Composite, dispersion liquid, conductive coating, conductive material, electronic equipment, method for producing composite, copolymer, and method for producing copolymer

Abstract

SOLUTION: A composite includes a π-conjugated polymer and a dopant polymer having a copolymer including a first repeating unit and a second repeating unit. The first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group. The second repeating unit has a structure derived from a second monomer that is a radical polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring having 12 or more carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composite, a dispersion, a conductive paint, a conductive material, an electronic device, a method for producing a composite, a copolymer, and a method for producing a copolymer. [Background technology]

[0002] Patent Documents 1 and 2 disclose conductive polymer composites containing a π-conjugated polymer and a dopant polymer. Non-Patent Document 1 discloses a technique for sulfonating polystyrene using concentrated sulfuric acid in an amount 18.4 times the mass of the raw polymer. Non-Patent Document 2 discloses styrenesulfonate ethyl ester. [Prior art document] [Patent documents] [Patent Document 1] JP 2022-068178 A [Patent Document 2] International Publication No. 2010 / 095649 [Non-patent literature] [Non-Patent Document 1] Akira Takahashi, Soichi Shimoyama, and Hiromi Kagawa, "Preparation of Polystyrene Sulfonic Acid and Some of its Properties," Journal of Industrial Chemistry, Chemical Society of Japan, accepted February 20, 1958, Vol. 61, No. 12, pp. 1617-1619 [Non-Patent Document 2] Hisao Eguchi, Shoichi Nishiyama, Shinichi Ishikawa, "Tosoh's Organic Synthesis Technology and Organic Intermediate Product Group," Tosoh Research and Technical Report, Tosoh Corporation, 2003, Vol. 47, pp. 85-89 Summary of the Invention [Means for solving the problem]

[0003] In a first aspect of the present invention, a composite is provided. The composite includes, for example, a π-conjugated polymer. The composite includes, for example, a dopant polymer having a copolymer including a first repeating unit and a second repeating unit. In the composite, the first repeating unit has, for example, a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group. In the composite, the second repeating unit has, for example, a structure derived from a second monomer that is a radically polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms.

[0004] In any of the above conjugates, the second monomer may be substantially free of a hydrophilic group.In any of the above conjugates, the second monomer may be substantially free of at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydroxyl group, and an amino group.

[0005] In any of the above composites, the second monomer may be at least one compound selected from the group consisting of (meth)acrylic acid derivatives, (meth)acrylic acid esters and derivatives thereof, and (meth)acrylamide derivatives, or a vinyl compound. In any of the above composites, the second monomer may have at least one functional group selected from the group consisting of substituted or unsubstituted alkyl groups having 12 or more carbon atoms, substituted or unsubstituted aromatic ring groups having 12 or more carbon atoms, and substituted or unsubstituted alicyclic ring groups having 12 or more carbon atoms.

[0006] In any of the above composites, the hydrophilicity of the second monomer may be lower than the hydrophilicity of the first monomer. In any of the above composites, the first monomer may be at least one compound selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, Nt-butylacrylamidosulfonic acid, 2-sulfoethyl methacrylate, derivatives thereof, and salts thereof.

[0007] In a second aspect of the present invention, a dispersion of a complex is provided. The dispersion contains, for example, any of the complexes according to the first aspect. The dispersion contains, for example, water as a dispersion medium for the complex.

[0008] In a third aspect of the present invention, a dispersion of a complex is provided. The dispersion contains, for example, any of the complexes according to the first aspect. The dispersion contains, for example, an organic solvent as a dispersion medium for the complex. The dispersion medium may be substantially free of water and dispersants.

[0009] In a fourth aspect of the present invention, there is provided a conductive paint. The conductive paint includes, for example, any of the composites according to the first aspect. The dispersion includes, for example, a dispersion medium that disperses and holds the composite.

[0010] In a fifth aspect of the present invention, there is provided a conductive material. The conductive material includes, for example, any of the composites according to the first aspect. The conductive material has, for example, a film or sheet shape, a thread or fiber shape, or a mesh shape.

[0011] In a sixth aspect of the present invention, there is provided an electronic device, which includes, for example, a conductive material containing any of the composites according to the first aspect.

[0012] A seventh aspect of the present invention provides a method for producing a composite. The production method includes, for example, an oil-solubilizing step in which the sulfonic acid group or a salt thereof of a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group is modified to impart oil-solubility to the first monomer. The production method includes, for example, a first polymerization step in which the oil-soluble first monomer is radically polymerized with a radically polymerizable second monomer. The production method includes, for example, a water-solubilizing step in which water-solubility is imparted to the copolymer obtained in the first polymerization step. The production method includes, for example, a second polymerization step in which a third monomer that forms a π-conjugated polymer is polymerized in an aqueous solution of the water-soluble copolymer to obtain a composite containing the π-conjugated polymer and the copolymer.

[0013] In any of the above production methods, the oil-solubilizing step may include reacting a sulfonic acid group or a salt thereof of the first monomer with an alkylamine salt. In any of the above production methods, the first polymerization step may include radically polymerizing the oil-soluble first monomer and an oil-soluble second monomer in an organic solvent to produce an oil-soluble copolymer. In any of the above production methods, the first monomer may be a water-soluble monomer. In any of the above production methods, the second monomer may be an oil-soluble monomer. In any of the above production methods, the first polymerization step may include radically polymerizing the first monomer and the second monomer under conditions substantially absent of a water-soluble monomer different from the first monomer.

[0014] In an eighth aspect of the present invention, a method for producing a composite is provided. The production method includes, for example, a preparation step of preparing a water-soluble copolymer containing a first repeat unit and a second repeat unit. The production method also includes, for example, a polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in an aqueous solution of the water-soluble copolymer to obtain a composite containing the π-conjugated polymer and the copolymer. In the production method, the first repeat unit has, for example, a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group. In the production method, the second repeat unit has, for example, a structure derived from a second monomer that is a radically polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms.

[0015] A ninth aspect of the present invention provides a method for producing a composite. The production method includes, for example, a preparation step of preparing an oil-soluble copolymer comprising a first repeating unit and a second repeating unit. The production method includes, for example, a solubilization step of imparting water solubility to the oil-soluble copolymer. The production method includes, for example, a polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in an aqueous solution of the copolymer that has been made water-soluble to obtain a composite comprising the π-conjugated polymer and the copolymer. In the production method, the first repeating unit has, for example, a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group. In the production method, the second repeating unit has, for example, a structure derived from a second monomer that is a radically polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms.

[0016] A tenth aspect of the present invention provides a copolymer. The copolymer includes, for example, a first repeating unit and a second repeating unit. In the copolymer, the first repeating unit has, for example, a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group. In the copolymer, the second repeating unit has, for example, a structure derived from a second monomer that is a radically polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms. In the copolymer, the hydrophilicity of the second monomer is, for example, lower than that of the first monomer.

[0017] In an eleventh aspect of the present invention, there is provided a method for producing a copolymer. The production method includes, for example, an oil-solubilizing step in which a water-soluble first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group is modified to impart oil-solubility to the first monomer, and a polymerization step in which, for example, in an organic solvent, the oil-soluble first monomer is radically polymerized with an oil-soluble, radically polymerizable second monomer to obtain an oil-soluble copolymer. The production method also includes, for example, a water-solubilizing step in which water-solubility is imparted to the oil-soluble copolymer to obtain a water-soluble copolymer.

[0018] The above summary of the invention does not list all of the necessary features of the present invention, and subcombinations of these features may also constitute inventions. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described below through embodiments of the invention, but the following embodiments do not limit the invention according to the claims. Furthermore, not all combinations of features described in the embodiments are necessarily essential to the solution of the invention. In this specification, when a numerical range is expressed as "A to B," this expression means A or more and B or less.

[0020] In recent years, conductive polymer compositions have been attracting attention as materials for (i) electronic components, electronic devices such as electrical products containing the electronic components, (ii) conductive materials used in the electronic components, electromagnetic wave shields, antistatic films, etc., and (iii) conductive paints used in the preparation of the conductive materials, antistatic treatments or antifouling treatments for articles, etc. The conductive polymer composition contains, for example, a π-conjugated polymer and a dopant polymer that dopes the π-conjugated polymer.

[0021] Conventionally, various studies have been conducted on the structure of monomers constituting π-conjugated polymers or dopant polymers for the purpose of improving conductivity, improving the stability of electrical properties, improving solubility in solvents, etc. In response to this, the present inventors have conceived of imparting a new function other than conductivity to a composite of a π-conjugated polymer and a dopant polymer by functionalizing the monomers constituting the π-conjugated polymer and / or the dopant polymer.

[0022] As a result of extensive research, the present inventors have found that functionalizing the monomers that constitute the dopant polymer makes it possible to obtain a composite having new functions while maintaining electrical properties suitable for applications such as electronic devices, conductive materials, and conductive paints. The present inventors have also discovered a novel dopant polymer and a method for producing the same. Specifically, the present inventors have discovered a dopant polymer that has high solubility in solvents with low polarity and a method for producing the same. For example, the present inventors have discovered a dopant polymer that has high solubility in at least one of ethanol, isopropyl alcohol, n-butanol, and toluene compared to polystyrene sulfonic acid, which is commonly used as a dopant polymer for conductive polymer compositions, and a method for producing the same.

