Slurry compositions, conductive compositions, and molded articles, as well as methods for manufacturing them.

Abstract

To provide a conductive composition that offers superior conductivity and yields a molded article with high strength.SOLUTION: A slurry composition comprises carbon fibers, π-conjugated polymers, a dopant with an organic acid group that reacts with the π-conjugated polymers to express conductivity, a resin A, and water. The water has a compounding ratio of 30-60 mass%.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a slurry composition, a conductive composition, a molded body, and methods for producing them.

Background Art

[0002] Conventionally, compositions having conductivity have been proposed. For example, Patent Document 1 describes a polyolefin-based resin composition for a conductive part, which is obtained by blending a polyolefin resin (a), a carbon nanostructure (b), and a thermoplastic elastomer (c), wherein the polyolefin resin (a) is 43 to 89% by mass, the carbon nanostructure (b) is 1 to 7% by mass, and the thermoplastic elastomer (c) is 10 to 50% by mass, based on the total of the polyolefin resin (a), the carbon nanostructure (b), and the thermoplastic elastomer (c). Such a composition is described as being excellent in fluidity and capable of providing a conductive part having excellent conductivity, as well as further excellent mechanical strength, particularly tensile strength and impact resistance.

[0003] Further, Patent Document 2 describes a method for producing a slurry, which includes a mixing step of obtaining a mixed liquid by mixing resin particles having an average particle diameter of 1 μm or more and 700 μm or less, a fibrous carbon nanostructure, and a dispersion medium, and a dispersion step of subjecting the mixed liquid to a dispersion treatment using a wet media-less disperser under the condition that the pressure (gauge pressure) applied to the mixed liquid is 5 MPa or less to obtain a slurry. According to such a method for producing a slurry, it is described that a slurry in which the fibrous carbon nanostructure is well dispersed can be easily produced.

[0004] Furthermore, Patent Document 3 describes composite resin material particles, which are raw materials for manufacturing resin molded articles, characterized in that a dispersed mixed layer is formed on at least the entire surface or a portion of the resin material particles, in which conductive nanomaterial is dispersed and mixed from the surface toward the interior of the resin material particles, and in the dispersed mixed layer, the conductive nanomaterial is dispersed and mixed within the resin material, and the entire dispersed mixed layer forms a conductive layer. It is stated that with such composite resin material particles, the conductive nanomaterial is firmly embedded in the dispersed mixed layer to form a conductive dispersed mixed layer, so that the conductive nanomaterial is firmly fixed from the surface toward the interior of the composite resin material particles and does not peel off.

[0005] Furthermore, Patent Document 4 describes a conductive resin composition comprising (A) a conductive fibrous filler, (B) a conductive resin, and (C) a non-conductive matrix which is an organic polymer resin containing at least one group selected from the group consisting of carboxylic acids, sulfonic acids, phosphonic acids, phosphinic acids, and salts thereof, characterized in that the composition of the composition has a specific content ratio. It is stated that such a conductive resin composition is a resin composition with excellent conductivity and transparency, and that by laminating this conductive composition as a thin film on the surface of a non-conductive molded product, a molded product with low surface resistance and high transparency or surface gloss can be provided. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-076641 [Patent Document 2] International Publication No. 2018 / 066458 [Patent Document 3] Japanese Patent Publication No. 2010-189621 [Patent Document 4] Japanese Patent Publication No. 2004-210843 [Overview of the project] [Problems that the invention aims to solve]

[0007] There is a need for a conductive composition that can produce molded articles with excellent conductivity and high strength.

[0008] The present invention provides a conductive composition containing predetermined components, which, through their synergistic effects, can produce a molded article with excellent conductivity and high strength. It also provides a slurry composition used to obtain the conductive composition, and a molded article obtained from the conductive composition. Furthermore, it provides a method for manufacturing the slurry composition, the conductive composition, and the molded article. [Means for solving the problem]

[0009] The inventors diligently conducted research and found a way to solve the above problems, thus completing the present invention. The present invention is as follows (1) to (9). (1) Carbon fiber and π-conjugated polymers and A dopant having an organic acid group that reacts with the aforementioned π-conjugated polymer to exhibit conductivity, Resin A and Water and, A slurry composition comprising the above, wherein the proportion of water is 30 to 60% by mass. (2) Carbon fiber and The reaction product of a π-conjugated polymer and a dopant having an organic acid group that reacts with it to exhibit conductivity, Resin X and, A conductive composition containing the following: (3) The conductive composition according to (2) above, wherein the mass ratio of the carbon fiber to the resin X is 1:1 to 1000. (4) Carbon fiber and, The reaction product of a π-conjugated polymer and a dopant having an organic acid group that reacts with it to exhibit conductivity, Resin X and, A molded body containing the above. (5) The molded article according to (4) above, wherein the mass ratio of the carbon fiber to the resin X is 1:1 to 1000. (6) Carbon fiber and, a π-conjugated polymer, a dopant having an organic acid group that reacts with the π-conjugated polymer to exhibit conductivity, granular resin A, water, are blended and stirred to obtain the slurry composition according to (1) above, a stirring step; a mixing step of mixing the slurry composition and resin B; A method for producing a conductive composition, comprising obtaining the conductive composition according to (2) or (3) above. (7) The method for producing a conductive composition according to (6) above, wherein in the stirring step, the mixture is rotated and revolved to obtain the slurry composition. (8) The mixing step is granulating the slurry composition and mixing the resin B and the granulated slurry composition, the method for producing a conductive composition according to (6) or (7) above. (9) A method for producing a molded article, comprising a molding step of molding the conductive composition according to (2) or (3) above to obtain the molded article according to (4) above.

Advantages of the Invention

[0010] According to the present invention, it is possible to provide a conductive composition that contains predetermined components and, due to their synergistic effects, can obtain a molded article with excellent conductivity and high strength. Further, it is possible to provide a slurry composition used to obtain the conductive composition. Also, it is possible to provide a molded article obtained from the conductive composition. Furthermore, it is possible to provide methods for producing the slurry composition, the conductive composition, and the molded article.

Brief Description of the Drawings

[0011] [Figure 1]This is an electron micrograph (SEM image) obtained by observing the slurry (1) of Example 1 after drying at a magnification of 30,000 using a scanning electron microscope. [Figure 2] This is a photograph obtained by observing the test piece (1) of Example 1 at a magnification of 5,000 using an optical microscope. [Figure 3] This is an electron micrograph (SEM image) obtained by observing the slurry (1) of Comparative Example 1 after drying at a magnification of 5,000 using a scanning electron microscope.

Mode for Carrying Out the Invention

[0012] [Slurry Composition of the Present Invention] The slurry composition of the present invention will be described. The slurry composition of the present invention is prepared by blending carbon fiber, π-conjugated polymer, a dopant having an organic acid group that reacts with the π-conjugated polymer to exhibit conductivity, resin A, and water, and the blending ratio of the water is 30 to 60% by mass.

[0013] <Carbon Fiber> The carbon fiber contained in the slurry composition of the present invention means a fibrous material mainly composed of carbon.

[0014] Examples of the carbon fiber include single-walled carbon nanotubes, multi-walled carbon nanotubes, vapor-grown carbon fibers, and carbon nanofibers.

[0015] Here, the single-walled carbon nanotube is a fibrous material mainly composed of carbon, having a pipe shape, a cross-sectional diameter (outer diameter) of 0.5 to 5 nm, preferably 1 to 4 nm, and a length of 1 to 30 μm, preferably 3 to 8 μm. The aspect ratio (length / cross-sectional diameter) of the single-walled carbon nanotube is preferably 500 to 5000, more preferably 2000 to 3000.

