JP2009255568A - Method for manufacturing resin molded article containing fine carbon fiber localized on surface layer by transferring process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low cost resin molded article of which the physical integrities do not fall, and which can efficiently express electroconductivity even when a small amount of a fine carbon fiber is added. <P>SOLUTION: With a target resin plate on the surface of which an electricity controlling layer is planned to be accumulated, another resin plate containing fine carbon fibers is brought into contact. Then, both resin plates are heat-treated at 100 to 400°C for 1 to 60 minutes. Then, both resin plates are separated from each other. Thus, the target resin plate having fine carbon fibers having been transferred from the above another resin plate is produced. The resin molded article and its manufacturing method are provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a technique for improving the conductivity of a resin molded body containing fine carbon fibers by heating and transferring treatment.

In recent years, with the rapid development of electronics technology, information processing devices and electronic office equipment are rapidly spreading. With the rapid spread of such electronic devices, troubles such as electromagnetic interference in which noise generated from electronic components affects peripheral devices and malfunctions due to static electricity have become a major problem. In order to solve these problems, materials excellent in conductivity and antistatic properties are required in this field. Conventionally, in a polymer material with poor conductivity, a conductive polymer material imparted with a conductivity function by blending a highly conductive conductive filler or the like has been widely used.

Conventionally, metal fibers and metal powders, carbon black, carbon nanotubes, and the like are generally used as the conductive filler. However, recently discovered carbon nanotubes are in increasing demand in a wide range of industrial fields.

One carbon nanotube of a fine carbon fiber is an electronic device, electrical wiring, thermoelectric conversion element material, building material using physical properties such as chemical properties, electrical properties, mechanical properties, thermal conductivity, and structural properties. Heat dissipation materials for electromagnetic waves, electromagnetic shielding materials, field emission cathode materials for flat panel displays, electrode bonding materials, resin composite materials, transparent conductive films, electromagnetic wave absorbers, catalyst support materials, electrodes / hydrogen storage materials, reinforcing materials, black pigments, etc. The application of is expected.

However, in conductive composite materials using these conductive fillers, the dispersibility of the conductive filler greatly affects the conductivity of the resin composition. Has the problem of being needed.

In the production of conductive materials, researches such as production of an antistatic plate by compression, casting, injection, extrusion or stretching method, production of an antistatic film using a conductive paint, and production of an electromagnetic shielding material are being conducted.

There is a description that the carbon fiber is exposed to the surface of the resin by heating and pressurizing the resin molded body containing the carbon fiber at a temperature equal to or higher than the melting point of the resin (see, for example, Patent Document 1). . However, this carbon fiber is not a carbon nanotube.

There is a description of an antistatic resin molded body in which a carbon nanotube-containing resin solvent is applied in a plurality of times on a resin substrate, and the antistatic resin molded body is directed from the surface of the antistatic layer toward the resin substrate. It is disclosed that carbon nanotubes are sequentially reduced (for example, see Patent Document 2).

There is a description of an antistatic resin molded body in which a carbon nanotube-containing resin solvent is coated on a resin substrate, and it is disclosed that this antistatic resin molded body has carbon nanotubes exposed on the antistatic surface. (For example, refer to Patent Document 3 and Patent Document 4). These antistatic resin moldings have a problem that the resin substrate and the coating layer are easily peeled off.

It is described that when a resin molded body containing carbon fibers is heated below the glass transition temperature, the carbon fibers float on the surface of the molded body and the conductivity is improved (for example, see Patent Document 5).

There is a description that the resin molded body containing carbon fiber was heat-treated at a temperature equal to or lower than the Vicat softening point to reduce the volume resistance value (see, for example, Patent Document 6). These techniques also use carbon fibers instead of carbon nanotubes.

Japanese Patent Laid-Open No. 10-50144 JP 2006-35774 A JP 2007-112133 A Japanese Patent No. 2004-253796 Japanese Patent Laid-Open No. 8-80579 Japanese Patent Laid-Open No. 11-43548

Thus, various attempts have been made to improve the conductivity of the conductive filler-containing resin material. However, there is no description about a method of bringing a fine carbon fiber into a surface layer of the target resin plate by bringing a resin plate containing the fine carbon fiber into contact with the target resin plate.

The problem to be solved by the present invention is to provide a resin molded body in which fine carbon fibers are localized on the surface layer by migration treatment.