[0023] (A. Complex) According to this embodiment, there is provided a composite including a π-conjugated polymer and a dopant polymer. In this embodiment, the dopant polymer has a copolymer including a first repeat unit and a second repeat unit.

[0024] In this embodiment, the first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group, and the second repeating unit has a structure derived from a second monomer that is a radical polymerizable monomer.

[0025] In this embodiment, the second monomer may have a lower hydrophilicity than the first monomer. The first monomer may be a water-soluble monomer, and the second monomer may be an oil-soluble monomer. Details of the first and second monomers will be described later.

[0026] The oil-soluble monomer may be a compound that is substantially free of hydrophilic groups. The oil-soluble monomer may be a compound that is substantially free of hydrophilic groups. The hydrophilic group may be at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydroxyl group, and an amino group. An example of a compound that is substantially free of hydrophilic groups is a compound in which the ratio of the number of hydrophilic groups contained in the compound to the number of carbon atoms contained in the structure excluding the hydrophilic groups is less than 10%. The compound that is substantially free of hydrophilic groups may also be a compound in which the above ratio is less than 5%.

[0027] The composite may be a conductive composite. The composite may be a hydrophobic conductive composite. The degree of hydrophobicity of the composite is indicated, for example, by the water contact angle. The composite according to this embodiment has a water contact angle of, for example, 20° or more due to the inclusion of the second repeating unit. The composite may have a water contact angle of 30° or more, a water contact angle of 40° or more, a water contact angle of 50° or more, a water contact angle of 60° or more, a water contact angle of 70° or more, a water contact angle of 80° or more, a water contact angle of 90° or more, a water contact angle of 100° or more, or a water contact angle greater than 100°.

[0028] The water contact angle is measured, for example, by the following procedure. First, a sample of a film having a coating of the composite is prepared. Specifically, a coating solution containing the composite is applied to the surface of a PET film "Lumirror 188T60" manufactured by Toray Industries, Inc. using a bar coater No. 4. The coating solution is applied in an amount of 15 × 10 -3 ~55×10 -3 g-complex / m 2 The coating is applied so that the thickness of the coating after drying will be 0.02 to 0.05 μm. Next, the Lumirror 188T60 coated with the coating liquid is dried for 1 minute at 105°C. The drying process is carried out using a hot air dryer. This produces a sample of the above film.

[0029] Next, the water contact angle of the composite was measured using a film sample prepared by the above procedure. Specifically, 20 μL of ion-exchanged water was deposited on the surface of the film. 30 seconds after the deposition of the ion-exchanged water, the contact angle was measured using a contact angle meter (Kyowa Interface Science Co., Ltd., DMo-601).

[0030] (dispersion) According to this embodiment, a dispersion of the above-mentioned composite is provided. The dispersion may be an aqueous dispersion or a non-aqueous dispersion. Aqueous dispersions are superior to non-aqueous dispersions in, for example, coatability to hydrophilic substrates and environmental safety. Non-aqueous dispersions are superior to aqueous dispersions in, for example, coatability to hydrophobic substrates, drying properties, miscibility with oil-soluble compounds, and the like.

[0031] For example, a conductive coating is formed on the surface of a substrate by applying a dispersion liquid to the surface of the substrate and then drying the dispersion liquid. The shape of the substrate is not particularly limited. Examples of the shape of the substrate include a plate, a film or sheet, a thread or fiber, and a mesh. The plate, film, or sheet substrate may be a porous membrane. The fiber or mesh substrate may be a nonwoven fabric.

[0032] Examples of methods for applying the dispersion include spin coating, bar coating, immersion, comma coating, spray coating, roll coating, screen printing, flexographic printing, gravure printing, inkjet printing, etc. Examples of methods for drying the dispersion include heating with a hot air circulation oven, a hot plate, etc.

[0033] In one embodiment, the dispersion contains the above-described complex and water as a dispersion medium for the complex. In this case, the dispersion medium may be substantially free of a dispersant. The content of the dispersant may be less than 30 parts by mass per 100 parts by mass of water, or may be less than 10 parts by mass per 100 parts by mass of water.

[0034] Examples of dispersants include low molecular weight surfactants, polymeric surfactants, etc. The surfactant may be anionic, nonionic, cationic, or amphoteric.

[0035] The viscosity of the aqueous dispersion may be 100 mPa·s or less at room temperature, 50 mPa·s or less, or 30 mPa·s or less.

[0036] In another embodiment, the dispersion liquid contains the above-described complex and an organic solvent as a dispersion medium for the complex. In this case, the dispersion medium may be substantially free of water. The water content may be less than 30 parts by mass per 100 parts by mass of the organic solvent, or may be less than 20 parts by mass per 100 parts by mass of the organic solvent. The dispersion medium may be substantially free of a dispersant. The dispersant content may be less than 30 parts by mass per 100 parts by mass of the organic solvent, or may be less than 10 parts by mass per 100 parts by mass of the organic solvent.

[0037] Examples of organic solvents include water-soluble organic solvents, water-insoluble organic solvents, and mixed solvents of water-soluble and water-insoluble organic solvents. A water-soluble organic solvent is, for example, an organic solvent that dissolves in an amount of 1 g or more in 100 g of water at 20°C. A water-insoluble organic solvent is, for example, an organic solvent that dissolves in an amount of less than 1 g in 100 g of water at 20°C. One type of water-soluble organic solvent may be used alone, or two or more types of water-soluble organic solvents may be used in combination. One type of water-insoluble organic solvent may be used alone, or two or more types of water-insoluble organic solvents may be used in combination.

[0038] Examples of water-soluble organic solvents include alcohol solvents, ether solvents, ketone solvents, nitrogen atom-containing solvents, and ester solvents. Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether. Examples of ether solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, and diethylene glycol diethyl ether. Examples of ketone solvents include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, and diacetone alcohol. Examples of nitrogen atom-containing solvents include N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, and isobutyl acetate.

[0039] Examples of non-water-soluble organic solvents include hydrocarbon solvents. Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of aliphatic hydrocarbon solvents include hexane, cyclohexane, pentane, heptane, octane, nonane, decane, and dodecane. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, and isopropylbenzene.

[0040] Examples of dispersants include low molecular weight surfactants, polymeric surfactants, etc. The surfactant may be anionic, nonionic, cationic, or amphoteric.

[0041] (conductive paint) According to this embodiment, there is provided a conductive paint containing the above-mentioned composite. The conductive paint may be a water-based paint, a solvent-based paint, or a reaction-curing paint.

[0042] In one embodiment, the conductive paint includes, for example, (i) a conductive agent and (ii) a dispersion medium or solvent that disperses or dissolves the conductive agent. The conductive agent includes, for example, the above-mentioned complex. The conductive agent may be the above-mentioned complex.

[0043] In another embodiment, the conductive paint includes (i) a conductive agent, (ii) at least one of a high-conductivity agent and a film-forming agent, and (iii) a dispersion medium or solvent that disperses or dissolves the conductive agent and at least one of the high-conductivity agent and the film-forming agent. The conductive agent includes, for example, the above-mentioned complex. The conductive agent may be, for example, the above-mentioned complex. The high-conductivity agent includes, for example, a water-soluble organic solvent. The high-conductivity agent may be, for example, a water-soluble organic solvent. Examples of the water-soluble organic solvent include dimethyl sulfoxide and ethylene glycol. Examples of the film-forming agent include any resin. Examples of the above-mentioned resin include polyester resin, acrylic resin, polyvinyl alcohol, etc.

[0044] The conductive paint contains, for example, 0.001 to 2 parts by mass of a conductive agent relative to 100 parts by mass of the dispersion medium or solvent. The conductive paint may contain 0.01 to 1 part by mass of a conductive agent relative to 100 parts by mass of the dispersion medium or solvent.

[0045] Examples of the dispersion medium or solvent include a sol, a gel, and a liquid. The dispersion medium or solvent may be water or an organic solvent. The dispersion medium or solvent may include a single organic solvent or multiple types of organic solvents. The organic solvent may be the same compound as the compound described in relation to the dispersion liquid described above.

[0046] The conductive paint may further include a dispersant. The conductive paint may include a single dispersant or multiple types of dispersants. The dispersant may be the same compound as the compounds described in relation to the dispersion liquid described above.

[0047] The conductive paint contains, for example, 0.0001 to 10 parts by mass of a dispersant relative to 100 parts by mass of the dispersion medium or solvent. The conductive paint may contain 0.001 to 5 parts by mass of a dispersant relative to 100 parts by mass of the dispersion medium or solvent.