[0016] Furthermore, multi-walled carbon nanotubes are fibrous structures mainly composed of carbon, shaped like pipes, with a cross-sectional diameter (outer diameter) of 6 to 100 nm, preferably 8 to 30 nm, and a length of 1 to 30 μm, preferably 3 to 15 μm. The aspect ratio (length / cross-sectional diameter) of the multi-walled carbon nanotube is preferably 50 to 350, and more preferably 100 to 200.

[0017] Furthermore, gas-phase carbon fiber refers to fibrous graphite synthesized using the gas-phase method. The gas-phase carbon fibers preferably have a cross-sectional diameter (outer diameter) of 50 to 500 nm, and more preferably 100 to 200 nm. Furthermore, the length is preferably 1 to 30 μm, and more preferably 3 to 10 μm. The aspect ratio (length / cross-sectional diameter) of the gas-phase carbon fiber is preferably 10 to 100, and more preferably 20 to 60.

[0018] Furthermore, carbon nanofibers are fibrous materials mainly composed of carbon, with a cross-sectional diameter (outer diameter) of 100 to 1000 nm, preferably 300 to 700 nm, and a length of 1 to 50 μm, preferably 5 to 15 μm. The aspect ratio (length / cross-sectional diameter) of the carbon nanofiber is preferably 5 to 100, and more preferably 5 to 30.

[0019] The slurry composition of the present invention is made by blending carbon fibers as described above. The blending ratio of carbon fibers in the total blend is preferably 0.5 to 35% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 10% by mass. The slurry composition of the present invention, in which the carbon fiber content is within this range, exhibits excellent granulation properties.

[0020] <π-conjugated polymer> The π-conjugated polymer contained in the slurry composition of the present invention exhibits conductivity by doping it with a dopant having an organic acid group, which reacts with the π-conjugated polymer to exhibit conductivity, as described later.

[0021] Examples of π-conjugated polymers included in the slurry composition of the present invention include polythiophene, polyselenophene, polyparaphenylene, polyparaphenylenevinylene, polythiophenevinylene, polyaniline, polypyrrole, poly3,4-ethylenedioxythiophene, poly3-methoxythiophene, poly3,4-dimethoxythiophene, poly3-hexylthiophene, poly3-methylpyrrole, poly3-methylthiophene, poly-o-toluidine, poly-o-anisidine, poly-o-ethylaniline, and polysec-butylaniline.

[0022] The π-conjugated polymer contained in the slurry composition of the present invention is of the non-self-doped type. The non-self-doped π-conjugated polymer is preferably a π-conjugated polymer that substantially lacks ionic groups (such as anionic groups like sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, phosphinic acid groups, or salts thereof). Here, a π-conjugated polymer substantially lacking ionic groups refers to a π-conjugated polymer in which the content of repeating units having ionic groups is 0 to 10 mol% (preferably 0 to 5 mol%, more preferably 0 to 1 mol%, and even more preferably 0 mol% or more and less than 0.1 mol%) relative to the total number of repeating units.

[0023] The number-average molecular weight of the π-conjugated polymer is preferably between 10,000 and 300,000. This number-average molecular weight is a value measured by GPC using a solvent that makes the π-conjugated polymer skeleton soluble after the doping component has been removed, and is a reference value that includes the decomposition of the π-conjugated polymer at the doping removal process (such as alkali treatment or electrolysis).

[0024] The slurry composition of the present invention is made by blending the above-described π-conjugated polymer. The blending ratio of the π-conjugated polymer in the total blend is preferably 1 to 35% by mass, more preferably 4 to 20% by mass, and even more preferably 7 to 11% by mass. The slurry composition of the present invention, in which the blending ratio of π-conjugated polymers is within this range, exhibits excellent granulation properties.

[0025] <Dopant> The dopant contained in the slurry composition of the present invention reacts with the π-conjugated polymer to exhibit conductivity and has an organic acid group. The dopant having an organic acid group that reacts with the π-conjugated polymer to exhibit conductivity, as contained in the slurry composition of the present invention, will hereinafter also be referred to as "dopant Y".

[0026] Dopant Y may be a low molecular weight (e.g., a molecule with a molecular weight of 1500 or less) or a high molecular weight (e.g., a molecule with a molecular weight of over 1500), but it is preferable that it be a low molecular weight.

[0027] Examples of dopant Y include organic carboxylic acids. These can be aliphatic, aromatic, or cyclic aliphatic compounds containing one or more carboxyl groups. Examples include formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, and triphenylacetic acid.

[0028] Furthermore, organic sulfonic acids can be cited as dopant Y. Specifically, these include alkyl-substituted organic sulfonic acid ions (methanesulfonic acid and dodecylsulfonic acid, etc.), cyclic sulfonic acid ions (camphorsulfonic acid ions, etc.), alkyl-substituted or unsubstituted benzene mono or disulfonic acid ions (benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and benzenedisulfonic acid, etc.), and alkyl-substituted or unsubstituted ions of naphthalenesulfonic acid having 1 to 4 sulfonic acid groups (2-naphthalenesulfonic acid and 1,7-naphthol). Examples include tarlendisulfonic acid, anthracene sulfonate ions, anthraquinone sulfonate ions, alkyl-substituted or unsubstituted biphenyl sulfonate ions (alkylbiphenyl sulfonate and biphenyl disulfonic acid, etc.), substituted or unsubstituted aromatic polymer sulfonate ions (polystyrene sulfonate and naphthalene sulfonate formalin condensate, etc.), sulfosuccinate esters (polyoxyethylene alkyl sulfosuccinate and di-2-ethylhexyl sulfosuccinate, etc.), etc.

[0029] The slurry composition of the present invention is made by incorporating the dopant Y described above. The proportion of dopant Y in the total composition is preferably 3 to 40% by mass, more preferably 8 to 25% by mass, and even more preferably 2 to 18% by mass. The slurry composition of the present invention, in which the dopant Y content is within this range, exhibits excellent granulation properties.

[0030] It is preferable that dopant Y and the aforementioned π-conjugated polymer form an ionic bond. For example, if dopant Y is dodecylbenzenesulfonic acid and the π-conjugated polymer is polyaniline, they are considered to form an ionic bond. When dopant Y reacts with a π-conjugated polymer, reaction products are generated. These reaction products are electrically conductive.

[0031] It is preferable to calculate the amount of dopant Y and π-conjugated polymer that will react without excess or deficiency based on the number of reactive groups in each, and then determine the ratio of their blending rates based on that amount. For example, when dopant Y is dodecylbenzenesulfonic acid and the π-conjugated polymer is polyaniline, the mass ratio of the blending ratio of dopant Y to the π-conjugated polymer is preferably 5:2 to 5:4, more preferably 5:2.5 to 5:3.5, and even more preferably 5:3. However, it is believed that in the slurry composition of the present invention, not all of the dopant Y and the π-conjugated polymer have reacted, but rather that they are in an equilibrium state where only a portion have reacted (or an intermediate state leading to equilibrium). In other words, the slurry composition of the present invention is thought to contain not only the reaction product of dopant Y and π-conjugated polymer, but also dopant Y alone and / or π-conjugated polymer alone.

