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, t-butyl acetate, propiate Phosphate t- butyl, propylene glycol monobutyl t- butyl ether acetate, .gamma.-butyrolactone and can mixtures thereof and the like.

  In addition, the usage-amount of an organic solvent has preferable 0-1,000 mL with respect to 1 mol of monomers, and 0-500 mL is especially preferable. If the amount of the organic solvent used is 1,000 mL or less, the reaction vessel will not be excessive, which is economical.

[Other ingredients]
(Surfactant)
In the present invention, a surfactant may be added to improve wettability to a workpiece such as a substrate. Examples of such surfactants include nonionic, cationic, and anionic surfactants. Specific examples include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene carboxylic acid ester, sorbitan ester, and polyoxyethylene sorbitan ester, alkyl trimethyl ammonium chloride, alkyl benzyl ammonium. Cationic surfactants such as chloride, anionic surfactants such as alkyl or alkyl allyl sulfate, alkyl or alkyl allyl sulfonate, dialkyl sulfosuccinate, and zwitterionic surfactants such as amino acid type and betaine type, Examples thereof include acetylene alcohol surfactants and acetylene alcohol surfactants whose hydroxy groups are converted into polyethylene oxide or polypropylene oxide.

(High conductivity agent)
In the present invention, an organic solvent may be added separately from the main solvent for the purpose of improving the conductivity of the conductive polymer composite. Examples of such an additive solvent include polar solvents. Specifically, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidone ( NMP), sulfolane and mixtures thereof. The addition amount is preferably 1.0 to 30.0% by mass, and particularly preferably 3.0 to 10.0% by mass.

(Neutralizer)
In the present invention, the pH of the conductive polymer composite in the aqueous solution is acidic. For the purpose of neutralizing this, a nitrogen-containing aromatic cyclic compound described in paragraphs [0033] to [0045] of JP-A-2006-96975 and a positive ion described in paragraph [0127] of Japanese Patent No. 5264723 are disclosed. Ions can be added to control the pH to neutral. By making the pH of the solution close to neutral, it is possible to prevent the occurrence of rust when applied to a printing press.

  With the conductive polymer composite of the present invention as described above, it is possible to form a conductive film having good filterability and film formation by spin coating, high transparency, and low surface roughness.

[Conductive film]
The conductive polymer composite (solution) obtained as described above can form a conductive film by applying it to a workpiece such as a substrate. Examples of the method for applying the conductive polymer composite (solution) include spin coater coating, bar coater, dipping, comma coating, spray coating, roll coating, screen printing, flexographic printing, gravure printing, inkjet printing, and the like. It is done. After the application, a conductive film can be formed by performing heat treatment with a hot-air circulating furnace, a hot plate, IR irradiation, UV irradiation, or the like.

  Thus, the conductive polymer composite of the present invention can be formed into a conductive film by coating and forming a film on a substrate or the like. Moreover, since the conductive film formed in this way is excellent in conductivity and transparency, it can function as a transparent electrode layer and a hole injection layer.

[substrate]
Moreover, in this invention, the board | substrate with which the electrically conductive film was formed with the conductive polymer composite of the above-mentioned this invention is provided.
Examples of the substrate include a glass substrate, a quartz substrate, a photomask blank substrate, a resin substrate, a compound semiconductor wafer such as a silicon wafer, a gallium arsenide wafer, and an indium phosphide wafer, a flexible substrate, and the like. It can also be applied on a photoresist film and used as an antistatic topcoat.

As described above, in the conductive polymer composite of the present invention, the (B) component dopant polymer containing a super strong acid sulfo group forms a composite with the (A) component π-conjugated polymer. Therefore, a low-viscosity, good filterability, good film formation property by spin coating, and when forming a film, a conductive film having good transparency, flatness, durability, and conductivity is formed. It becomes possible. In addition, such a conductive polymer composite has good affinity for an organic solvent and an organic substrate, and good film formability for both organic and inorganic substrates.
Moreover, since the electrically conductive film formed with such a conductive polymer composite is excellent in electroconductivity, transparency, etc., it can function as a transparent electrode layer.