[0048] The conductive paint may further contain various materials to the extent that the conductivity is not significantly impaired. Examples of the above materials include (i) resin materials such as polyolefin resin, polyester resin, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, ethylene-(meth)acrylic acid copolymer, styrene-maleic acid resin, styrene-butadiene resin, butadiene resin, acrylonitrile-butadiene resin, poly(meth)acrylonitrile resin, (meth)acrylamide resin, acid-unmodified polyethylene resin, chlorinated polyethylene resin, chlorinated polypropylene resin, modified nylon resin, tackifying resins such as rosin-based and terpene-based resins, phenolic resin, epoxy resin, polyurethane resin, and silicone resin; and (ii) silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, and molybdenum carbide. (iii) nitrides such as boron nitride, titanium nitride, and zirconium nitride; (iv) borides such as zirconium boride; (v) oxides such as titanium oxide (titania), calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica, and colloidal silica; (vi) titanate compounds such as calcium titanate, magnesium titanate, and strontium titanate; (vii) sulfides such as molybdenum disulfide; (viii) fluorides such as magnesium fluoride and carbon fluoride; (xi) metal soaps such as aluminum stearate, calcium stearate, zinc stearate, and magnesium stearate; and (x) inorganic materials such as talc, bentonite, talc, calcium carbonate, bentonite, kaolin, glass fiber, and mica.

[0049] The above materials may be used alone or in combination. The content of the above materials in the conductive paint is not particularly limited, but the content may be 50% by mass or less relative to 100% by mass of the conductive paint. The content may be 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0050] The conductive coating material may further contain various additives to the extent that the conductivity is not significantly impaired. Examples of the additives include a thixotropic agent, an antifoaming agent, an antiblocking agent, a flame retardant, a tackifier, a hydrolysis inhibitor, a leveling agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, a pigment, and a dye.

[0051] The additives may be used alone or in combination. The content of the additives in the conductive paint is not particularly limited, but may be 50% by mass or less relative to 100% by mass of the conductive paint. The content may be 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0052] In one embodiment, the conductive paint is applied to the surface of an article to impart conductivity to the article. The conductive paint is used, for example, in the production of conductive materials or electronic devices described below. In another embodiment, the conductive paint is applied to the surface of an article to impart antifouling, water-repellent, or oil-repellent properties to the article. In yet another embodiment, the conductive paint is applied to the surface of an article to impart electromagnetic wave shielding properties to the article.

[0053] (Conductive materials) According to this embodiment, a conductive material including the above-described composite is provided. The above-described conductive material has, for example, a plate-like or linear shape. The plate-like conductive material is used, for example, as an electronic substrate. The linear conductive material is used, for example, as wiring. The above-described conductive material has, for example, a film or sheet-like shape, a thread-like or fibrous shape, or a mesh-like shape. The film-like or sheet-like conductive material is used, for example, as a flexible substrate, a polarizing plate, a protective film, a carrier tape, an anti-fingerprint film, etc. The thread-like or fibrous conductive material is used, for example, in textiles, carpets, beds, etc. The mesh-like conductive material is used, for example, in electrodes, solar cells, etc.

[0054] (electronic equipment) According to this embodiment, an electronic device including the conductive material is provided. Examples of the electronic device include electronic components and electrical products including the electronic components. Examples of the electronic components include organic EL elements, dye-sensitized solar cell panels, and electrolytic capacitors. For example, the composite functions as a transparent electrode layer or a hole injection layer of an organic EL element. Examples of the electrical product include organic EL displays, solar power generation devices, home appliances, mobile devices, and communication devices.

[0055] (B. π-conjugated polymers) The π-conjugated polymer is, for example, a polymer of a third monomer that forms a π-conjugated chain. The π-conjugated polymer may be a homopolymer or a copolymer. The π-conjugated chain has a structure in which single bonds and double bonds are alternately arranged.

[0056] (Third Monomer) Examples of the third monomer include (i) monocyclic aromatic compounds such as pyrroles, thiophenes, thiophene vinylenes, selenophenes, tellurophenes, phenylenes, phenylene vinylenes, and anilines, (ii) polycyclic aromatic compounds such as acenes, and (iii) acetylenes. The third monomer may be one or more compounds selected from the group consisting of monocyclic aromatic compounds, polycyclic aromatic compounds, and acetylenes, or salts thereof.

[0057] The compound used as the third monomer may be substituted with one or more functional groups selected from the group consisting of an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, a cyano group, and a halogen atom, thereby further improving the conductivity of the π-conjugated polymer.

[0058] Specific examples of pyrroles 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, and 3-methyl-4-hexyloxypyrrole. Specific examples of thiophenes include 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-octadecyl ... Examples of thiophene include decyloxythiophene, 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, and 3-methyl-4-carboxybutylthiophene.Specific examples of anilines include aniline, 2-methylaniline, 3-isobutylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-anilinesulfonic acid, and 3-anilinesulfonic acid.

[0059] The third monomer is preferably one or more compounds selected from the group consisting of pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, and 3,4-ethylenedioxythiophene, or salts thereof. These compounds or salts thereof are suitable for use as the third monomer, for example, from the viewpoint of reactivity and the resistance value of the reaction product. The third monomer is more preferably pyrrole and / or 3,4-ethylenedioxythiophene. The third monomer is even more preferably either pyrrole or 3,4-ethylenedioxythiophene.

[0060] The π-conjugated polymer may be a polythiophene-based conductive polymer. The π-conjugated polymer may be a polymer of one or more compounds selected from the group consisting of pyrrole, thiophene, selenophene, tellurophene, aniline, polycyclic aromatic compounds, and derivatives thereof, or salts thereof. The π-conjugated polymer may be polypyrrole, poly(3,4-ethylenedioxythiophene), or a derivative thereof. The π-conjugated polymer may be poly(3,4-ethylenedioxythiophene) or a derivative thereof. The π-conjugated polymer may be poly(3,4-ethylenedioxythiophene).

[0061] (Method of producing π-conjugated polymer) The π-conjugated polymer is produced using any known polymerization method. An example of a method for polymerizing a π-conjugated polymer is chemical oxidative polymerization in an electrolytic substrate solvent. More specifically, a raw material monomer of the π-conjugated polymer (the third monomer described above) is polymerized using an oxidizing agent in an aqueous solution of the dopant polymer. This results in a composite containing the π-conjugated polymer and the dopant polymer. Specifically, an aqueous dispersion of the π-conjugated polymer doped with the dopant polymer is obtained. Details of the method for producing a π-conjugated polymer will be described later as a method for producing a composite.

[0062] (C. Dopant Polymer) In this embodiment, the dopant polymer comprises a copolymer comprising a first repeat unit and a second repeat unit. The dopant polymer may be a copolymer comprising a first repeat unit and a second repeat unit.

[0063] As described above, in this embodiment, the first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group. In this embodiment, the second repeating unit has a structure derived from a second monomer that is a radical polymerizable monomer. As described above, the hydrophilicity of the second monomer may be less than that of the first monomer.

[0064] The molecular weight of the copolymer constituting the dopant polymer is not particularly limited. According to the solution polymerization method, for example, a copolymer having a weight-average molecular weight of about 3,000 to 2,000,000 can be obtained. The weight-average molecular weight of the copolymer may be 10,000 to 1,000,000. When the weight-average molecular weight is 10,000 or more, the dispersibility of the composite is improved. When the weight-average molecular weight is 1,000,000 or less, the doping rate of the π-conjugated polymer is improved, and a composite having excellent conductivity can be obtained.

[0065] (First Monomer) As described above, the first monomer has a sulfonic acid group or a salt thereof and a polymerizable vinyl group. The first monomer may be a water-soluble monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group.

[0066] The first monomer is preferably one or more compounds selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, Nt-butylacrylamidosulfonic acid, 2-sulfoethyl methacrylate, and derivatives thereof, or salts thereof. The first monomer may be one or more compounds selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, Nt-butylacrylamidosulfonic acid, and 2-sulfoethyl methacrylate, or salts thereof.

[0067] As the first monomer, styrene sulfonic acid, vinyl sulfonic acid, and salts thereof are preferably used. More preferably, a salt of either styrene sulfonic acid or vinyl sulfonic acid is used as the first monomer. Examples of salts of the above compounds include sodium salts, potassium salts, and lithium salts. The salts of the above compounds may be sodium salts. The first monomer may be sodium styrene sulfonate or sodium vinyl sulfonate.

[0068] (Second Monomer) As described above, the second monomer is a radical polymerizable monomer. Examples of the radical polymerizable monomer include at least one compound selected from the group consisting of (meth)acrylic acid derivatives, (meth)acrylic acid esters and derivatives thereof, and (meth)acrylamide derivatives, or vinyl compounds thereof.

[0069] The second monomer may be an oil-soluble radical polymerizable monomer. In this embodiment, a compound having a lower degree of hydrophilicity than the first monomer is used as the second monomer. For example, a water-soluble monomer is used as the first monomer, and an oil-soluble monomer is used as the second monomer.

[0070] The second monomer may be a radical polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 6 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 6 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 6 or more carbon atoms. Since the functional group exhibits hydrophobicity, the second monomer may be oil-soluble. This makes the second monomer less hydrophilic than the first monomer.

[0071] The second monomer may be a radical polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms. The oil-soluble radical polymerizable monomer may be a radical polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 12 to 30 carbon atoms, a substituted or unsubstituted aromatic ring group having 12 to 30 carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 to 30 carbon atoms. The above functional groups are hydrophobic, and therefore the second monomer is oil-soluble. This results in a lower degree of hydrophilicity of the second monomer than that of the first monomer.