When fine carbon fiber or the like is used as a conductive filler, high conductivity cannot usually be exhibited by addition at a low concentration. On the other hand, if conductivity is imparted by adding a high concentration of the filler, the original physical properties of the resin are lowered. In addition, since fine carbon fibers are expensive, a method for improving conductivity to show high conductivity by adding a small amount of fine carbon fibers to the whole resin in order to produce a low-cost conductive composite material. Is required.

In order to solve the above-mentioned problems, as a result of earnest studies, in the technology for improving the conductivity of the resin molded body containing fine carbon fibers, the resin plate containing fine carbon fibers is brought into contact with the target resin plate and subjected to heat treatment. Then, by holding the heated state and then peeling, the fine carbon fibers are transferred to the surface layer of the peeling plate, and it is found that conductivity can be added to the resin plate that did not show conductivity, and the invention is completed. It has come. The present invention has the following contents.

A resin molded body in which an antistatic layer is accumulated on at least one surface of the resin molded body, the antistatic layer including fine carbon fibers, and an axis perpendicular to the surface of the antistatic layer in the arrangement state of the fine carbon fibers A resin molded product, wherein the number of fine carbon fibers having an inclination of 0 degree or more and less than 45 degrees is 20 to 60% by mass of the total number of fine carbon fibers.

The resin molding is characterized in that the fine carbon fibers are randomly oriented in a three-dimensional direction.

A resin molded body according to the resin molded body, wherein a plurality of carbon tubes are in electrical contact with each other at a surface layer portion of the resin molded body.

The resin molded body, wherein the resin molded body has a surface resistivity of 10 ¹ to 10 ¹² Ω / □.

In the resin molded body, the resin constituting the molded body is a thermoplastic resin.

The thermoplastic resin is cellulose acetate, ethyl cellulose, polydimethylsiloxane, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl pyrrolidine, sucrose octaacetate, polycarbonate (PC), polyethylene (PE), polypropylene (PP ), Polystyrene (PS), acrylotolyl / butanediene / styrene resin (ABS), polyvinyl chloride (PVC), acrylonitrile / styrene resin (AS), methacrylic resin (PMMA), vinyl chloride (PVC), polyamide (PA), polyacetal (POM), modified polyphenylene ether (m-PPE), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), ultra-high polymer Polyethylene (UHPE), polyphenylene sulfide (PPS), polyimide (PI), polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyethersulfone (PES), polyetheretherketone (PEEK), liquid crystal The resin constituting the resin molded body containing at least one selected from a polymer (LCP), polytetrafluoroethylene (PTFE), and polyurethane (PU) is one kind of thermoplastic resin. A resin molding.

The resin molded body, wherein the fine carbon fiber has an outer diameter of 0.5 to 800 nm.

The resin molding in which the fine carbon fiber is a single-layer fine carbon fiber, a double-layer fine carbon fiber, or a multilayer fine carbon fiber.

The fine carbon fiber is a network-like carbon fiber structure composed of carbon fibers having an outer diameter of 15 to 200 nm, and the carbon fiber structure is a mode in which a plurality of the fine carbon fibers extend, It has a granular part that binds the fine carbon fibers to each other, and the granular part is formed in the growth process of the fine carbon fiber, and is 1.3 times the size of the external shape of the fine carbon fiber. A resin molded product characterized by having

A resin plate containing another fine carbon fiber is brought into contact with the target resin plate on which the antistatic layer is to be accumulated on the surface, and is heated at 100 to 400 ° C., and kept in a heated state for 1 to 60 minutes. A method for producing a resin molded body, wherein the antistatic layer is accumulated by transferring the fine carbon fibers to the surface layer of the target resin plate by peeling the two resin plates from each other.

In the method for producing a resin molded body, the resin molded body containing a fine carbon fiber having a viscosity at 100 to 400 ° C. higher than that of the target resin plate at 100 to 400 ° C. is used. Manufacturing method.

In the method for producing a resin molded body, the resin material for the resin board containing fine carbon fibers is not compatible with the target resin board.

In the method for producing a resin molded body, the absolute value of the difference between the surface tension of the target resin plate and the surface tension of the fine carbon fiber is T1, and the surface tension of the resin plate containing the fine carbon fiber and the carbon fiber Wherein the resin plate containing fine carbon fibers is selected so that T1 <T2 when the absolute value of the difference from the surface tension of T2 is T2, and is brought into contact with the target resin plate Manufacturing method.