[0032] <Resin A> The resin A contained in the slurry composition of the present invention may be a thermosetting resin (such as a particulate phenolic resin before curing), but it is preferably a thermoplastic resin. Resin A is a resin that does not fall under the category of a π-conjugated polymer, nor a reaction product formed by the reaction of dopant Y with a π-conjugated polymer.

[0033] It is also preferable that resin A substantially lacks ionic groups (anionic groups such as sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, phosphinic acid groups, or salts thereof). Here, resin A substantially lacking ionic groups means resin A in which the content of ionic groups is 0 to 5 mol% (preferably 0 to 0.5 mol%, more preferably 0 mol% or more and less than 0.1 mol%, and even more preferably 0 mol% or more and less than 0.05 mol%) relative to the total number of repeating units.

[0034] Examples of thermoplastic resins that can be used as resin A include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluoroethylene, styrene-butadiene-acrylonitrile resin (ABS resin), acrylonitrile-styrene resin (AS resin), acrylic resins such as polymethyl methacrylate (PMMA), polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polylactic acid, polycaprolactone, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyesters such as glass fiber reinforced polyethylene terephthalate and polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, amorphous polyarylate, liquid crystal polymer, polyetheretherketone, polyimide, polyamideimide, polylactic acid, cellulose derivatives such as cellulose esters, and copolymers thereof.

[0035] Resin A may contain two or more types of thermoplastic resins.

[0036] It is preferable that resin A has a melting point lower than the thermal decomposition temperature of the aforementioned π-conjugated polymer. For example, if the π-conjugated polymer is polyaniline, the thermal decomposition temperature of polyaniline is approximately 250°C, so it is preferable that resin A has a melting point of 250°C or lower. The thermal decomposition temperature referred to here is the temperature determined by JIS K7120.

[0037] Resin A is preferably in granular form. Furthermore, the particle size is preferably 1 to 1000 μm, and more preferably 5 to 800 μm. The average particle size of the particles is preferably 5 to 800 μm, and more preferably 5 to 700 μm. Here, the average particle size of resin A is defined as the D50 value in the volume-based cumulative particle size distribution obtained by laser diffraction / scattering particle size measurement.

[0038] The slurry composition of the present invention is made by blending resin A as described above. The blending ratio of resin A in the total composition is preferably 5 to 55% by mass, more preferably 15 to 40% by mass, and even more preferably 20 to 35% by mass. The slurry composition of the present invention, in which the blending ratio of resin A is within this range, exhibits excellent granulation properties.

[0039] <Water> The slurry composition of the present invention contains water. The proportion of water in the slurry composition of the present invention is 30 to 60% by mass, preferably 32 to 55% by mass, and more preferably 34 to 50% by mass. The slurry composition of the present invention, having a water content within this range, exhibits excellent granulation properties.

[0040] <Other> The slurry composition of the present invention is obtained by blending carbon fibers, a π-conjugated polymer, dopant Y, resin A, and water, as described above. The slurry composition of the present invention may also contain organic solvents, ionic liquids, and the like as other components.

[0041] The slurry composition of the present invention preferably contains polyphenols as other components. In this case, carbon fibers tend to re-aggregate less easily, and as a result, the dispersibility of the slurry composition of the present invention tends to be higher.

[0042] In the slurry composition of the present invention, the content of the organic solvent, ionic liquid, and polyphenol is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, independently of the total mass of the slurry composition. There is no lower limit to the above content, for example, each can be 0% by mass or more independently. The total content of other components in the slurry composition of the present invention is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on the total mass of the slurry composition. There is no lower limit to the above content, for example, 0% by mass or more. The slurry composition of the present invention may also preferably contain organic solvents and ionic liquids.

[0043] The slurry composition of the present invention exhibits high dispersibility, with each component being well dispersed. Although the reason for this is not entirely clear, the inventors hypothesize that some or all of the reaction products between dopant Y and the π-conjugated polymer dissolve in water, coating the carbon fibers and making them less prone to re-aggregation. They also hypothesize that dopant Y alone acts as a dispersant for the carbon fibers, contributing to the dispersion and prevention of re-aggregation of the carbon fibers.

[0044] [Conductive composition of the present invention] The conductive composition of the present invention will be described below. The conductive composition of the present invention comprises carbon fibers, a reaction product of a π-conjugated polymer and a dopant having an organic acid group that reacts with it to exhibit conductivity, and a resin X.

[0045] <Carbon fiber> The conductive composition of the present invention contains the same carbon fibers as those contained in the slurry composition of the present invention described above.

[0046] The carbon fiber content in the conductive composition of the present invention is, for example, 0.1 to 37% by mass, preferably 0.1 to 5.0% by mass, more preferably 0.15 to 4.0% by mass, and even more preferably 0.2 to 3.0% by mass. From the conductive composition of the present invention, in which the carbon fiber content is within this range, a molded article with superior conductivity and higher strength can be obtained.

[0047] The carbon fiber content is defined as the value obtained by the direct ashing method (JIS K7250).

[0048] <Reaction product of a π-conjugated polymer and a dopant having an organic acid group that reacts with it to exhibit conductivity> The conductive composition of the present invention comprises a reaction product of a π-conjugated polymer and a dopant (dopant Y) having an organic acid group that reacts with it to exhibit conductivity. Such a reaction product will also be referred to as "reaction product Z" below. Here, each of the π-conjugated polymer and dopant Y may be the same as the π-conjugated polymer and dopant Y contained in the slurry composition of the present invention described above.

[0049] A π-conjugated polymer and dopant Y form a chemical bond. For example, if dopant Y is dodecylbenzenesulfonic acid and the π-conjugated polymer is polyaniline, they are thought to form an ionic bond. However, within the conductive composition of the present invention, it is considered that not all of the π-conjugated polymer and dopant Y have reacted, but rather that only a portion have reacted, resulting in an equilibrium state (or a state in the process of reaching equilibrium). Therefore, the conductive composition of the present invention is considered to contain, in addition to the reaction product Z, a single dopant Y and / or a single π-conjugated polymer.

[0050] The content of the reaction product Z in the conductive composition of the present invention is, for example, 0.4 to 30% by mass, preferably 0.5 to 16.0% by mass, more preferably 1.0 to 12.0% by mass, and even more preferably 2.0 to 9.0% by mass. From the conductive composition of the present invention, in which the content of reaction product Z is within this range, a molded article with superior conductivity and higher strength can be obtained.

[0051] The content of reaction product Z can be determined by separating the other components from the conductive composition of the present invention, excluding reaction product Z, and determining the content of each component. Content of reaction product Z = (conductive composition of the present invention - other components) / conductive composition of the present invention

[0052] The content of the π-conjugated polymer in the conductive composition of the present invention is, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 6% by mass or less, and even more preferably 3% by mass or less. There is no lower limit to the above content, for example, 0% by mass or more. From the conductive composition of the present invention, in which the content of π-conjugated polymers is within this range, a molded article with superior conductivity and higher strength can be obtained.

[0053] The content of the π-conjugated polymer refers to the value obtained by measuring the conductive composition of the present invention by Soxhlet extraction after pulverization. Here, it is preferable that the solvent used in the Soxhlet extraction does not dissolve resin X. If resin X is soluble in the solvent, resin X is removed beforehand by recrystallization. Specifically, if the π-conjugated polymer is polyaniline, the π-conjugated polymer can be extracted using Soxhlet extraction with N-methylpyrrolidone as the solvent. After removing the solvent using a known drying method, the content can be determined by measuring the mass. Furthermore, if the conductive composition contains dopant Y, a process to remove dopant Y from the pulverized conductive composition is performed before carrying out the Soxhlet extraction method. For example, a method to remove dopant Y from the conductive composition may involve using water or alcohol as a solvent and employing the Soxhlet extraction method to extract and remove dopant Y from the conductive composition.