[0072] The alkyl group may be a straight-chain alkyl group or a branched alkyl group. The alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group. Examples of the alkyl group include a dodecyl group (sometimes referred to as a lauryl group), a tridecyl group, a tetradecyl group, a pentadecyl group, an octadecyl group (sometimes referred to as a stearyl group), an icosyl group, a heneicosyl group, a docosyl group, a triacontyl group, and a tetracontyl group.

[0073] The aromatic ring group may be a benzene ring, a naphthalene ring, or an anthracene ring. Examples of the aromatic ring group include alkylbenzenes such as dodecylbenzene and nonylphenyl, and alkylnaphthalenes.

[0074] The alicyclic ring group may be a cyclohexyl ring, a dicyclopentanyl ring, or an adamantyl ring. Examples of the alicyclic ring group include dimethyladamantane and dicyclopentanyloxyethyl.

[0075] As the second monomer, a (meth)acrylic acid alkyl ester or a (meth)acrylamide alkyl is preferably used. The second monomer may be a (meth)acrylic acid alkyl ester or a (meth)acrylamide alkyl having an unsubstituted alkyl group with 6 to 30 carbon atoms. The second monomer may be a (meth)acrylic acid alkyl ester or a (meth)acrylamide alkyl having an unsubstituted alkyl group with 12 to 30 carbon atoms.

[0076] The second monomer may be at least one compound selected from the group consisting of (meth)acrylic acid derivatives, (meth)acrylic acid esters and derivatives thereof, and (meth)acrylamide derivatives, or a vinyl compound. The above compounds may have at least one functional group selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted alkyl groups, and substituted or unsubstituted alicyclic ring groups. In one embodiment, the second monomer has at least one functional group selected from the group consisting of substituted or unsubstituted alkyl groups having 6 or more carbon atoms, substituted or unsubstituted alkyl groups having 6 or more carbon atoms, and substituted or unsubstituted alicyclic ring groups having 6 or more carbon atoms. In another embodiment, the second monomer has at least one functional group selected from the group consisting of substituted or unsubstituted alkyl groups having 12 or more carbon atoms, substituted or unsubstituted aromatic ring groups having 12 or more carbon atoms, and substituted or unsubstituted alicyclic ring groups having 12 or more carbon atoms.

[0077] The upper limit of the number of carbon atoms in the functional group is not particularly limited, but the upper limit may be 30. When the number of carbon atoms in the functional group is 30 or less, steric hindrance caused by the functional group can be relatively suppressed. Furthermore, when the number of carbon atoms in the functional group is 30 or less, the melting point of the second monomer can be lower than when the number of carbon atoms exceeds 30. As a result, the solubility and / or handleability of the second monomer are improved. Furthermore, it is easier to achieve high purity of the second monomer and / or dopant polymer.

[0078] The second monomer may be a compound substantially free of hydrophilic groups. The second monomer may be a compound having the above-described alkyl group, aromatic ring group, and / or alicyclic ring group, and substantially free of hydrophilic groups. The compound substantially free of hydrophilic groups may be a compound free of hydrophilic groups. This allows the second monomer to be oil-soluble. As a result, the degree of hydrophilicity of the second monomer is lower than that of the first monomer. The hydrophilic group may be at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydroxyl group, and an amino group. An example of a compound substantially free of hydrophilic groups is a compound in which the ratio of the number of hydrophilic groups contained in the compound to the number of carbon atoms contained in the structure excluding the hydrophilic groups is less than 10%. The compound substantially free of hydrophilic groups may be a compound in which the above ratio is less than 5%.

[0079] (Method for producing dopant polymer) As described above, in this embodiment, the second monomer is a compound that is less hydrophilic than the first monomer. For example, a water-soluble monomer is used as the first monomer, and an oil-soluble monomer is used as the second monomer.

[0080] The polymerization method for the first monomer and the second monomer is not particularly limited, and any known polymerization method can be used. Examples of the polymerization method include solution polymerization and living radical polymerization. According to the solution polymerization method, the raw material monomers of the copolymer can be uniformly polymerized in a parent solvent. As a result, a relatively uniform composition can be obtained. According to the living radical polymerization method, the uniformity of the dopant polymer structure can be further improved. Examples of the living radical polymerization method include a method using a metal complex (ATRP method), a method using a thiocarbonyl compound (RAFT method), and a method using a nitroxide compound (NMP method).

[0081] If the hydrophilicity of the first monomer and the second monomer differs significantly, the first monomer and the second monomer tend to separate in the polymerization system during polymerization. Separation of the first monomer and the second monomer in the polymerization system can result in the respective monomers being polymerized in different polymerization sites, or the polymer being partially or entirely precipitated from the polymerization system. As a result, the composition of the dopant polymer obtained by polymerizing the first monomer and the second monomer can be non-uniform.

[0082] When a π-conjugated polymer is synthesized in the presence of a dopant polymer having a non-uniform composition, the polymerization stability of the π-conjugated polymer deteriorates, affecting the quality of a conductive polymer composition containing the π-conjugated polymer and the dopant polymer. For example, the performance of a conductive coating prepared using the conductive polymer composition may not meet predetermined standards, or the conductive coating may not function adequately. Therefore, it is preferable to uniformly polymerize the raw material monomers of the copolymer in a suitable solvent.

[0083] One method for uniformly polymerizing raw material monomers for the copolymer in a polymerizable solvent is to select the monomers for the copolymer constituting the dopant polymer from among a plurality of monomers having relatively similar degrees of hydrophilicity. However, this method does not allow copolymerization of a plurality of monomers having relatively large differences in degrees of hydrophilicity, as in the present embodiment.

[0084] Another method for uniformly polymerizing raw material monomers for a copolymer in a polymerizable solvent is to polymerize multiple monomers with different degrees of hydrophilicity and a polar monomer having a hydrophilic group and a polymerizable vinyl group in an aqueous solution. However, this method cannot copolymerize multiple monomers with relatively large differences in hydrophilicity, such as when the second monomer has an alkyl group containing 6 or more carbon atoms, an aromatic ring group containing 6 or more carbon atoms, or an alicyclic ring group containing 6 or more carbon atoms. In particular, this method cannot copolymerize multiple monomers with large differences in hydrophilicity, such as when the second monomer has an alkyl group containing 12 or more carbon atoms, an aromatic ring group containing 12 or more carbon atoms, or an alicyclic ring group containing 12 or more carbon atoms.

[0085] The present inventors have found that a copolymer having a substantially uniform composition can be obtained by oil-solubilizing a first monomer and then polymerizing the oil-solubilized first monomer with a second monomer. According to this embodiment, a method for producing a copolymer includes an oil-solubilizing step in which a sulfonic acid group or a salt thereof of the first monomer is modified to impart oil-solubility to the first monomer, and a polymerization step in which the oil-solubilized first monomer is radically polymerized with the second monomer to obtain an oil-soluble copolymer. The method for producing a copolymer may further include a water-solubilizing step in which water-solubility is imparted to the oil-soluble copolymer to obtain a water-soluble copolymer.

[0086] The oil-solubilizing step may be a step of modifying a sulfonic acid group or a salt thereof of a water-soluble first monomer to impart oil-solubility to the first monomer, and the polymerization step may be a step of radically polymerizing the oil-soluble first monomer and an oil-soluble second monomer in an organic solvent to obtain an oil-soluble copolymer.

[0087] In this embodiment, the second monomer may be a radical polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 6 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 6 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 6 or more carbon atoms. The second monomer may also be a radical polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms. The upper limit of the number of carbon atoms in the functional group is not particularly limited, but the upper limit of the number of carbon atoms may be 30.

[0088] (Polymerization solvent) Any known solvent may be used in the polymerization reaction of the copolymer constituting the dopant polymer. For example, a solvent capable of dissolving the first monomer, the second monomer, and the copolymer thereof may be used. This allows the copolymer to have a substantially uniform composition.

[0089] Examples of the solvent include protic polar solvents, aprotic polar solvents, and mixtures thereof. Examples of protic polar solvents include methanol, ethanol, and 2-methoxyethanol. Examples of aprotic polar solvents include acetonitrile, dimethylacetamide, dimethylformamide, and dimethylsulfoxide.

[0090] (Polymerization initiator) Any known polymerization initiator may be used in the polymerization reaction of the copolymer constituting the dopant polymer. For example, a suitable polymerization initiator is used depending on the polymerization method, polymerization conditions, and solubility in the polymerization system and / or solvent. The 10-hour half-life temperature of the polymerization initiator may be about 50 to 110°C. When the 10-hour half-life temperature is 50°C or higher, a decrease in polymerization efficiency is suppressed. When the 10-hour half-life temperature is 110°C or lower, a decrease in energy efficiency is suppressed.

[0091] The polymerization initiator may be one or more selected from the group consisting of an azobis compound, an organic peroxide, an inorganic peroxide, and a redox initiator system. An example of an azobis compound is 2,2'-azobis-isobutyronitrile. An example of an organic peroxide is benzoyl peroxide. An example of an inorganic peroxide is sodium persulfate. An example of a redox initiator system is a combination of an azobis compound, an organic peroxide, an inorganic peroxide, or the like, with an amine or the like.