In the method for producing a resin molded body, a release sheet for easily peeling the target resin plate from the hot plate is polytetrafluoroethylene (PTFE), polyetheretherketone (PEEK), polysulfone (PSF), polyphenylene. A method for producing a resin molded body comprising using any one of sulfide (PPS), polyetherimide (PEI), polyethersulfone (PES), and polyimide (PI).

A method for improving the conductivity of a resin molded body having a surface resistivity of 10 ¹² Ω / □ or less using the method for producing the resin molded body until the surface resistivity is 10 ¹² Ω / □ or less.

In the method for producing a resin molded body, the resin molded body that has been heated is cooled in stages.

A method of using the resin molded body as a conductive material, an electromagnetic wave shield, an electromagnetic wave absorber, an infrared shield, or a heating element.

In the conductive addition method of the present invention, a resin plate containing fine carbon fibers is brought into contact with a target resin plate for which an antistatic layer is to be accumulated, heat-treated, and the heated state is maintained. It is characterized in that the fine carbon fibers are transferred to the surface layer of the target resin plate by peeling the resin plates from each other. Before the treatment, fine carbon fibers were not present on the surface layer of the resin molded body, but the object of imparting or improving conductivity from the resin plate containing fine carbon fibers by the treatment of the present invention. Part of the fine carbon fibers can be moved to the surface layer portion of the resin plate and can also be present in the surface layer portion. The presence of the fine carbon fiber at a high concentration in the surface layer of the resin molded body is particularly effective in reducing the surface resistance. The resin molded body produced by the present invention is characterized by the arrangement of fine carbon fibers. The fine carbon fibers in the antistatic layer formed after the transfer treatment are measured by measuring the arrangement of 50 fine carbon fibers with a microscope, and 10 to 30 of the 50 are from the antistatic layer surface side toward the resin molded body side. It is arranged at 0 degree or more and less than 45 degree in the vertical direction. This is due to the movement of the fine carbon fibers described below, and when the two resin plates are peeled off, the fine carbon fibers stand up against the surface layer portion.

In addition, when making it transfer to a surface layer part, four mechanisms can be guessed. The first is a phenomenon in which fine carbon fibers diffuse and move from the resin plate containing fine carbon fibers to the target resin plate in the molten resin plate. At this time, the fine carbon fibers easily move parallel to the fiber direction of the fine carbon fibers due to Brownian motion, and as a result, the fine carbon fibers contact the surface of both resin plates from the surface of the antistatic layer toward the resin molding side. There are many things arranged in the vertical direction. Second, when the resin plates are separated from each other, the resin containing fine carbon fibers adheres to the surface layer portion of the target resin plate. Third, in the case where fine carbon fibers exist across the interface between two types of resins, the fine carbon fibers move from the larger surface tension of each resin to the smaller one. The fourth is a phenomenon that when heated, the resin is in a molten state, and when a resin plate containing fine carbon fibers is bonded to the upper side, it moves to the surface layer portion of the target resin plate placed on the lower side by gravity. These four phenomena may be caused to act independently.

The resin molded body of the present invention is a resin molded body in which an antistatic layer is accumulated on one side of the resin molded body, wherein the antistatic layer includes fine carbon fibers, and the fine carbon fibers are resin from the surface of the antistatic layer. The fine carbon fibers are arranged in the vertical direction at 0 degree or more and less than 45 degrees toward the molded body side, and the fine carbon fibers having the above-mentioned angles are present in an amount of 20 to 60% by mass. Since the plurality of carbon nanotubes are present at a high concentration and are in electrical contact with each other, even when the concentration of the conductive filler added to the entire resin molded body is low, the carbon nanotube has high conductivity. Further, the physical properties of the resin molded body are not deteriorated, and there is no possibility that the antistatic layer is peeled off.

SEM photograph of the first intermediate of carbon nanotube Schematic diagram of lamination method of CNT resin composite and resin plate Scanning electron microscope (SEM) photograph of the cross section of the sample with carbon nanotubes transferred to the resin surface SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample subjected to migration treatment at 200 ° C. for 2 minutes SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample subjected to migration treatment at 300 ° C. for 2 minutes SEM photograph of cross section of CNT thin film / HDPE substrate of [HDPE] / [20 wt% CNT / PP] sample subjected to migration treatment at 200 ° C. for 2 minutes SEM photograph of cross section of CNT thin film / HDPE substrate of [HDPE] / [20 wt% CNT / PP] sample transferred at 300 ° C. for 2 minutes SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample subjected to migration treatment at 300 ° C. for 2 minutes SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample subjected to migration treatment at 300 ° C. for 5 minutes SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample transferred at 300 ° C. for 10 minutes SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample subjected to migration treatment at 300 ° C. for 15 minutes SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample subjected to migration treatment at 300 ° C. for 20 minutes SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample subjected to migration treatment at 300 ° C. for 25 minutes SEM photograph of CNT thin film / PC substrate cross section of [PC] / [20 wt% CNT / PP] sample subjected to migration treatment at 300 ° C. for 30 minutes

Hereinafter, the present invention will be described in detail.