[0054] The content of dopant Y in the conductive composition of the present invention is, for example, 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. There is no lower limit to the above content, for example, 0% by mass or more. From the conductive composition of the present invention, in which the dopant Y content is within this range, a molded article with superior conductivity and higher strength can be obtained.

[0055] The dopant Y content is defined as the value obtained by Soxhlet extraction. Specifically, the dopant Y can be extracted using Soxhlet extraction with water or alcohol as a solvent, and after removing the water using a known drying method, the content can be determined by measuring the mass.

[0056] In the conductive composition of the present invention, the total content of reaction product Z, dopant Y (dopant Y alone), and π-conjugated polymer (π-conjugated polymer alone) is, for example, 0.4 to 30% by mass, preferably 0.5 to 16.0% by mass, more preferably 1.0 to 12.0% by mass, and even more preferably 2.0 to 9.0% by mass. From the conductive composition of the present invention having a reaction product Z content within this range, a molded article with superior conductivity and higher strength can be obtained.

[0057] <Resin X> The conductive composition of the present invention comprises resin X. Resin X is a resin that does not fall under the category of reaction product Z or π-conjugated polymer. Resin X may be a thermosetting resin (such as particulate phenolic resin before curing), but it is preferably a thermoplastic resin. Resin X may be the same thermoplastic resin as resin A contained in the slurry composition of the present invention described above.

[0058] Resin X may contain two or more types of thermoplastic resins. However, it is preferable that resin X is a single type of thermoplastic resin.

[0059] The content of resin X in the conductive composition of the present invention is, for example, 35 to 99.5% by mass, preferably 60 to 99% by mass, more preferably 70 to 97% by mass, and even more preferably 80 to 95% by mass. From the conductive composition of the present invention, in which the content of resin X is within this range, a molded article with superior conductivity and higher strength can be obtained.

[0060] The content of resin X is defined as the value obtained by the dissolution-reprecipitation method. Specifically, a solvent that can act as a good solvent is directly mixed with the resin X contained in the conductive composition of the present invention. After recovering the solution by filtering out the insoluble portion using a filter, the resin X precipitates when the solution and a solvent that can act as a poor solvent for the resin X are directly mixed. After filtering out the precipitated resin X using a filter, the resin X content can be obtained by drying it using a known drying method and then measuring its mass.

[0061] The mass ratio of the aforementioned carbon fiber to resin X is preferably 1:1 to 1000, more preferably 1:5 to 750, even more preferably 1:30 to 500, and particularly preferably 1:50 to 400. In this case, the conductive composition of the present invention can be obtained, which provides a molded article with excellent conductivity and high strength.

[0062] <Solvent> The conductive composition of the present invention may contain a solvent such as water or an organic solvent, but the content of the solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. There is no lower limit to the above content, for example, it may be 0% by mass or more.

[0063] The solvent content is defined as the value obtained by measuring the loss on drying (Test method for loss on drying and residue of chemical products, JIS K0067).

[0064] <Other> The conductive composition of the present invention comprises carbon fibers, a reaction product Z, and a resin X, as described above. The conductive composition of the present invention may contain other components, which may include, for example, the same components as those that may be included in the slurry composition of the present invention (ionic liquids, polyphenols, etc.). In the conductive composition of the present invention, the content of the ionic liquid and the polyphenol is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, independently of the total mass of the conductive composition. There is no lower limit to the above content; for example, each can be 0% by mass or more independently. The total content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. There is no lower limit to the above content, for example, 0% by mass or more. The content of these other components is determined by extraction and separation using a solvent that dissolves the relevant substance.

[0065] [Molded body of the present invention] The molded article of the present invention will be described below. The molded article of the present invention is a molded article comprising carbon fibers, a reaction product of a π-conjugated polymer and a dopant having an organic acid group that reacts with it to exhibit conductivity, and a resin X.

[0066] The molded article of the present invention can be obtained, for example, by placing the conductive composition of the present invention into a mold and heating it.

[0067] <Carbon fiber> The molded article of the present invention contains the same carbon fibers as those contained in the slurry composition and conductive composition of the present invention described above.

[0068] The carbon fiber content in the molded article of the present invention is, for example, 0.1 to 37% by mass, preferably 0.1 to 5.0% by mass, more preferably 0.15 to 4.0% by mass, and even more preferably 0.2 to 3.0% by mass. The molded articles of the present invention, having a carbon fiber content within this range, exhibit superior conductivity and higher strength.

[0069] The carbon fiber content is defined as the value obtained by the direct ashing method (JIS K7250).

[0070] <Reaction product of a π-conjugated polymer and a dopant having an organic acid group that reacts with it to exhibit conductivity> The molded article of the present invention comprises a π-conjugated polymer, a dopant (dopant Y) having an organic acid group that reacts with it to exhibit conductivity, and a reaction product (reaction product Z). Here, each of the π-conjugated polymer and dopant Y may be the same as the π-conjugated polymer and dopant Y contained in the slurry composition of the present invention described above.

[0071] A π-conjugated polymer and dopant Y form a chemical bond. For example, if dopant Y is dodecylbenzenesulfonic acid and the π-conjugated polymer is polyaniline, they are thought to form an ionic bond. However, within the molded body of the present invention, it is thought that not all of the π-conjugated polymer and dopant Y have reacted, but rather that only a portion have reacted, resulting in an equilibrium state (or a state in the process of reaching equilibrium). Therefore, the molded article of the present invention is considered to contain, in addition to the reaction product Z, a single dopant Y and / or a single π-conjugated polymer.

[0072] The content of reaction product Z in the molded article of the present invention is, for example, 0.4 to 30% by mass, preferably 0.5 to 16.0% by mass, more preferably 1.0 to 12.0% by mass, and even more preferably 2.0 to 9.0% by mass. The molded article of the present invention, having a reaction product Z content within this range, exhibits superior conductivity and higher strength.

[0073] The content of reaction product Z can be determined by separating the other components from the molded article of the present invention, excluding reaction product Z, and determining the content of each component. Content of reaction product Z = (Molded body of the present invention - other components) / Molded body of the present invention

[0074] The content of the π-conjugated polymer in the molded article of the present invention is, for example, 15% by mass or less, may be 10% by mass or less, preferably 6% by mass or less, more preferably 3% by mass or less, even more preferably 1.0% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less. There is no lower limit to the above content, for example, 0% by mass or more. The molded articles of the present invention, having a π-conjugated polymer content within this range, exhibit superior conductivity and higher strength.

[0075] The content of the π-conjugated polymer refers to the value obtained by measuring the Soxhlet extraction method after crushing the molded article of the present invention. Here, it is preferable that the solvent used in the Soxhlet extraction method does not dissolve resin X. If resin X is soluble in the solvent, resin X is removed beforehand by recrystallization. Specifically, if the π-conjugated polymer is polyaniline, the π-conjugated polymer can be extracted using Soxhlet extraction with N-methylpyrrolidone as the solvent. After removing the solvent using a known drying method, the content can be determined by measuring the mass. Furthermore, if the molded product contains dopant Y, a process to remove dopant Y from the pulverized molded product is performed before carrying out the Soxhlet extraction method. One example of a process to remove dopant Y from the molded product is to use water or alcohol as a solvent and extract and remove dopant Y from the molded product using the Soxhlet extraction method.