  Hereinafter, the present invention will be specifically described with reference to synthesis examples, preparation examples, comparative preparation examples, examples, and comparative examples, but the present invention is not limited thereto.

The monomers used in the synthesis examples are shown below.

Monomer 1: benzyltrimethylammonium = 3,3,3-trifluoro-2-methacryloyloxy-2-trifluoromethylpropane-1-sulfonate Monomer 2: benzyltrimethylammonium = 3,3,3-trifluoro-2- ( 3-Methacryloyloxy-1-adamantanecarbonyloxy) -2-trifluoromethylpropane-1-sulfonate Monomer 3: Benzyltrimethylammonium = 3,3,3-trifluoro-2-trifluoromethyl-2- (4-vinyl) Benzoyloxy) propane-1-sulfonate Monomer 4: Tetrabutylammonium = 3,3,3-trifluoro-2- (4-methacryloyloxy-1-benzoyloxy) -2-trifluoromethylpropane-1-sulfonate

[Synthesis of dopant polymer]
(Synthesis Example 1)
A solution prepared by dissolving 48.1 g of monomer 1 and 5.13 g of 2,2′-azobis (isobutyric acid) dimethyl in 112.5 g of methanol in 37.5 g of methanol stirred at 64 ° C. in a nitrogen atmosphere over 4 hours. It was dripped. The mixture was further stirred at 64 ° C. for 4 hours. After cooling to room temperature, it was added dropwise to 1,000 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and dried in vacuo at 50 ° C. for 15 hours to obtain 26.2 g of a white polymer.
The obtained white polymer was dissolved in 912 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and the following analysis results were obtained.
Weight average molecular weight (Mw) = 42,000
Molecular weight distribution (Mw / Mn) = 1.61
This polymer compound is referred to as (dopant polymer 1).

(Synthesis Example 2)
To 37.5 g of methanol stirred at 64 ° C. under a nitrogen atmosphere, 24.0 g of monomer 1, 9.5 g of lithium styrenesulfonate, and 5.13 g of 2,2′-azobis (isobutyric acid) dimethyl were added to 112.5 g of methanol. The dissolved solution was added dropwise over 4 hours. The mixture was further stirred at 64 ° C. for 4 hours. After cooling to room temperature, it was added dropwise to 1,000 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 ° C. for 15 hours to obtain 41.5 g of a white polymer.
The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt and a lithium salt were converted into sulfo groups using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio (molar ratio) Monomer 1: Styrenesulfonic acid = 1: 1
Weight average molecular weight (Mw) = 46,000
Molecular weight distribution (Mw / Mn) = 1.76
This polymer compound is referred to as (dopant polymer 2).

(Synthesis Example 3)
To 37.5 g of methanol stirred at 64 ° C. in a nitrogen atmosphere, 32.8 g of monomer 2, 9.5 g of lithium styrenesulfonate, and 5.13 g of 2,2′-azobis (isobutyric acid) dimethyl were added to 112.5 g of methanol. The dissolved solution was added dropwise over 4 hours. The mixture was further stirred at 64 ° C. for 4 hours. After cooling to room temperature, it was added dropwise to 1,000 g of ethyl acetate with vigorous stirring. The resulting solid was collected by filtration and dried in vacuo at 50 ° C. for 15 hours to obtain 46.2 g of a white polymer.
The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt and a lithium salt were converted into sulfo groups using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio (molar ratio) Monomer 2: Styrenesulfonic acid = 1: 1
Weight average molecular weight (Mw) = 46,000
Molecular weight distribution (Mw / Mn) = 1.52
This polymer compound is referred to as (dopant polymer 3).