In the method for producing a resin molded body, it is preferable to use a sheet for mold release for making the target resin plate easily peeled off from the hot plate, having a glass transition temperature higher than that of the resin of the resin molded body. Alternatively, resins having low compatibility with each other are preferably combined. Specifically, polytetrafluoroethylene (PTFE), polyether ether ketone (PEEK), polysulfone (PSF), polyphenylene sulfide (PPS), polyetherimide (PEI), polyether having a high glass transition temperature are used for the resin plate. It is preferable to use sulfone (PES), polyimide (PI) or the like.

Here, the term “electrically in contact” as used in the present invention means that a plurality of carbon non-tubes partially approach each other, and a continuous conductive path is formed to be in an energized state.

The fine carbon fiber concentration added to the resin molded body is preferably 0.1 to 20% by weight with respect to the resin. By using this method, it is possible to produce a resin molded product exhibiting high conductivity even when a low concentration of fine carbon fiber is added.

The addition amount of the fine carbon fiber of the present invention is in the range of 0.01 to 20% by weight, preferably 0.2 to 15% by weight, more preferably 0 to 100% by weight of the conductive composite material. 5 to 10% by weight. Thus, when there are few fine carbon fibers than 0.1 weight%, desired electroconductivity cannot be obtained. Further, when the fine carbon fiber is 20% by weight or more, the fine carbon fiber is bulky, so that a good conductive composite material cannot be produced.

About the heating temperature of this invention, it is the range of glass transition temperature-20-20 + 250 degreeC of resin used as the material of a resin molding, Preferably it is + 50- + 200 degreeC, More preferably, it is + 100- + 200 degreeC. In addition, when the treatment is performed at a temperature higher than the glass transition temperature by 250 ° C. or more, the properties of the resin are modified, and a good conductive composite material cannot be produced.

The conductive addition method of the present invention proceeds only with the heating process, but in some cases, a pressurizing process may be combined. The applied pressure is in the range of 1 to 100 MPa, preferably 1 to 50 MPa, and more preferably 1 to 20 MPa.

About the heating and pressurization time of this invention, it is the range of 1-60 minutes, Preferably it is 1-30 minutes, More preferably, it is 15-30 minutes.

After the heating and pressurizing treatment of the present invention, sufficient conductivity can be obtained even if the resin molded body is air-cooled, but if necessary, the molded body can be reduced by gradually reducing the heating temperature of the molded body. The mechanical properties can be improved while maintaining the state in which the rearrangement of the fine carbon fibers inside is stabilized and the conductivity is improved.

The resin material constituting the resin molded body of the present invention is preferably a thermoplastic resin. Examples of the thermoplastic resin material include cellulose acetate, ethyl cellulose, polydimethylsiloxane, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl pyrrolidine, sucrose octaacetate, polycarbonate (PC), polyethylene (PE), Polypropylene (PP), polystyrene (PS), acrylotolyl / butanediene / styrene resin (ABS), polyvinyl chloride (PVC), acrylonitrile / styrene resin (AS), methacrylic resin (PMMA), vinyl chloride (PVC), polyamide (PA ), Polyacetal (POM), modified polyphenylene ether (m-PPE), polybutylene terephthalate (PBT), polyethylene terephthalate (PE) ), Ultra high molecular weight polyethylene (UHPE), polyphenylene sulfide (PPS), polyimide (PI), polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyethersulfone (PES), polyetheretherketone (PEEK), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyurethane (PU), and resins obtained by modifying these.

In order to improve the conductivity and mechanical properties of the resin, fillers other than fine carbon fibers may be added as necessary. In the conductive filler of the present invention, carbon fiber, carbon black, metal fiber, carbon fibril, metal whisker, ceramic fiber or ceramic whisker are shown and can be used depending on the purpose.