[0076] The dopant Y content in the molded article of the present invention is, for example, 20% by mass or less, may be 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1.0% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less. There is no lower limit to the above content, for example, 0% by mass or more. The molded article of the present invention, having a dopant Y content within this range, exhibits superior conductivity and higher strength.

[0077] The dopant Y content is defined as the value obtained by Soxhlet extraction. Specifically, the dopant Y can be extracted using Soxhlet extraction with water or alcohol as a solvent, and after removing the water using a known drying method, the content can be determined by measuring the mass.

[0078] In the molded article of the present invention, the total content of reaction product Z, dopant Y (dopant Y alone), and π-conjugated polymer (π-conjugated polymer alone) is, for example, 0.4 to 30% by mass, preferably 0.5 to 16.0% by mass, more preferably 1.0 to 12.0% by mass, and even more preferably 2.0 to 9.0% by mass. The molded article of the present invention having a reaction product Z content within this range exhibits superior conductivity and higher strength.

[0079] <Resin X> The molded article of the present invention contains resin X. Resin X is a resin that does not fall under the category of reaction product Z or π-conjugated polymer. Resin X may be a thermosetting resin (such as particulate phenolic resin before curing), but it is preferably a thermoplastic resin. Resin X may be the same thermoplastic resin as resin A contained in the slurry composition of the present invention described above.

[0080] Resin X may contain two or more types of thermoplastic resins. However, it is preferable that resin X is a single type of thermoplastic resin.

[0081] The resin X content in the molded article of the present invention is, for example, 35 to 99.5% by mass, preferably 60 to 99% by mass, more preferably 70 to 97% by mass, and even more preferably 80 to 95% by mass. The molded article of the present invention, having a resin X content within this range, exhibits superior conductivity and higher strength.

[0082] The content of resin X is defined as the value obtained by the dissolution-reprecipitation method. Specifically, a solvent that can act as a good solvent for the resin X contained in the molded article of the present invention is directly mixed, and after the insoluble portion is filtered out using a filter and the solution is recovered, the resin X is precipitated by directly mixing the solution with a solvent that can act as a poor solvent for the resin X. After filtering out the precipitated resin X using a filter, the resin X content can be obtained by drying it using a known drying method and then measuring its mass.

[0083] The mass ratio of the aforementioned carbon fiber to resin X is preferably 1:1 to 1000, more preferably 1:5 to 750, even more preferably 1:30 to 500, and particularly preferably 1:50 to 400. In this case, the molded article of the present invention has superior conductivity and high strength.

[0084] <Solvent> The molded article of the present invention may contain a solvent such as water or an organic solvent, but the content of the solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. There is no lower limit to the above content, for example, it may be 0% by mass or more.

[0085] The solvent content is defined as the value obtained by measuring the loss on drying (Test method for loss on drying and residue of chemical products, JIS K0067).

[0086] <Other> The molded article of the present invention comprises carbon fibers, a reaction product Z, and a resin X, as described above. The molded article of the present invention may contain other components, which may include, for example, the same components as those that may be included in the slurry composition of the present invention (ionic liquids, polyphenols, etc.). In the molded article of the present invention, the content of the ionic liquid and the polyphenol is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, independently of the total mass of the conductive composition. There is no lower limit to the above content; for example, they may be 0% by mass or more, independently of each other. The total content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. There is no lower limit to the above content, for example, 0% by mass or more.

[0087] [Method for producing the conductive composition of the present invention] The method for producing the conductive composition of the present invention will be described below. The present invention provides a method for producing a conductive composition, comprising: a stirring step of stirring a mixture of carbon fibers, a π-conjugated polymer, a dopant having an organic acid group that reacts with the π-conjugated polymer to exhibit conductivity, granular resin A, and water to obtain a slurry composition of the present invention; and a mixing step of mixing the slurry composition with resin B, thereby obtaining the conductive composition of the present invention.

[0088] <Agitation process> The stirring step included in the method for producing the conductive composition of the present invention will be described. The conductive composition of the present invention is prepared using the same carbon fibers, π-conjugated polymer, dopant Y, and resin A as those contained in the slurry composition of the present invention described above. These are then placed together with water into a stirring container (preferably one attached to a stirring device; the same method is preferred for stirring hereafter). The blending ratio of each component is preferably the same as the blending ratio of each component in the slurry composition of the present invention. Then, the mixture is stirred to obtain the slurry composition of the present invention. In this case, stirring is preferably rotational stirring.

[0089] Rotational and revolutionary stirring is a method of stirring in which a container holding the materials is tilted and rotated and revolutionized at high speed (similar to the movement of planets around the sun, planetary motion, or celestial motion), and the materials are mixed by the convection and shear stress caused by the centrifugal force generated. Conventional, known agitators can be used as the rotating and revolving agitators. These agitators are sometimes also called rotating and revolving mixers, planetary agitators, or agitators and defoamers.

[0090] The inventors have discovered that this type of rotational and orbital stirring can suppress the heat generation of the material while simultaneously improving the dispersibility of each component in a short time. For example, the inventors have found that when the material is subjected to stirring using a homogenizer (such as an ultrasonic homogenizer or a high-pressure homogenizer), a ball mill, a media-less homomixer, or a disperser, the material may be altered due to heat generation, damaged due to high load, or re-aggregation may occur after drying.

[0091] <Mixing process> The mixing step included in the method for producing the conductive composition of the present invention will be described. In the mixing step, the slurry composition of the present invention obtained by the stirring step is mixed with resin B to obtain the conductive composition of the present invention.

[0092] For example, the conductive composition of the present invention can be obtained by drying the slurry composition to make a powder, then putting it into a twin-screw kneader together with resin B and mixing thoroughly.

[0093] In the mixing step, it is preferable to granulate the slurry composition of the present invention obtained by the stirring step to obtain granules, and then mix the granules with resin B. Because it uses granulated material mixed with resin B, rather than powdered material, it offers excellent workability. Furthermore, it helps to minimize contamination in factories and other industrial settings.

[0094] For example, granules (such as cylindrical granules) can be obtained by loading the slurry composition of the present invention into an extruder and extruding it under appropriate conditions. Here, it is preferable to adjust the moisture content of the slurry composition of the present invention to 30 to 60% by mass before loading it into the extruder.

[0095] Alternatively, for example, the slurry composition of the present invention may be dried to form a powder, water may be added to achieve a moisture content of 15 to 35% by mass, and then the mixture may be fed into an extruder and extruded under appropriate conditions to obtain granules (such as cylindrical granules).

[0096] To obtain granules, it is preferable to apply an extrusion granulation method using an extrusion granulator. Other methods such as agitation granulation, fluidized bed granulation, and tumbling granulation can also be applied.

[0097] It is preferable to dry the slurry composition before mixing it with resin B. Similarly, if granules are obtained from the slurry composition, it is preferable to dry the granules before mixing them with resin B. The slurry composition is dried, and it is preferable that the moisture content of the slurry composition be 0.5% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less. There is no lower limit to the above moisture content; for example, it can be 0% by mass or more.

[0098] The method for drying the slurry composition (and the granules obtained therefrom) is not particularly limited. For example, the granules can be dried by applying hot air, such as in a hot air dryer or a fluidized bed dryer. In addition, the granules can be dried by other known general drying methods.