(Synthesis Example 4)
To 37.5 g of methanol stirred at 64 ° C. under a nitrogen atmosphere, 27.0 g of monomer 3, 9.5 g of lithium styrenesulfonate, and 2.82 g of 2,2′-azobis (isobutyric acid) dimethyl were added to 112.5 g of methanol. The dissolved solution was added dropwise over 4 hours. The mixture was further stirred at 64 ° C. for 4 hours. After cooling to room temperature, it was added dropwise to 1,000 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and dried in vacuo at 50 ° C. for 15 hours to obtain 47.3 g of a white polymer.
The obtained white polymer was dissolved in 421 g of methanol, and an ammonium salt and a lithium salt were converted into sulfo groups using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio (molar ratio) Monomer 3: Styrenesulfonic acid = 1: 1
Weight average molecular weight (Mw) = 55,000
Molecular weight distribution (Mw / Mn) = 1.81
This polymer compound is referred to as (dopant polymer 4).

(Synthesis Example 5)
In 37.5 g of methanol stirred at 64 ° C. in a nitrogen atmosphere, 34.6 g of monomer 4, 9.5 g of lithium styrenesulfonate, and 2.82 g of 2,2′-azobis (isobutyric acid) dimethyl were added to 112.5 g of methanol. The dissolved solution was added dropwise over 4 hours. The mixture was further stirred at 64 ° C. for 4 hours. After cooling to room temperature, it was added dropwise to 1,000 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and dried in vacuo at 50 ° C. for 15 hours to obtain 50.2 g of a white polymer.
The obtained white polymer was dissolved in 421 g of methanol, and an ammonium salt and a lithium salt were converted into sulfo groups using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio (molar ratio) Monomer 4: Styrenesulfonic acid = 1: 1
Weight average molecular weight (Mw) = 56,000
Molecular weight distribution (Mw / Mn) = 1.68
This polymer compound is referred to as (dopant polymer 5).

(Synthesis Example 6)
To 37.5 g of methanol stirred at 64 ° C. in a nitrogen atmosphere, 52.5 g of monomer 2 and 7.0 g of 2- (1,1,1,3,3,3-hexafluoro-2-propanol) styrene and 2 , 2′-azobis (isobutyric acid) dimethyl 5.13 g in methanol 112.5 g was added dropwise over 4 hours. The mixture was further stirred at 64 ° C. for 4 hours. After cooling to room temperature, it was added dropwise to 1,000 g of ethyl acetate with vigorous stirring. The resulting solid was filtered off and dried in vacuo at 50 ° C. for 15 hours to obtain 43.2 g of a white polymer.
The obtained white polymer was dissolved in 912 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio (molar ratio) Monomer 2: 4- (1,1,1,3,3,3-hexafluoro-2-propanol) styrene = 4: 1
Weight average molecular weight (Mw) = 41,000
Molecular weight distribution (Mw / Mn) = 1.64
This polymer compound is referred to as (dopant polymer 6).

(Synthesis Example 7)
To 37.5 g of methanol stirred at 64 ° C. in a nitrogen atmosphere, 52.5 g of monomer 2 and methacrylic acid-bis 3,5- (2-hydroxy-1,1,1,3,3,3-hexafluoro- A solution prepared by dissolving 13.1 g of 2-propyl) cyclohexyl and 5.13 g of 2,2′-azobis (isobutyric acid) dimethyl in 112.5 g of methanol was added dropwise over 4 hours. The mixture was further stirred at 64 ° C. for 4 hours. After cooling to room temperature, it was added dropwise to 1,000 g of ethyl acetate with vigorous stirring. The resulting solid was collected by filtration and vacuum dried at 50 ° C. for 15 hours to obtain 61.2 g of a white polymer.
The obtained white polymer was dissolved in 912 g of pure water, and the ammonium salt was converted into a sulfo group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio (molar ratio) Monomer 2: Methacrylic acid-bis 3,5- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 4: 1
Weight average molecular weight (Mw) = 23,000
Molecular weight distribution (Mw / Mn) = 1.61
This polymer compound is referred to as (dopant polymer 7).