[0092] (chain transfer agent) Any known chain transfer agent may be used in the polymerization reaction of the copolymer constituting the dopant polymer. This allows the molecular weight of the dopant polymer to be adjusted. Examples of chain transfer agents include alcohols, mercaptans, and halogenated carbons. Examples of alcohols include catechol. Examples of mercaptans include n-dodecyl mercaptan. Examples of halogenated carbons include carbon tetrachloride.

[0093] (Purification of dopant polymer) The copolymer obtained by the above polymerization (sometimes simply referred to as a dopant polymer) may be purified using any known purification method. The purification method is appropriately selected depending on the purpose of purification.

[0094] In one embodiment, when the purpose is to remove low molecular weight components, (i) a method of precipitating a dopant polymer and washing the precipitated dopant polymer, (ii) a method of removing low molecular weight components using an ultrafiltration membrane, etc. Examples of low molecular weight components include a chemical oxidation polymerization catalyst, a residual monomer, and an initiator residue.

[0095] In another embodiment, when the purpose is to remove ionic impurities, examples of the method include (i) a method of washing the dopant polymer with an acidic reagent and / or an alkaline reagent, and (ii) a method of removing ionic impurities with a cationic and / or anionic ion exchange resin. In yet another embodiment, when the purpose is to remove or replace the solvent, examples of the method include a method of removing or replacing the solvent by vacuum drying, distillation under reduced pressure, etc.

[0096] (D. Method for Producing the Composite) In this embodiment, the method for producing a composite includes, for example, a step of preparing a dopant polymer. The method for producing a composite includes, for example, a step of polymerizing a raw material monomer of a π-conjugated polymer (the third monomer described above) in an aqueous solution of the dopant polymer. This results in an aqueous dispersion of a π-conjugated polymer doped with the dopant polymer. The polymerization may be oxidative polymerization.

[0097] According to this embodiment, the dopant polymer contains a novel copolymer obtained by polymerizing a plurality of monomers having relatively large differences in hydrophilicity. This provides the composite containing the dopant polymer and the π-conjugated polymer with new functions other than electrical conductivity. Examples of the new functions include water repellency, solvent dispersibility, releasability, and adhesiveness.

[0098] More specifically, in this embodiment, the method for producing the conjugate includes, for example, (a) a preparation step of preparing a water-soluble copolymer including a first repeat unit and a second repeat unit, and (b) a polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in an aqueous solution of the water-soluble copolymer to obtain a conjugate including the π-conjugated polymer and the copolymer.

[0099] As described above, the first repeat unit has a structure derived from the first polymer, and the second repeat unit has a structure derived from the second polymer. The water-soluble copolymer may be a water-soluble dopant polymer.

[0100] The first monomer may be a water-soluble monomer. The second monomer may be an oil-soluble monomer. The second monomer may be less hydrophilic than the first monomer.

[0101] The second monomer may be a radical polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 6 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 6 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 6 or more carbon atoms. The second monomer may be a radical polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms. The upper limit of the number of carbon atoms in the functional group is not particularly limited, but the upper limit of the number of carbon atoms may be 30.

[0102] (a. Preparation of Water-Soluble Copolymer) In this embodiment, the preparation step of preparing the water-soluble copolymer includes, for example, obtaining the water-soluble copolymer, which includes, for example, purchasing the water-soluble copolymer or preparing the water-soluble copolymer.

[0103] (Water-soluble dopant polymer) In this embodiment, the step of preparing the water-soluble copolymer includes a preparation step of preparing an oil-soluble copolymer including a first repeat unit and a second repeat unit, and a water-solubilization step of imparting water solubility to the oil-soluble copolymer. As described above, the first repeat unit has a structure derived from a first polymer. The second repeat unit has a structure derived from a second polymer. The oil-soluble copolymer may be an oil-soluble dopant polymer.

[0104] (oil-soluble dopant polymer) The preparation step of preparing the oil-soluble copolymer includes, for example, obtaining the oil-soluble copolymer, which includes, for example, purchasing the oil-soluble copolymer or preparing the oil-soluble copolymer.

[0105] In this embodiment, the step of preparing the oil-soluble copolymer includes, for example, an oil-solubilizing step of modifying the sulfonic acid group or a salt thereof of a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group to impart oil-solubility to the first monomer, and a polymerization step of radically polymerizing the oil-soluble first monomer with a second monomer. This results in a copolymer. More specifically, an oil-soluble copolymer is obtained.

[0106] In this embodiment, the oil-solubilizing step includes, for example, reacting the sulfonic acid group or a salt thereof of the first monomer with an alkylamine salt, which may be a primary amine salt, a secondary amine salt, or a tertiary amine salt.

[0107] As described below, the complex can be purified using an ion exchange resin. Primary amine salts are more easily adsorbed to ion exchange resins than secondary amine salts and tertiary amine salts. Furthermore, secondary amine salts are more easily adsorbed to ion exchange resins than tertiary amine salts. Therefore, by using a primary amine salt or a secondary amine salt as the alkylamine salt, the complex can be easily purified. When a primary amine salt is used as the alkylamine salt, purification of the complex becomes very easy.

[0108] Examples of primary amines include mono-n-octylamine, mono-2-ethylhexylamine, mono-n-dodecylamine, etc. Examples of secondary amines include di-n-butylamine, di-n-octylamine, di-n-dodecylamine, etc. Examples of tertiary amines include tri-n-butylamine, tri-n-hexylamine, tri-n-octylamine, etc.

[0109] In this embodiment, the polymerization step includes, for example, radically polymerizing an oil-soluble first monomer and an oil-soluble second monomer in an organic solvent to produce an oil-soluble copolymer. The polymerization step includes, for example, radically polymerizing the first monomer and the second monomer in the substantial absence of a water-soluble monomer different from the first monomer. The water-soluble monomer different from the first monomer may be a polar monomer having a hydrophilic group and a polymerizable vinyl group. The polymerization step may also include radically polymerizing the first monomer and the second monomer in the substantial absence of a monomer different from the first monomer and the second monomer.

[0110] In this case, the first monomer may be a water-soluble monomer, and the second monomer may be an oil-soluble monomer. The second monomer is preferably a radically polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 6 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 6 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 6 or more carbon atoms. The second monomer is more preferably a radically polymerizable monomer having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms. The upper limit of the number of carbon atoms in the functional group is not particularly limited, but the upper limit may be 30.

[0111] (Properties of oil-soluble dopant polymers) In this embodiment, the oil-soluble dopant polymer has a second repeat unit derived from the second monomer described above, which results in a dopant polymer that is soluble in low-polarity solvents.

[0112] According to one embodiment, a dopant polymer is obtained that has a higher solubility in at least one of ethanol, isopropyl alcohol, n-butanol, and toluene than polystyrene sulfonic acid, which is commonly used as a dopant polymer for conductive polymer compositions. According to another embodiment, a dopant polymer is obtained that is soluble in methyl ethyl ketone (MEK) and / or toluene.

[0113] For example, when the second polymer is lauryl methacrylate, the oil-soluble dopant polymer is soluble in ethanol, isopropyl alcohol (IPA), n-butanol (nBuOH), and toluene. For example, when the second polymer is stearyl methacrylate, the oil-soluble dopant polymer is soluble in ethanol, isopropyl alcohol (IPA), n-butanol (nBuOH), methyl ethyl ketone (MEK), and toluene.

[0114] In one embodiment, the oil-soluble dopant polymer exhibits relatively greater solubility in solvents less polar than water, hi another embodiment, the oil-soluble dopant polymer exhibits relatively greater solubility in solvents less polar than methanol.

[0115] The degree of polarity of various solvents is determined, for example, by the Rohrschneider polarity parameter. The above-mentioned solvents with low polarity may have a Rohrschneider polarity parameter of less than 5. The above-mentioned solvents with low polarity may have a Rohrschneider polarity parameter of less than 4.4. For example, the polarity parameter of water is 10.2, and the polarity parameter of ethanol is 4.3. The polarity parameter of isopropyl alcohol is 3.9, and the polarity parameter of toluene is 2.4.

[0116] Examples of the solvents with low polarity include alcohols, ketones, and aromatic hydrocarbons. Examples of the alcohols include ethanol, propanol, isopropyl alcohol (IPA), butanol, and n-butanol (nBuOH). Examples of the ketones include methyl ethyl ketone (MEK) and methyl isobutyl ketone. Examples of the aromatic hydrocarbons include toluene, benzene, and xylene.

[0117] (Water-solubilization treatment) In this embodiment, the oil-soluble copolymer has a structure derived from the first monomer to which oil solubility has been imparted. The oil-soluble first monomer can be obtained, for example, by modifying the sulfonic acid group or its salt of a first monomer having a sulfonic acid group or its salt and a polymerizable vinyl group in the oil-solubilizing step described above. In this embodiment, the water-solubilizing step includes, for example, modifying the structure derived from the sulfonic acid group of the first monomer modified in the oil-solubilizing step. The water-solubilizing step includes, for example, (i) reacting the oil-soluble copolymer with (ii) a compound that is more basic than the compound used to modify the sulfonic acid group or its salt in the oil-solubilizing step, and whose salt with the sulfonic acid group is water-soluble. Examples of such compounds include strongly basic alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

[0118] For example, if the sulfonic acid group or its salt of the first monomer is modified with an alkylamine salt in the oil-solubilizing step, the alkylamine group is eliminated from the structure derived from the sulfonic acid group of the first monomer in the water-solubilizing step, thereby making the oil-soluble copolymer water-soluble.