In the fine carbon fiber used in the present invention, single-layer, double-layer, and multilayer fine carbon fibers are shown and can be used according to the purpose. In the present invention, multilayer fine carbon fibers are preferred. The method for producing fine carbon fibers is not particularly limited, and any conventionally known method such as a vapor phase growth method using a catalyst, an arc discharge method, a laser evaporation method, and a HiPco method (High-pressure carbon monooxide process) can be used. A manufacturing method may be used.

For example, a method for producing a single-layer fine carbon fiber by laser vapor deposition is shown below. Prepare graphite powder and nickel and cobalt fine powder mixing rod as raw materials. This mixed lot is heated to 1250 ° C. in an electric furnace under an argon atmosphere of 665 hPa (500 Torr), and irradiated with a second harmonic pulse of 350 mJ / Pulse Nd: YAG laser to evaporate carbon and metal fine particles. Thus, a fine carbon fiber having a single layer can be produced.

The above manufacturing method is merely a typical example, and the metal type, gas type, electric furnace temperature, laser wavelength, and the like may be changed. In addition, other than laser deposition methods, for example, HiPco method, vapor phase growth method, arc discharge method, carbon monoxide thermal decomposition method, template method in which organic molecules are inserted into fine pores, thermal decomposition, fullerene -You may use the single layer fine carbon fiber produced by other methods, such as a metal co-evaporation method.

For example, a method for producing a two-layer fine carbon fiber by a constant temperature arc discharge method is shown below. The substrate was a surface-treated Si substrate, and the treatment method was a solution obtained by immersing alumina powder in a solution in which the catalyst metal and the catalyst auxiliary metal were dissolved for 30 minutes, and then dispersing by ultrasonic treatment for 3 hours. Was applied to a Si substrate and kept in air at 120 ° C. and dried. A substrate was installed in the reaction chamber of the fine carbon fiber production apparatus, a mixed gas of hydrogen and methane was used as a reaction gas, the supply amount of gas was 500 sccm for hydrogen, 10 sccm for methane, and the pressure in the reaction chamber was 70 Torr. As the cathode part, a rod-like discharge part made of Ta was used. Next, a DC voltage was applied between the anode part and the cathode part, and between the anode part and the substrate, and the discharge voltage was controlled so that the discharge current was constant at 2.5A. When the temperature of the cathode part is 2300 ° C. due to discharge, the normal glow discharge state is changed to an abnormal glow discharge state, and the discharge current is 2.5 A, the discharge voltage is 700 V, and the reaction gas temperature is 3000 ° C. for 10 minutes. Single-layer and double-layer fine carbon fibers can be produced on the entire substrate.

The above manufacturing method is merely an example, and various conditions such as the type of metal and the type of gas may be changed. Moreover, you may use the two-layered fine carbon fiber produced by production methods other than the arc discharge method.

For example, a method for producing a multi-layered fine carbon fiber having a three-dimensional structure by a vapor deposition method is shown below. Basically, an organic compound such as a hydrocarbon is chemically pyrolyzed by CVD using transition metal ultrafine particles as a catalyst to obtain a fiber structure (hereinafter referred to as an intermediate), which is further subjected to high-temperature heat treatment to produce multilayer fine particles. Carbon fibers can be made.

As the raw material organic compound, hydrocarbons such as benzene, toluene and xylene, and alcohols such as carbon monoxide and ethanol are used, but it is preferable to use at least two or more carbon compounds having different decomposition temperatures as the carbon source. . Note that at least two or more carbon compounds do not necessarily use two or more types of raw material organic compounds, and even when one type of raw material organic compound is used, the fiber structure In the body synthesis process, for example, a reaction such as hydrogen dealkylation of toluene or xylene occurs, and in the subsequent thermal decomposition reaction system, it becomes two or more carbon compounds having different decomposition temperatures. Including embodiments. The atmosphere gas is an inert gas such as argon, helium, xenon or hydrogen, and the catalyst is a transition metal such as iron, cobalt or molybdenum, or a transition metal compound such as ferrocene or metal acetate, and sulfur or thiophene or iron sulfide. Use a mixture of sulfur compounds such as

The synthesis of the intermediate is carried out by using a CVD method such as hydrocarbon, which is usually performed, by evaporating the mixture of hydrocarbon and catalyst as raw materials, introducing hydrogen gas or the like into the reaction furnace as a carrier gas, Pyrolysis at a temperature of 1300 ° C. As a result, the number of a plurality of fine carbon fiber structures (intermediates) having a sparse three-dimensional structure in which fibers having an outer diameter of 15 to 200 nm are bonded together by granular materials grown using the catalyst particles as nuclei. Synthesize an aggregate of centimeters to tens of centimeters.