[Preparation of conductive polymer composite dispersion]
(Preparation Example 1)
3.82 g of 3,4-ethylenedioxythiophene and a solution of 12.5 g of dopant polymer 1 dissolved in 1,000 mL of ultrapure water were mixed at 30 ° C.
While maintaining the mixed solution thus obtained at 30 ° C., 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while stirring. The reaction was stirred for 4 hours.
1,000 mL of ultrapure water was added to the resulting reaction solution, and about 1,000 mL of the solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water are added to the processing solution that has been subjected to the filtration, and about 2,000 mL of the processing solution is removed using an ultrafiltration method. To this was added 2,000 mL of ion-exchanged water, and about 2,000 mL of liquid was removed using an ultrafiltration method. This operation was repeated three times.
Furthermore, 2,000 mL of ion-exchanged water was added to the obtained processing solution, and about 2,000 mL of the processing solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain 1.3% by mass of a blue conductive polymer composite dispersion 1.

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

(Preparation Example 2)
12.5 g of dopant polymer 1 is changed to 14.0 g of dopant polymer 2, the amount of 3,4-ethylenedioxythiophene is 2.41 g, the amount of sodium persulfate is 5.31 g, ferric sulfate The conductive polymer composite dispersion 2 was obtained in the same manner as in Preparation Example 1 except that the blending amount of was changed to 1.50 g.

(Preparation Example 3)
12.5 g of dopant polymer 1 is changed to 13.0 g of dopant polymer 3, the amount of 3,4-ethylenedioxythiophene is 2.72 g, the amount of sodium persulfate is 6.00 g, ferric sulfate A conductive polymer composite dispersion 3 was obtained by the same method as in Preparation Example 1 except that the amount of was changed to 1.60 g.

(Preparation Example 4)
12.5 g of dopant polymer 1 is changed to 12.4 g of dopant polymer 4, 8.40 g of sodium persulfate is changed to 4.50 g of ammonium persulfate, and the amount of 3,4-ethylenedioxythiophene is 2.04 g. The conductive polymer composite dispersion 4 was obtained in the same manner as in Preparation Example 1 except that the blending amount of ferric sulfate was changed to 1.23 g.

(Preparation Example 5)
12.5 g of dopant polymer 1 is changed to 13.1 g of dopant polymer 5, 8.40 g of sodium persulfate is changed to 5.31 g of ammonium persulfate, and the amount of 3,4-ethylenedioxythiophene is 2.41 g. The conductive polymer composite dispersion 5 was obtained in the same manner as in Preparation Example 1 except that the amount of ferric sulfate was changed to 1.50 g.

(Preparation Example 6)
4.65 g of 3,4-ethylenedithiothiophene and a solution of 14.0 g of dopant polymer 2 dissolved in 1,000 mL of ultrapure water were mixed at 30 ° C.
While maintaining the mixed solution thus obtained at 30 ° C., 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while stirring. The reaction was stirred for 4 hours.
1,000 mL of ultrapure water was added to the resulting reaction solution, and about 1,000 mL of the solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water are added to the processing solution that has been subjected to the filtration, and about 2,000 mL of the processing solution is removed using an ultrafiltration method. To this, 2,000 mL of ion-exchanged water was added, and about 2,000 mL of liquid was removed using an ultrafiltration method. This operation was repeated three times.
Furthermore, 2,000 mL of ion-exchanged water was added to the obtained processing solution, and about 2,000 mL of the processing solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain 1.3% by weight of a blue conductive polymer composite dispersion 6.

(Preparation Example 7)
3.87 g of 3,4-dimethoxythiophene and a solution of 14.0 g of dopant polymer 2 dissolved in 1,000 mL of ultrapure water were mixed at 30 ° C.
While maintaining the mixed solution thus obtained at 30 ° C., 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while stirring. The reaction was stirred for 4 hours.
1,000 mL of ultrapure water was added to the resulting reaction solution, and about 1,000 mL of the solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water are added to the processing solution that has been subjected to the filtration, and about 2,000 mL of the processing solution is removed using an ultrafiltration method. To this was added 2,000 mL of ion-exchanged water, and about 2,000 mL of liquid was removed using an ultrafiltration method. This operation was repeated three times.
Furthermore, 2,000 mL of ion-exchanged water was added to the obtained processing solution, and about 2,000 mL of the processing solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain 1.3% by mass of a blue conductive polymer composite dispersion 7.