[0119] (b. Polymerization stage of the complex) According to this embodiment, the method includes a step of polymerizing a third monomer in an aqueous solution of the water-soluble copolymer (for example, the copolymer to which water solubility has been imparted) prepared in the above preparation step. This results in an aqueous dispersion of a complex containing a π-conjugated polymer and the copolymer. As a method for polymerizing the third monomer, any polymerization method known as a method for producing a π-conjugated polymer can be used. As described above, an example of a method for producing a π-conjugated polymer is chemical oxidative polymerization in an electrolytic substrate solvent.

[0120] The ratio of the dopant polymer to the third monomer is not particularly limited, but the ratio of the mass of the dopant polymer to the mass of the third monomer is preferably 0.5 to 10 times, and more preferably 1 to 5 times. When the ratio of the mass of the dopant polymer to the mass of the third monomer is 0.5 times or more, the stability of the composite or composition containing the composite is improved. When this ratio is 1 time or more, the stability of the composite or composition containing the composite is further improved. When the ratio of the mass of the dopant polymer to the mass of the third monomer is 10 times or less, the conductivity of the composite or composition containing the composite is improved. When this ratio is 5 times or less, the conductivity of the composite or composition containing the composite is further improved.

[0121] Any known chemical oxidation polymerization catalyst can be used as the oxidizing agent. More specifically, the oxidizing agent may be one or more compounds selected from the group consisting of iron compounds, copper compounds, and persulfates. Examples of iron compounds include (i) iron(III) chloride and iron(III) sulfate. Examples of copper compounds include copper(II) chloride, copper(II) sulfate, copper(II) tetrafluoroborate, and copper(II) hexafluorophosphate. Examples of persulfates include sodium persulfate, potassium persulfate, and ammonium persulfate.

[0122] (Purification of the complex) The composite obtained by the above polymerization may be purified using any known purification method. The purification method is appropriately selected depending on the purpose of the purification. In one embodiment, when the purpose is to remove low molecular weight components, (i) a method of precipitating the composite and washing the precipitated composite, or (ii) a method of removing low molecular weight components using an ultrafiltration membrane, etc. are used. Examples of low molecular weight components include a chemical oxidation polymerization catalyst, residual monomers, and initiator residues.

[0123] In another embodiment, when the purpose is to remove ionic impurities, examples of the method include (i) a method of washing the complex with an acidic reagent and / or an alkaline reagent, and (ii) a method of removing ionic impurities with a cationic and / or anionic ion exchange resin. In yet another embodiment, when the purpose is to remove or replace the solvent, examples of the method include a method of removing or replacing the solvent by vacuum drying, distillation under reduced pressure, etc.

[0124] (Microparticulation of the complex) The composite obtained by the polymerization or the purified composite may be microparticulated by any known microparticulation treatment. This improves the solvent stability of the composite or the π-conjugated polymer. Examples of microparticulation treatment include a method of mixing a medium such as zirconia beads and then shaking using a paint shaker, a method of stirring using a homogenizer, a method of high-pressure treatment using a high-pressure homogenizer, and a method of ultrasonic treatment using an ultrasonic homogenizer. [Example]

[0125] The present invention will be described in more detail below with reference to the following examples. It should be noted that the present invention is not limited to the following production examples, synthesis examples, or examples. Furthermore, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0126] (Production Example 1) In Production Example 1, mono-n-octylamine p-styrenesulfonate (sometimes referred to as MOASS), an example of the first monomer, was prepared by the following procedure.

[0127] First, 155 parts of 10% hydrochloric acid was weighed into a glass beaker. While stirring the hydrochloric acid with a PTFE stirrer in an ice bath, 54.9 parts of mono-n-octylamine was slowly added to the hydrochloric acid. This prepared an aqueous solution of mono-n-octylamine hydrochloride.

[0128] Next, 100 parts of sodium p-styrenesulfonate (Spinomer NaSS, manufactured by Tosoh Finechem Corporation; sometimes simply referred to as NaSS) and 900 parts of ion-exchanged water were weighed into another glass beaker. The solution was stirred at room temperature using a PTFE stirrer until the NaSS was completely dissolved.

[0129] Next, while continuing to stir the NaSS aqueous solution, the mono-n-octylamine hydrochloride aqueous solution was slowly added to the NaSS aqueous solution. The reaction solution was then stirred at room temperature for 1 hour. As the reaction progressed, the reaction product, MOASS, precipitated from the reaction solution. After stirring was completed, the reaction solution was filtered to recover the precipitated MOASS.

[0130] The recovered MOASS was washed with water to remove the by-product NaCl, and then dried at room temperature until it reached a constant weight, yielding 110 parts of MOASS.

[0131] (Synthesis Example 1) In Synthesis Example 1, a dopant polymer was prepared by polymerizing MOASS, an example of a first monomer, and stearyl methacrylate (sometimes referred to as SMA), an example of a second polymer. The dopant polymer was prepared by the following procedure.

[0132] First, 15 parts of MOASS, 15 parts of SMA, and 50 parts of N,N-dimethylformamide (sometimes referred to as DMF) as a solvent were weighed into a four-neck flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube. Stirring was started while introducing nitrogen gas into the flask, and the mixture was heated until the internal temperature reached 80°C. This allowed the MOASS and SMA to dissolve in the DMF.

[0133] Next, 0.45 parts of 2,2'-azobis(isobutyronitrile) (sometimes referred to as AIBN) and 20 parts of DMF were weighed into a glass beaker. After confirming that the AIBN had dissolved in the DMF, the DMF solution of AIBN was transferred to a dropping funnel and added dropwise over 4 hours to a four-neck flask with the internal temperature maintained at 80°C. After the dropping of the DMF solution of AIBN was completed, stirring was continued for 3 hours while the internal temperature was maintained at 80°C. This produced a DMF solution of the dopant polymer (sometimes referred to as Ds-1).

[0134] Next, the dopant polymer was purified according to the following procedure. First, 450 parts of methyl ethyl ketone (sometimes referred to as MEK) was weighed into a glass beaker. While stirring the MEK, 50 parts of a DMF solution of the dopant polymer (Ds-1) was slowly added to the MEK, causing a precipitate to form. The reaction solution was filtered to recover the precipitate. 200 parts of MEK was added to the recovered precipitate, and the mixture was stirred, followed by filtration to recover the precipitate. This procedure was repeated twice. This resulted in a purified recovered product.

[0135] Next, the dopant polymer was water-soluble according to the following procedure. First, 300 parts of ion-exchanged water and 1 part of sodium hydroxide were added to the purified recovered material and stirred. After confirming that the recovered material had dissolved in the aqueous sodium hydroxide solution, the aqueous solution was transferred to a recovery flask, and 150 parts of the liquid was removed from the aqueous solution under reduced pressure using a rotary evaporator. Next, the aqueous solution remaining in the recovery flask was transferred to another beaker, and while stirring the aqueous solution, 45 parts of Duolite C255LFH (a cation exchange resin manufactured by Sumika Chemtex Co., Ltd.; hereinafter referred to as C255LFH) was added to the aqueous solution. The aqueous solution was then stirred for 1 hour. After stirring was completed, the ion-exchange resin was removed from the aqueous solution by filtration. Ion-exchanged water was added to the aqueous solution from which the ion-exchange resin had been removed, and the polymer content was adjusted to 5%. This resulted in an aqueous solution of the dopant polymer (sometimes referred to as Dw-1).

[0136] (Synthesis Examples 2 to 4) DMF solutions of dopant polymers of Synthesis Examples 2 to 4 (Ds-2, Ds-3, Ds-4) and aqueous solutions of dopant polymers (Dw-2, Dw-3, Dw-4) were prepared in the same manner as in Synthesis Example 1, except that the monomer compositions were changed as shown in Table 1. In addition, DMF solutions and aqueous solutions of dopant polymers of Synthesis Example 5 were prepared in the same manner as in Synthesis Example 1. In Table 1, the numbers indicate weight fractions, and the numbers in parentheses indicate molar fractions.

[0137] [Table 1]

[0138] Table 2 shows the copolymerization ratios of the first monomer and the second monomer in the dopant polymers prepared in Synthesis Examples 1 to 3. Table 2 also shows the acid values ​​(mgNaOH / g) of the dopant polymers prepared in Synthesis Examples 1 to 3. The acid values ​​were determined by measuring the isoelectric point of each dopant polymer aqueous solution sample using an automatic titrator (HIRANUMA COM-1750) with a 0.1 mol / L sodium hydroxide aqueous solution as the standard solution. Each dopant polymer aqueous solution sample was prepared by precisely weighing each dopant polymer aqueous solution to a polymer content of 1 g and then diluting with ion-exchange water to a total weight of 50 g.