[0099] Resin B may be a thermosetting resin (such as particulate phenolic resin before curing), but it is preferably a thermoplastic resin. It is preferable that resin B is the same type of thermoplastic resin as resin A contained in the slurry composition of the present invention described above.

[0100] Resin B may contain two or more types of thermoplastic resins.

[0101] A mixture of resin B and the aforementioned resin A becomes the aforementioned resin X.

[0102] The method for mixing the granules and resin B is not particularly limited. For example, the granules and resin B can be mixed using conventionally known twin-screw kneaders, kneader kneaders, or open-roll kneaders. The mixing temperature depends on the types of resin A, resin B, reaction product Z, and π-conjugated polymer, but it is preferable to use a temperature that is above the melting point of resin A and / or resin B, and below the thermal decomposition temperature of reaction product Z and / or π-conjugated polymer. As for the specific mixing temperature, for example, 100 to 240°C is preferred, and 120 to 220°C is more preferred.

[0103] By this method of producing the conductive composition of the present invention, it is possible to obtain a conductive composition of the present invention that has excellent conductivity and high strength in a molded article.

[0104] The above describes a preferred embodiment of the method for manufacturing the conductive composition. On the other hand, the conductive composition of the present invention may be, for example, obtained by drying the slurry composition (and granules obtained therefrom) of the present invention. The method for manufacturing the slurry composition (and its granules) and the method for drying the slurry composition (and granules obtained therefrom) are as described above. Alternatively, the conductive composition may be obtained by heating and mixing the slurry composition (preferably its dried form) without adding resin B. Examples of equipment used for heating and mixing include conventionally known twin-screw kneaders, kneader kneaders, and open-roll kneaders. The mixing temperature during heating and mixing depends on the types of resin A, reaction product Z, and π-conjugated polymer, but is preferably, for example, above the melting point of resin A and below the thermal decomposition temperature of reaction product Z and / or π-conjugated polymer. The specific mixing temperature during heating is preferably 100 to 240°C, and more preferably 120 to 220°C.

[0105] <Method for manufacturing the molded article of the present invention> The method for manufacturing the molded article of the present invention will be described below. The present invention provides a method for manufacturing a molded article, comprising a molding step of molding the conductive composition of the present invention to obtain the molded article of the present invention.

[0106] The method for manufacturing a molded article of the present invention may be, for example, a method comprising a molding step following a stirring step and a mixing step in the method for manufacturing a conductive composition of the present invention.

[0107] In the molding process, if the resin X is thermosetting, the molded article of the present invention can be obtained by, for example, placing the conductive composition of the present invention into a mold and heating and compressing it.

[0108] When the resin X contained in the conductive composition of the present invention is thermoplastic, a molded article can be obtained by molding methods such as injection molding, extrusion molding, or blow molding. [Examples]

[0109] The present invention will be described with reference to examples. The present invention is not limited to the embodiments described below.

[0110] <Example 1> (Agitation process) The following were prepared as carbon fibers, a π-conjugated polymer, a dopant (dopant Y) having an organic acid group that reacts with the π-conjugated polymer to exhibit conductivity, and resin A.

[0111] • Carbon fiber: Single-walled carbon nanotube (OCSiAl, Tuball93), cross-sectional diameter 2nm, aspect ratio 2500 • π-conjugated polymer: Polyaniline (Regulus, PANI-PA), particle size 1-20 μm • Dopant Y: Dodecylbenzenesulfonic acid (soft type) (manufactured by Tokyo Chemical Industry Co., Ltd., D0989) • Resin A: Granular polypropylene (particle size 5-20 μm)

[0112] Next, carbon fibers, π-conjugated polymer, dopant Y, and resin A were added to a stirring vessel along with water, and the mixture was stirred by rotation and revolution. Here, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was set to 1:3:5:10 (by mass). Water was added so that the mass ratio of the total mass of these components to water was 19:15. In this case, the water content is 44.1% by mass. Furthermore, for rotational and orbital stirring, a rotational and orbital stirring machine (AR-100, Awatori Rentaro, manufactured by Shinky Co., Ltd.) was used, and the mixture was stirred for 20 minutes at an orbital speed of 2000 rpm.

[0113] As a result, a slurry composition with shape retention properties at rest was obtained. The slurry composition obtained here will be referred to as "Slurry (1)". The slurry composition obtained here corresponds to the slurry composition of the present invention.

[0114] The slurry (1) was dried in a hot air dryer and then observed at 30,000x magnification using a scanning electron microscope. The resulting electron microscope image (SEM image) is shown in Figure 1. From Figure 1, it can be said that the carbon fibers are well dispersed, indicating high dispersibility.

[0115] (Mixing process) Next, the slurry (1) was loaded into an extrusion granulator (Dalton, Basket Granulator BR-200) and processed under conditions suitable for the slurry material, resulting in the acquisition of granulated material (cylindrical granules). This confirmed that slurry (1) has high granulation properties. Afterward, the granules were dried with hot air until they were completely dry. The granules retained their shape after drying. The granules obtained here will be referred to as "granules (1)".

[0116] (Mixing process) Polypropylene resin was prepared as resin B. Then, the granules (1) and resin B were loaded into a twin-screw kneader with a mass ratio of 5:95, and the mixture was melt-kneaded under conditions suitable for resin B to obtain a mixture. The temperature during melt-kneading was 190°C. The mixture obtained here corresponds to the conductive composition of the present invention.

[0117] (molding process) Subsequently, the obtained mixture was subjected to hot press molding using a hot press molding machine (MP-2F, manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a molded body measuring 50 mm x 50 mm and 1 mm thick. The molded body obtained here will be referred to as "test piece (1)". Furthermore, the molded article obtained here corresponds to the molded article of the present invention.

[0118] Then, the resistance of test piece (1) was measured using the four-probe method (based on JIS K7194) with a low resistivity meter (Loresta-GX MCP-T700) manufactured by Nitto Seiko Analytech Co., Ltd. As a result, the resistivity of test piece (1) was 1000 Ω·m.

[0119] Test piece (1) was observed at 5,000x magnification using an optical microscope. The resulting electron microscope image is shown in Figure 2. From Figure 2, it was confirmed that the carbon fibers and reaction product Z were dispersed without aggregation.

[0120] Furthermore, for test piece (1), the tensile modulus (MPa) (based on JIS K7161), tensile strength (MPa) (based on JIS K7161), tensile elongation (%) (based on JIS K7161), flexural modulus (MPa) (based on JIS K7171), flexural strength (MPa) (based on JIS K7171), and Izod impact value (KJ / m) were measured. 2 The following measurements were taken (based on JIS K7160). The results are shown in Table 1. Table 1 also shows the measurement results obtained by performing the same measurements on a molded body of the same shape (referred to as "Test Piece (0)"), which was created using only the polypropylene used as resin B and the same method.

[0121] [Table 1]

[0122] As shown in Table 1, compared to test piece (0), test piece (1) has the following properties: tensile modulus (MPa), tensile strength (MPa), flexural modulus (MPa), flexural strength (MPa), and Izod impact value (KJ / m). 2 ) increased.

[0123] <Example 2> In Example 1, the granules (1) and resin B were mixed in a mass ratio of 5:95 during the mixing process. In Example 2, however, the granules were loaded into a twin-screw kneader in a mass ratio of 10:90 and mixed to obtain the mixture. Otherwise, the same procedure as in Example 1 was performed to obtain the same test piece (test piece (2)) and subject it to the same test. As a result, the resistivity of test piece (2) was 15 Ω·m. Furthermore, in the same manner as with test piece (1) in Example 1, test piece (2) was subjected to the same measurements as test piece (0): tensile modulus (MPa), tensile strength (MPa), flexural modulus (MPa), flexural strength (MPa), and Izod impact value (KJ / m). 2 ) increased.