(Preparation Example 8)
A solution prepared by dissolving 4.62 g of (2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-yl) methanol and 14.0 g of dopant polymer 2 in 1,000 mL of ultrapure water. Were mixed at 30 ° C.
While maintaining the mixed solution thus obtained at 30 ° C., 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while stirring. The reaction was stirred for 4 hours.
1,000 mL of ultrapure water was added to the resulting reaction solution, and about 1,000 mL of the solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water are added to the processing solution that has been subjected to the filtration, and about 2,000 mL of the processing solution is removed using an ultrafiltration method. To this, 2,000 mL of ion-exchanged water was added, and about 2,000 mL of liquid was removed using an ultrafiltration method. This operation was repeated three times.
Furthermore, 2,000 mL of ion-exchanged water was added to the obtained processing solution, and about 2,000 mL of the processing solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain 1.3% by mass of a blue conductive polymer composite dispersion 8.

(Preparation Example 9)
4.16 g of 3,4-propylenedioxythiophene and a solution of 14.0 g of dopant polymer 2 dissolved in 1,000 mL of ultrapure water were mixed at 30 ° C.
While maintaining the mixed solution thus obtained at 30 ° C., 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an oxidation catalyst solution of ferric sulfate were slowly added while stirring. The reaction was stirred for 4 hours.
1,000 mL of ultrapure water was added to the resulting reaction solution, and about 1,000 mL of the solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water are added to the processing solution that has been subjected to the filtration, and about 2,000 mL of the processing solution is removed using an ultrafiltration method. To this was added 2,000 mL of ion-exchanged water, and about 2,000 mL of liquid was removed using an ultrafiltration method. This operation was repeated three times.
Furthermore, 2,000 mL of ion-exchanged water was added to the obtained processing solution, and about 2,000 mL of the processing solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain 1.3% by mass of a blue conductive polymer composite dispersion 9.

(Preparation Example 10)
12.5 g of dopant polymer 1 is changed to 16.0 g of dopant polymer 6, the amount of 3,4-ethylenedioxythiophene is 2.41 g, the amount of sodium persulfate is 5.31 g, ferric sulfate A conductive polymer composite dispersion 10 was obtained by the same method as in Preparation Example 1 except that the amount of was changed to 1.50 g.

(Preparation Example 11)
12.5 g of dopant polymer 1 is changed to 18.0 g of dopant polymer 7, the amount of 3,4-ethylenedioxythiophene is 2.41 g, the amount of sodium persulfate is 5.31 g, ferric sulfate The conductive polymer composite dispersion liquid 11 was obtained in the same manner as in Preparation Example 1 except that the amount of was changed to 1.50 g.

(Preparation Example 12)
The conductive polymer composite dispersion 2 and the conductive polymer composite dispersion 11 were blended at a ratio of 1: 1 to obtain a conductive polymer composite dispersion 12.

(Comparative Preparation Example 1)
5.0 g of 3,4-ethylenedioxythiophene and a solution obtained by diluting 83.3 g of a polystyrene sulfonic acid aqueous solution (18.0% by mass from Aldrich) with 250 mL of ion-exchanged water were mixed at 30 ° C. Otherwise, the preparation was carried out in the same manner as in Preparation Example 1 to obtain 1.3% by mass of a blue comparative conductive polymer composite dispersion 1 (PEDOT-PSS dispersion). This comparative conductive polymer composite dispersion 1 contains only polystyrene sulfonic acid as a dopant polymer.

[Example]
20 g of the 1.3% by mass of the conductive polymer composite dispersion 1 to 12 obtained in Preparation Examples 1 to 12, 5 g of dimethyl sulfoxide, and 0.5 g of Surfynol 465 as a surfactant / antifoaming agent were mixed. Then, it filtered using the regenerated cellulose filter (made by ADVANTEC) with the hole diameter of 0.45 micrometer, and prepared the conductive polymer composition, and was set as Examples 1-12, respectively.

[Comparative example]
A conductive polymer composition was prepared in the same manner as in Example except that the comparative conductive polymer composite 1 obtained in Comparative Preparation Example 1 was used, and this was used as Comparative Example 1.