[0139] In measuring the acid value of each dopant polymer aqueous solution, the isoelectric point of each dopant polymer aqueous solution was 1. This suggests that the second monomer was not hydrolyzed during the polymerization reaction.

[0140] The copolymerization ratio (molar fraction) was calculated using the measured acid value according to the following formulas (1) and (2). In formulas (1) and (2), M1 is the molar fraction of the first monomer, and M2 is the molar fraction of the second monomer. W1 is the molecular weight (g / mol) of the first monomer, and W2 is the molecular weight (g / mol) of the second monomer. W N is the molecular weight of sodium hydroxide (g / mol). Av is the acid number of the dopant polymer (mgNaOH / g).

[0141]

number

[0142] M2 = 100 - M1 (Equation 2)

[0143] [Table 2]

[0144] As shown in Table 2, the copolymerization ratio of each dopant polymer is approximately the same as the composition of the raw material monomers. This shows that the first monomer and the second monomer are copolymerized approximately uniformly. Furthermore, in the synthesis experiments of Synthesis Examples 1 to 3, each dopant polymer aqueous solution was obtained as a transparent aqueous solution. This shows that the first monomer and the second monomer are copolymerized approximately uniformly. From the results of Synthesis Examples 1 to 3, it is estimated that the first monomer and the second monomer are also copolymerized approximately uniformly in the dopant polymer of Synthesis Example 5.

[0145] Example 1 In Example 1, a waterborne conductive polymer composition was prepared by polymerizing 3,4-ethylenedioxythiophene (sometimes referred to as EDT) as a raw material monomer (the third monomer described above) of a π-conjugated polymer in the presence of the aqueous solution (Dw-1) of the dopant polymer obtained in Synthesis Example 1. The waterborne conductive polymer composition was prepared by the following procedure.

[0146] (Polymerization and Purification of Water-Based Conductive Polymer Composition) First, 0.5 parts of iron (III) sulfate n-hydrate, 1 part of EDT, 60 parts of the aqueous solution of the dopant polymer (Dw-1) obtained in Synthesis Example 1, and 180 parts of ion-exchanged water were weighed into a four-neck flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube. Stirring was started while introducing nitrogen gas into the flask, and the internal temperature was adjusted to 30°C.

[0147] Next, 2.5 parts of sodium persulfate and 20 parts of ion-exchanged water were weighed into a glass beaker. After confirming that the sodium persulfate had dissolved in the ion-exchanged water, the aqueous sodium persulfate solution was transferred to a dropping funnel and added dropwise over 4 hours to a four-neck flask with the internal temperature maintained at 30°C. After the dropping of the aqueous sodium persulfate solution was completed, stirring was continued for 3 hours while the internal temperature was maintained at 30°C.

[0148] Next, 30 parts of C255LFH (a cation exchange resin manufactured by Sumika Chemtex Co., Ltd.) and 30 parts of Duolite A368S (an anion exchange resin manufactured by Sumika Chemtex Co., Ltd., sometimes referred to as A368S) were added to the reaction solution, and stirring was continued for 1 hour. After stirring was completed, the ion exchange resin was removed from the reaction solution by filtration. This resulted in an aqueous conductive polymer composition (sometimes referred to as Cw-1).

[0149] (Examples 2 to 3 and Comparative Examples 1 to 2) Waterborne conductive polymer compositions (Cw-2, Cw-3, Cw-4, Cw-5) of Examples 2 and 3 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1, except that the composition of the raw materials was changed as shown in Table 3. In Table 3, the numbers in the charge amount row indicate the parts by weight of the charge of the dopant polymer aqueous solution with a polymer content of 5%. The numbers in parentheses in the charge amount row indicate the parts by weight of the polymer content in the dopant polymer aqueous solution.

[0150] Example 4 (Preparation of Solvent-Based Conductive Polymer Composition) First, 65 parts of MEK and 5 parts of methanol were weighed into a four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser. The solvent was heated with stirring until the internal temperature reached 60°C. Next, 30 parts of the aqueous conductive polymer composition (Cw-1) was slowly added to the four-neck flask with stirring to precipitate the conductive polymer composition.

[0151] The reaction solution was filtered to recover a precipitate. 100 parts of MEK was added to the recovered precipitate, and the mixture was stirred. The precipitate was then recovered by filtration. This procedure was repeated twice. A purified product was thus obtained.

[0152] Next, 2-propanol (sometimes referred to as IPA) was added as a dispersion solvent to the purified recovered material to prepare a slurry with a polymer content of 0.2%. The purified recovered material was dispersed in the slurry using a high-pressure homogenizer. This resulted in a solvent-based conductive polymer composition (sometimes referred to as Cs-1).

[0153] (Examples 5 to 7 and Comparative Examples 3 to 5) Solvent-based conductive polymer compositions (Cs-2, Cs-3, Cs-4, Cs-5, Cs-6, and Cs-7) of Examples 5 to 7 and Comparative Examples 3 to 5 were prepared in the same manner as in Example 4, except that the composition of the raw materials was changed as shown in Table 4. In Table 4, "Not measurable" in the row for surface resistivity indicates that the surface resistivity was higher than the upper limit of measurement of the surface resistance meter, and a measured value could not be obtained. Furthermore, "Not measurable" in the rows for "Total light transmittance" and "Haze" indicates that a uniform film could not be obtained, and the measured value varied greatly depending on the measurement position.

[0154] (evaluation) The surface resistivity, total light transmittance, and haze were measured for each of the conductive polymer compositions of Examples 1 to 7 and Comparative Examples 1 to 5. The water contact angle was also measured for the water-based conductive polymer compositions. The dispersion state and water content of the solvent-based conductive polymer compositions were measured using the following procedures. The evaluation results are shown in Tables 3 and 4.

[0155] (Surface resistivity) First, a coating solution containing a conductive polymer composition was prepared. For the aqueous conductive polymer composition, a diluted solution was prepared by adding 100 parts of methanol and 0.8 parts of a wetting agent (surfactant "Olfine EXP.4200" manufactured by Nissin Chemical Co., Ltd.) to 100 parts of an aqueous conductive polymer composition with a polymer content of 1.2%, and mixing them. This diluted solution was used as the coating solution. For the solvent-based conductive polymer composition, a high-pressure homogenized solution with a polymer content of 0.2% was used as the coating solution.

[0156] Next, each coating solution was applied to the surface of a PET film (Lumirror 188T60, manufactured by Toray Industries, Inc.) using a No. 4 bar coater. The PET film coated with the coating solution was dried at 105°C for 1 minute using a hot air dryer. This resulted in the production of a sample film coated with each conductive polymer composition. The surface resistivity of each sample film was measured using a surface resistivity meter (Hiresta-UP MCP-HT450, Probe URS, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) at an applied voltage of 10 V.

[0157] (Total light transmittance and haze) The total light transmittance and haze of the sample film used to measure the surface resistivity were measured using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0158] (water contact angle) A drop of 20 μL of ion-exchanged water was applied to the surface of the sample film used for measuring the surface resistivity. The contact angle was measured 30 seconds after the drop of ion-exchanged water was applied using a contact angle meter (DMo-601, manufactured by Kyowa Interface Science Co., Ltd.).

[0159] (dispersed state) The high-pressure homogenizer-treated solution with a polymer content of 0.2% was poured into a 50 mL glass bottle and allowed to stand for 1 day in an environment of 23° C. Thereafter, the presence or absence of precipitation and separation was visually confirmed.

[0160] (moisture content) Each solvent-based conductive polymer composition was filtered through a membrane filter with a collection particle size of 5 μm, and the volatile components separated by gas chromatography (Shimadzu Corporation, GC-2014) were quantified using a TCD detector with an external standard method. The water content is the weight fraction of water in the total volatile components.

[0161] [Table 3]

[0162] [Table 4]

[0163] Table 3 shows that the coatings of the aqueous conductive polymer compositions of Examples 1 to 3 have excellent water repellency, and Table 4 shows that the solvent-based conductive polymer compositions of Examples 4 to 7 have excellent dispersibility in the solvent and excellent coating conductivity.

[0164] (Solubility of dopant polymer) The solubility of the dopant polymer (MOASS and SMA copolymer) of Synthesis Example 1 in ethanol, IPA, n-butanol, MEK, and toluene was investigated using the following procedure. First, a 7.1% aqueous solution of the oil-soluble dopant polymer of Synthesis Example 1 was prepared. Next, the aqueous solution of the oil-soluble dopant polymer was dried in a dryer at 60°C for 12 hours to produce a film with a thickness of approximately 200 μm. Next, 0.5 g of the film and 15 g of each solvent were placed in a 20 mL screw cap bottle and allowed to stand for one day. Subsequently, ultrasonic treatment was performed for one hour using an ultrasonic cleaner (US-3, manufactured by SND Corporation) at a high-frequency power of 150 W and an oscillation frequency of 38 kHz.

[0165] The dissolution state of the film after ultrasonic treatment was visually observed. As a result, it was confirmed that the sample was soluble in all solvents. Note that polystyrene sulfonic acid, which is commonly used as a dopant polymer in conductive polymer compositions, is insoluble in ethanol, IPA, n-butanol, MEK, and toluene under the same conditions as above.