[0124] <Example 3> In Example 1, the granules (1) and resin B were mixed in a mass ratio of 5:95 during the mixing process. However, in Example 3, the mixture was loaded into a twin-screw kneader with a mass ratio of 20:80 and mixed to obtain the mixture. Otherwise, the same procedure as in Example 1 was performed to obtain the same test piece (test piece (3)) and subject it to the same test. As a result, the resistivity of test piece (3) was 0.2 Ω·m. Furthermore, test piece (3) was subjected to the same tensile modulus (MPa), tensile strength (MPa), flexural modulus (MPa), flexural strength (MPa), and Izod impact value (KJ / m) relative to test piece (0), as in the case of test piece (1) in Example 1. 2 ) increased.

[0125] <Example 4> In Example 3, granular polypropylene (particle size 5-20 μm) was used as resin A, but in Example 4, granular polypropylene with a particle size of 100-1000 μm and an average particle diameter of 600 μm was used as resin A. Otherwise, the same procedure as in Example 3 was followed to obtain the same test piece (test piece (4)) and subject it to the same test. As a result, the resistivity of test piece (4) was 0.2 Ω·m. Furthermore, test piece (4) was subjected to the same tensile modulus (MPa), tensile strength (MPa), flexural modulus (MPa), flexural strength (MPa), and Izod impact value (KJ / m) relative to test piece (0), as in the case of test piece (1) in Example 1. 2 ) increased.

[0126] <Example 5> In Example 3, granular polypropylene (particle size 5-20 μm) was used as resin A, while in Example 5, granular polyethylene with a particle size of 100-1000 μm and an average particle diameter of 500 μm was used as resin A. Furthermore, while polypropylene was used as resin B in Example 3, polyethylene was used as resin B in Example 5. The temperature during melt-mixing of the granules and resin B in a twin-screw kneader was 120°C. Otherwise, the same procedure as in Example 3 was performed to obtain the same test piece (test piece (5)) and subject it to the same test. As a result, the resistivity of test piece (5) was 0.1 Ω·m. Furthermore, test piece (5) was subjected to the same tensile modulus (MPa), tensile strength (MPa), flexural modulus (MPa), flexural strength (MPa), and Izod impact value (KJ / m) relative to test piece (0), as in the case of test piece (1) in Example 1. 2 ) increased.

[0127] <Example 6> In Example 3, granular polypropylene (particle size 5-20 μm) was used as resin A, while in Example 5, granular polylactic acid (TE-2000, manufactured by Unitika Corporation) with a particle size of 100-1000 μm and an average particle diameter of 650 μm was used as resin A. Furthermore, while polypropylene was used as resin B in Example 3, polylactic acid (TE-2000, manufactured by Unitika Corporation) was used as resin B in Example 6. The temperature during melt-mixing of the granules and resin B in a twin-screw kneader was 120°C. Otherwise, the same procedure as in Example 3 was performed to obtain the same test piece (test piece (6)) and subject it to the same test. As a result, the resistivity of test piece (6) was 0.07 Ω·m. Furthermore, test piece (6) was subjected to the same tensile modulus (MPa), tensile strength (MPa), flexural modulus (MPa), flexural strength (MPa), and Izod impact value (KJ / m) relative to test piece (0), as in the case of test piece (1) in Example 1. 2 ) increased.

[0128] <Example 7> In Example 1, during the stirring process, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 1:3:5:10 (by mass), and water was added so that the total mass of these components had a mass ratio of 19:15 (water content was 44.1% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. In Example 7, water was added so that the total mass of these components had a mass ratio of 19:20 (water content was 51.3% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner in the same way. Then, the same procedure as in Example 1 was performed to obtain slurry (7).

[0129] As a result, the obtained slurry (7) differed from the slurry (1) obtained in Example 1 in that it did not maintain its shape when stationary. However, its dispersibility was high, similar to that of Example 1.

[0130] Subsequently, the obtained slurry (7) was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, but it was not possible to obtain granules (cylindrical granules) that maintained their shape. In other words, it was confirmed that slurry (7) had lower granulation properties compared to slurry (1).

[0131] Therefore, after drying the slurry (7) with hot air until it was completely dry, water was added and kneaded to achieve a moisture content of 25% by mass. Then, the mixture was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, and granulated material (cylindrical granules) was obtained.

[0132] <Example 8> In Example 1, single-walled carbon nanotubes were used as carbon fibers in the stirring process, but in Example 8, vapor-processed carbon fibers (VGCF-H, manufactured by Showa Denko Corporation) were used instead. Then, the same procedure as in Example 1 was performed to obtain slurry (8).

[0133] As a result, the obtained slurry (8) differed from the slurry (1) obtained in Example 1 in that it did not maintain its shape when stationary. However, its dispersibility was high, similar to that of Example 1.

[0134] Subsequently, the obtained slurry (8) was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, but it was not possible to obtain granules (cylindrical granules) that maintained their shape. In other words, it was confirmed that slurry (8) had lower granulation properties compared to slurry (1).

[0135] Therefore, after drying the slurry (8) with hot air until it was completely dry, water was added and kneaded to achieve a moisture content of 25% by mass. Then, the mixture was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, and granulated material (cylindrical granules) was obtained.

[0136] <Example 9> In Example 1, single-walled carbon nanotubes were used as carbon fibers in the stirring process, but in Example 9, vapor-processed carbon fibers (VGCF-H, manufactured by Showa Denko Corporation) were used instead. In Example 1, during the stirring process, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 1:3:5:10 (mass ratio), and water was added so that the mass ratio of the total mass of these components to water was 19:15 (water content was 44.1% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. However, in Example 9, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 2:3:5:10 (mass ratio), and water was added so that the mass ratio of the total mass of these components to water was 20:15 (water content was 42.9% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. Then, the same procedure as in Example 1 was performed to obtain slurry (9).

[0137] Slurry (9), like slurry (1) obtained in Example 1, maintained its shape when stationary and was a highly dispersible slurry composition in which each component was sufficiently dispersed.

[0138] Subsequently, the obtained slurry (9) was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, and granulated material (cylindrical granules) was obtained. In other words, it was confirmed that slurry (9) has high granulation properties.

[0139] <Example 10> In Example 1, single-walled carbon nanotubes were used as carbon fibers in the stirring process, but in Example 10, vapor-processed carbon fibers (VGCF-H, manufactured by Showa Denko Corporation) were used instead. In Example 1, during the stirring process, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 1:3:5:10 (by mass), and water was added so that the total mass of these components had a mass ratio of 19:15 (water content was 44.1% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. In Example 10, however, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 2:3:5:10 (by mass), and water was added so that the total mass of these components had a mass ratio of 20:20 (water content was 50.0% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. Then, the same procedure as in Example 1 was performed to obtain slurry (10).

[0140] As a result, the obtained slurry (10) differed from the slurry (1) obtained in Example 1 in that it did not maintain its shape when stationary. However, its dispersibility was high, similar to that of Example 1.

[0141] Subsequently, the obtained slurry (10) was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, but it was not possible to obtain granules (cylindrical granules) that maintained their shape. In other words, it was confirmed that slurry (10) had lower granulation properties compared to slurry (1).