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

(Filterability)
In the preparation of the conductive polymer compositions of the above examples and comparative examples, when filtration was performed using a regenerated cellulose filter having a pore size of 0.45 μm, it was filtered, and the filter could be clogged and filtered. Those not present are shown in Table 1 as x.

(Applicability)
First, the conductive polymer composition was spin-coated (spin coated) on a Si wafer using 1H-360S SPINCOATER (manufactured by MIKASA) so that the film thickness was 100 ± 5 nm. Next, baking was performed at 120 ° C. for 5 minutes in a precision thermostat, and the solvent was removed to obtain a conductive film. The refractive index (n, k) at a wavelength of 636 nm was determined for this conductive film using a spectroscopic ellipsometer VASE (manufactured by JA Woollam) with a variable incident angle. Table 1 shows the case where a uniform film could be formed, and the case where the refractive index was measured, but the defect derived from particles or a portion where the striation occurred in the film was shown as x.

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

(conductivity)
First, 1.0 mL of the conductive polymer composition was dropped onto a SiO ₂ wafer having a diameter of 4 inches (100 mm), and after 10 seconds, the whole was spin-coated using a spinner. The spin coating conditions were adjusted so that the film thickness was 100 ± 5 nm. A conductive film was obtained by baking at 120 ° C. for 5 minutes in a precision thermostat and removing the solvent.
The electrical 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 determined from the measured value of the film thickness. 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 the conductivity evaluation method. RMS (root mean square roughness) was measured by AFM NANO-IM-8 (Image Metrology). The results are shown in Table 1.

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

  As shown in Table 1, Examples 1 to 12 containing polythiophene as a π-conjugated polymer and containing a dopant polymer having a repeating unit a have good filterability and are uniform by coating with a spin coater. Could get. Moreover, the conductivity was high, the transmittance for visible light of λ = 550 nm was good, and the surface roughness was also good.

  On the other hand, Comparative Example 1 using polystyrene sulfonic acid having no repeating unit a as a dopant polymer has poor filterability due to high viscosity, and as a result, spin coating results from particles and bubbles on the film. Striation occurred and a uniform coating film could not be obtained. Moreover, although the conductivity was high, the transmittance for visible light at λ = 550 nm and the surface roughness were inferior to those of Examples 1-12.

  As described above, the conductive polymer composite of the present invention has low viscosity and good filterability, good film formation by spin coating, and transparency and flatness when forming a film. It was revealed that a conductive film and a hole injection layer having good durability and conductivity can be formed.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (8)

(A) a π-conjugated polymer, and (B) a dopant polymer containing a repeating unit a represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000,
A conductive polymer composite comprising:

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² has a single bond, an ester group, an ether group, an ester group, or both of which may have 1 to 12 carbon atoms. A straight-chain, branched, or cyclic hydrocarbon group, Z is a single bond, a phenylene group, a naphthylene group, an ether group, or an ester group, and a is 0 <a ≦ 1.0. .) The repeating unit a in the component (B) includes one or more selected from repeating units a1 to a4 represented by the following general formulas (1-1) to (1-4). 2. The conductive polymer composite according to 1.

(Wherein R ¹ is the same as above. A1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4. ≦ 1.0 and 0 <a1 + a2 + a3 + a4 ≦ 1.0.) The conductive polymer composite according to claim 1, wherein the component (B) further contains a repeating unit b represented by the following general formula (2).

(Wherein b is 0 <b <1.0)   The conductive polymer composite according to any one of claims 1 to 3, wherein the component (B) is a block copolymer.   The component (A) is obtained by polymerizing one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurophene, aniline, polycyclic aromatic compounds, and derivatives thereof. The conductive polymer composite according to any one of claims 1 to 4, wherein the conductive polymer composite is characterized in that:   The conductive polymer composite according to any one of claims 1 to 5, wherein the conductive polymer composite is dispersible in water or an organic solvent.   A conductive film formed by the conductive polymer composite according to any one of claims 1 to 6, wherein the substrate is a substrate.   The substrate according to claim 7, wherein the conductive film functions as a transparent electrode layer.