[0166] Using the same procedure, the solubility of the dopant polymer (MOASS and LMA copolymer) of Synthesis Example 2 in various solvents was investigated. As a result, it was confirmed that the samples placed in ethanol, IPA, n-butanol, and toluene were dissolved. On the other hand, it was confirmed that a portion of the sample placed in MEK remained undissolved in the solvent.

[0167] Using the same procedure, the solubility of the dopant polymer (a copolymer of MOASS and MMA) of Synthesis Example 3 in various solvents was investigated, and it was confirmed that the sample remained in all solvents.

[0168] Using the same procedure, the solubility of the dopant polymer (MOASS and HMA copolymer) of Synthesis Example 5 in various solvents was investigated. As a result, it was confirmed that the samples placed in ethanol, IPA, and n-butanol were dissolved. On the other hand, it was confirmed that a portion of the samples placed in toluene and MEK remained undissolved in the solvent.

[0169] Although the present invention has been described above using embodiments, the technical scope of the present invention is not limited to the scope described in the above embodiments. It will be apparent to those skilled in the art that various modifications and improvements can be made to the above embodiments. It is clear from the claims that such modifications and improvements can also be included within the technical scope of the present invention.

[0170] It should be noted that the order of execution of each process, such as operations, procedures, steps, and stages, in the devices, systems, programs, and methods shown in the claims, specifications, and drawings is not specifically stated as "before," "prior to," etc., and that the processes can be performed in any order unless the output of a previous process is used in a subsequent process. Even if the operational flow in the claims, specifications, and drawings is described using "first," "next," etc. for convenience, this does not mean that the processes must be performed in this order.

[0171] [Item 1] a π-conjugated polymer; a dopant polymer having a copolymer including a first repeat unit and a second repeat unit; A complex comprising: the first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group, the second repeating unit has a structure derived from a second monomer that is a radical polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms; Complex. [Item 2] the second monomer is substantially free of hydrophilic groups; Item 1. The conjugate according to item 1. [Item 3] the second monomer is substantially free of at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydroxyl group, and an amino group; Item 1. The conjugate according to item 1. [Item 4] The second monomer is at least one compound selected from the group consisting of (meth)acrylic acid derivatives, (meth)acrylic acid esters and derivatives thereof, and (meth)acrylamide derivatives, or a vinyl compound, having at least one functional group selected from the group consisting of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms; Item 1. The conjugate according to item 1. [Item 5] The second monomer has a lower hydrophilicity than the first monomer. Item 1. The conjugate according to item 1. [Item 6] the first monomer is at least one compound selected from the group consisting of styrene sulfonic acid, vinyl sulfonic acid, Nt-butylacrylamidosulfonic acid, 2-sulfoethyl methacrylate, derivatives thereof, and salts thereof; Item 1. The conjugate according to item 1. [Item 7] The complex according to any one of items 1 to 6, Water as a dispersion medium for the complex; Including, dispersion liquid. [Item 8] The complex according to any one of items 1 to 6, an organic solvent as a dispersion medium for the complex; Including, dispersion liquid. [Item 9] The dispersion medium is substantially free of water and dispersants. Item 9. The dispersion according to item 8. [Item 10] The complex according to any one of items 1 to 6, a dispersion medium that disperses and holds the complex; 1. A conductive paint comprising: [Item 11] A conductive material comprising the composite according to any one of items 1 to 6, It has a film or sheet shape, a thread or fiber shape, or a mesh shape. Conductive materials. [Item 12] Item 1 to Item 6, comprising a conductive material containing the composite material; electronic equipment. [Item 13] an oil-solubilizing step of modifying the sulfonic acid group or the salt thereof of a first monomer having a sulfonic acid group or the salt thereof and a polymerizable vinyl group to impart oil-solubility to the first monomer; a first polymerization step of radically polymerizing the first monomer having oil solubility and a second monomer which is a radical polymerizable monomer; a water-solubilizing step of imparting water solubility to the copolymer obtained in the first polymerization step; a second polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in the aqueous solution of the copolymer to which water solubility has been imparted, to obtain a composite containing the π-conjugated polymer and the copolymer; A method for producing a complex comprising: [Item 14] The oil-solubilizing step comprises: reacting the sulfonic acid group or a salt thereof of the first monomer with an alkylamine salt; Including, Item 14. A method for producing the complex according to Item 13. [Item 15] The first polymerization step comprises: a step of radically polymerizing the oil-soluble first monomer and the oil-soluble second monomer in an organic solvent to prepare the oil-soluble copolymer; Including, Item 14. A method for producing the complex according to Item 13. [Item 16] the first monomer is a water-soluble monomer; the second monomer is an oil-soluble monomer; The first polymerization step comprises: radically polymerizing the first monomer and the second monomer in the substantial absence of a water-soluble monomer different from the first monomer; Including, Item 14. A method for producing the complex according to Item 13. [Item 17] providing a water-soluble copolymer comprising a first repeat unit and a second repeat unit; a polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in the water-soluble aqueous solution of the copolymer to obtain a composite including the π-conjugated polymer and the copolymer; and the first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group, the second repeating unit has a structure derived from a second monomer that is a radical polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms; Methods for producing composites. [Item 18] providing an oil-soluble copolymer comprising a first repeat unit and a second repeat unit; a water-solubilizing step of imparting water solubility to the oil-soluble copolymer; a polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in the aqueous solution of the copolymer to which water solubility has been imparted, to obtain a composite including the π-conjugated polymer and the copolymer; and the first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group, the second repeating unit has a structure derived from a second monomer that is a radical polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms; Methods for producing composites. [Item 19] A copolymer comprising a first repeat unit and a second repeat unit, the first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group, the second repeating unit has a structure derived from a second monomer that is a radical polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms; The second monomer has a lower hydrophilicity than the first monomer. Copolymer. [Item 20] an oil-solubilizing step of modifying the sulfonic acid group or a salt thereof of a water-soluble first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group to impart oil-solubility to the first monomer; a polymerization step of radically polymerizing the first monomer to which oil solubility has been imparted and a second monomer, which is an oil-soluble radical polymerizable monomer, in an organic solvent to obtain an oil-soluble copolymer; a water-solubilizing step of imparting water solubility to the oil-soluble copolymer to obtain a water-soluble copolymer; having Method for producing copolymers.

Claims

1. an oil-solubilizing step of modifying the sulfonic acid group or the salt thereof of a first monomer having a sulfonic acid group or the salt thereof and a polymerizable vinyl group to impart oil-solubility to the first monomer; a first polymerization step of radically polymerizing the first monomer having oil solubility and a second monomer which is a radical polymerizable monomer; a water-solubilizing step of imparting water solubility to the copolymer obtained in the first polymerization step; a second polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in the aqueous solution of the copolymer to which water solubility has been imparted, to obtain a composite containing the π-conjugated polymer and the copolymer; A method for producing a complex comprising:

2. The oil-solubilizing step comprises: reacting the sulfonic acid group or a salt thereof of the first monomer with an alkylamine salt; Including, A method for producing the complex of claim 1.

3. The first polymerization step comprises: a step of radically polymerizing the oil-soluble first monomer and the oil-soluble second monomer in an organic solvent to prepare the oil-soluble copolymer; Including, A method for producing the complex of claim 1.

4. the first monomer is a water-soluble monomer; the second monomer is an oil-soluble monomer; The first polymerization step comprises: radically polymerizing the first monomer and the second monomer in the substantial absence of a water-soluble monomer different from the first monomer; Including, A method for producing the complex of claim 1.

5. providing a water-soluble copolymer comprising a first repeat unit and a second repeat unit; a polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in the water-soluble aqueous solution of the copolymer to obtain a composite including the π-conjugated polymer and the copolymer; and the first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group, the second repeating unit has a structure derived from a second monomer which is a radical polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms; Methods for producing composites.

6. providing an oil-soluble copolymer comprising a first repeat unit and a second repeat unit; a water-solubilizing step of imparting water solubility to the oil-soluble copolymer; a polymerization step of polymerizing a third monomer that forms a π-conjugated polymer in the aqueous solution of the copolymer to which water solubility has been imparted, to obtain a composite including the π-conjugated polymer and the copolymer; and the first repeating unit has a structure derived from a first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group, the second repeating unit has a structure derived from a second monomer which is a radical polymerizable monomer having at least one of a substituted or unsubstituted alkyl group having 12 or more carbon atoms, a substituted or unsubstituted aromatic ring group having 12 or more carbon atoms, and a substituted or unsubstituted alicyclic ring group having 12 or more carbon atoms; Methods for producing composites.

7. an oil-solubilizing step of modifying the sulfonic acid group or a salt thereof of a water-soluble first monomer having a sulfonic acid group or a salt thereof and a polymerizable vinyl group to impart oil-solubility to the first monomer; a polymerization step of radically polymerizing the oil-soluble first monomer and an oil-soluble radically polymerizable second monomer in an organic solvent to obtain an oil-soluble copolymer; a water-solubilizing step of imparting water solubility to the oil-soluble copolymer to obtain a water-soluble copolymer; having Method for producing copolymers.

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