[0142] Therefore, after drying the slurry (10) with hot air until it was completely dry, water was added and kneaded to achieve a moisture content of 25% by mass. Then, the mixture was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, and granulated material (cylindrical granules) was obtained.

[0143] <Example 11> In Example 1, single-walled carbon nanotubes were used as carbon fibers in the stirring process, but in Example 11, carbon nanofibers (conductive carbon nanofibers manufactured by Almedio) were used instead. In Example 1, during the stirring process, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 1:3:5:10 (by mass), and water was added so that the total mass of these components had a mass ratio of 19:15 (water content was 44.1% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. In Example 11, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 1:3:5:10 (by mass), and water was added so that the total mass of these components had a mass ratio of 19:10 (water content was 34.5% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. Then, the same procedure as in Example 1 was performed to obtain slurry (11).

[0144] Slurry (11), like slurry (1) obtained in Example 1, maintained its shape when stationary and was a highly dispersible slurry composition in which each component was sufficiently dispersed.

[0145] Subsequently, the obtained slurry (11) was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, but it was not possible to obtain granules (cylindrical granules) that maintained their shape. In other words, it was confirmed that the granulation properties of slurry (11) were lower compared to slurry (1).

[0146] Therefore, the slurry (11) was dried by applying hot air until it was completely dry, then water was added and kneaded to achieve a moisture content of 25% by mass. After that, the mixture was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, and granulated material (cylindrical granules) was obtained.

[0147] <Example 12> In Example 1, single-walled carbon nanotubes were used as carbon fibers in the stirring process, but in Example 12, carbon nanofibers (conductive carbon nanofibers manufactured by Almedio) were used instead. Then, the same procedure as in Example 1 was performed to obtain slurry (12).

[0148] As a result, the obtained slurry (12) differed from the slurry (1) obtained in Example 1 in that it did not maintain its shape when stationary. However, its dispersibility was high, similar to that of Example 1.

[0149] Subsequently, the obtained slurry (12) was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, but it was not possible to obtain granules (cylindrical granules) that maintained their shape. In other words, it was confirmed that the granulation properties of slurry (12) were lower compared to slurry (1).

[0150] Therefore, after drying the slurry (12) with hot air until it was completely dry, water was added and kneaded to achieve a moisture content of 25% by mass. Then, the mixture was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, and granulated material (cylindrical granules) was obtained.

[0151] <Example 13> In Example 1, single-walled carbon nanotubes were used as carbon fibers in the stirring process, but in Example 13, carbon nanofibers (conductive carbon nanofibers manufactured by Almedio) were used instead. In Example 1, during the stirring process, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 1:3:5:10 (mass ratio), and water was added so that the mass ratio of the total mass of these components to water was 19:15 (water content was 44.1% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. In Example 13, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 2:3:5:10 (mass ratio), and water was added so that the mass ratio of the total mass of these components to water was 20:15 (water content was 42.9% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. Then, the same procedure as in Example 1 was performed to obtain slurry (13).

[0152] As a result, the obtained slurry (13) differed from the slurry (1) obtained in Example 1 in that it did not maintain its shape when stationary. However, its dispersibility was high, similar to that of Example 1.

[0153] Subsequently, the obtained slurry (13) was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, but it was not possible to obtain granules (cylindrical granules) that maintained their shape. In other words, it was confirmed that the granulation properties of slurry (13) were lower compared to slurry (1).

[0154] Therefore, the slurry (13) was dried by applying hot air until it was completely dry, then water was added and kneaded to achieve a moisture content of 25% by mass. After that, the mixture was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, and granulated material (cylindrical granules) was obtained.

[0155] <Example 14> In Example 1, single-walled carbon nanotubes were used as carbon fibers in the stirring process, but in Example 14, carbon nanofibers (conductive carbon nanofibers manufactured by Almedio) were used instead. In Example 1, during the stirring process, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 1:3:5:10 (mass ratio), and water was added so that the mass ratio of the total mass of these components to water was 19:15 (water content was 44.1% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. In Example 14, however, the mixing ratio of carbon fiber, π-conjugated polymer, dopant Y, and resin A was 3:3:5:10 (mass ratio), and water was added so that the mass ratio of the total mass of these components to water was 21:15 (water content was 41.7% by mass). This mixture was then placed in a stirring vessel and stirred in a rotational and orbital manner. Then, the same procedure as in Example 1 was performed to obtain slurry (14).

[0156] Slurry (14), like slurry (1) obtained in Example 1, maintained its shape when stationary and was a highly dispersible slurry composition in which each component was sufficiently dispersed.

[0157] Subsequently, the obtained slurry (14) was processed using the same extrusion granulator as in Example 1, under the same processing conditions and methods, and granulated material (cylindrical granules) was obtained. In other words, it was confirmed that slurry (14) has high granulation properties.

[0158] <Comparative Example 1> In Example 1, polyaniline was used in the stirring step, but it was not used in Comparative Example 1. Otherwise, the same procedure as in Example (1) was followed to obtain similar test pieces, which were then subjected to the same tests. The test piece prepared in Comparative Example 1 was found to have inferior electrical conductivity and lower strength (measured results for tensile modulus, tensile strength, flexural modulus, flexural strength, and Izod impact value) compared to the test piece prepared in either of the embodiments.

[0159] The obtained slurry was dried in a hot air dryer and then observed at 5,000x magnification using a scanning electron microscope. The resulting electron microscope image (SEM image) is shown in Figure 3. From Figure 3, it can be said that the carbon fibers are aggregated and the dispersibility is low.

[0160] The compositions and other details of the above examples and comparative examples are summarized in Table 2. Furthermore, if the obtained slurry maintained its shape while stationary, it was indicated with "○" in the "Slurry Properties" column of Table 2; if it did not maintain its shape while stationary, it was indicated with "×" in the same column. Furthermore, if the resulting slurry had high dispersibility (i.e., each component was sufficiently dispersed), it was indicated with "○" in the "Dispersibility" column of Table 2. Conversely, if the dispersibility was low, it was indicated with "×" in the same column. Furthermore, if granules with a maintained shape (cylindrical granules) were obtained using an extruder in the granulation process, the granulation performance was considered high, and this was indicated with "○" in the "Granulation Performance" column of Table 2. If such granules (cylindrical granules) were not obtained, the granulation performance was considered relatively low, and this was indicated with "△" in the same column. In addition, if it was necessary to add a granulation aid, such as bentonite, to granulate, this was indicated with "×" in the same column.

[0161] [Table 2]

Claims

1. Carbon fiber and π-conjugated polymers and A dopant having an organic acid group that reacts with the aforementioned π-conjugated polymer to exhibit conductivity, Granular resin A, Water and, A stirring step involves stirring a mixture containing the ingredients to obtain a slurry composition in which the water content is 30 to 60% by mass, A mixing step of granulating the slurry composition and mixing the resin B with the granulated slurry composition, Equipped with, The carbon fiber and, The reaction product of the π-conjugated polymer and the dopant, A resin X is a mixture of the aforementioned resin A and the aforementioned resin B, A method for producing a conductive composition, which yields a conductive composition containing the above.

2. A method for producing a conductive composition according to claim 1, wherein in the stirring step, the mixed material is stirred by rotation and revolution to obtain the slurry composition.

3. A conductive composition obtained by the manufacturing method described in claim 1 or 2 is molded, The carbon fiber and, The reaction product of the π-conjugated polymer and the dopant, The aforementioned resin X, A method for manufacturing a molded article, comprising a molding step to obtain a molded article containing a certain component.

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