The thermal cracking reaction of the hydrocarbon as a raw material mainly occurs on the surface of the granular particles grown using the catalyst particles or the core, and the recrystallization of carbon generated by the decomposition proceeds in a certain direction from the catalytic particles or granular materials. Grows in a fibrous form. However, by intentionally changing the balance between the thermal decomposition rate and the growth rate, for example, by using at least two or more carbon compounds having different decomposition temperatures as a carbon source as described above, the carbon material is only in a one-dimensional direction. The carbon material is grown three-dimensionally around the granular material without growing the material. Of course, the growth of such three-dimensional fine carbon fibers does not depend only on the balance between the thermal decomposition rate and the growth rate, but the crystal face selectivity of the catalyst particles, the residence time in the reactor, Although it is affected by the temperature distribution, etc., in general, when the growth rate is faster than the thermal decomposition rate as described above, the carbon material grows in a fibrous form, while the thermal decomposition rate is higher than the growth rate. When fast, the carbon material grows in the circumferential direction of the catalyst particles. Therefore, by intentionally changing the balance between the pyrolysis rate and the growth rate, the growth of the carbon material as described above can be formed in a certain direction, and a three-dimensional structure can be formed in the other direction under control. Is something you can do. In the intermediate to be produced, the composition of the catalyst, the residence time in the reaction furnace, the reaction temperature, and the gas temperature are used to easily form the three-dimensional structure as described above in which the fibers are bonded together by the granular material. Etc. are preferably optimized.

An intermediate obtained by heating and generating a mixed gas of catalyst and hydrocarbon at a constant temperature in the range of 800 to 1300 ° C. has a structure in which patch-like sheet pieces made of carbon atoms are bonded together, and Raman When spectroscopic analysis is performed, the D band is very large and there are many defects. Moreover, the produced | generated intermediate body contains the unreacted raw material, non-fibrous carbon material, a tar content, and a catalyst metal.

Therefore, in order to remove these residues from such an intermediate and obtain the desired fine carbon fiber structure with few defects, high-temperature heat treatment at 2400 to 3000 ° C. is performed by an appropriate method.

That is, for example, the intermediate is heated at 800 to 1200 ° C. to remove volatile components such as unreacted raw materials and tars, and then annealed at a high temperature of 2400 to 3000 ° C. to prepare the desired structure. At the same time, the catalyst metal contained in the fiber is removed by evaporation. At this time, in order to protect the substance structure, a reducing gas or a small amount of carbon monoxide gas may be added to the inert gas atmosphere.

When the intermediate is annealed at a temperature in the range of 2400 to 3000 ° C., the patch-like sheet pieces made of carbon atoms are bonded to each other to form a plurality of graphene sheet-like layers.

Further, before or after such high-temperature heat treatment, the step of crushing the equivalent circle average diameter of the fine carbon fiber structure to several centimeters, and the equivalent circle average diameter of the fine carbon fiber structure subjected to the crush treatment The fine carbon fiber which has a desired circle equivalent average diameter is produced through the process of grind | pulverizing to 50-100 micrometers.

The above manufacturing method is merely an example, and various conditions such as the type of metal and the type of gas may be changed. Moreover, you may use the multilayer fine carbon fiber produced by production methods other than a vapor phase growth method.

You may add an additive to the resin molding of this invention according to another use. For example, inorganic pigments, organic pigments, whiskers, thickeners, anti-settling agents, UV inhibitors, wetting agents, emulsifiers, anti-skinning agents, polymerization inhibitors, anti-sagging agents, antifoaming agents, anti-color separation agents, Leveling agents, drying agents, curing agents, curing accelerators, plasticizers, fireproofing / preventing agents, fungicides / algaeproofing agents, antibacterial agents, insecticides, marine antifouling agents, metal surface treatment agents, derusting agents, degreasing agents , Film forming agents, bleaching agents, colorants, wood sealers, sealants, sanding sealers, sealers, cement fillers or resin-containing cement pastes.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Synthesis Example 1)
An aggregate of carbon nanotube structures was synthesized using toluene as a raw material by the floating CVD method. A mixture of ferrocene and thiophene was used as a catalyst, and the reaction was performed in a hydrogen gas reducing atmosphere. Toluene and the catalyst were heated to 380 ° C. together with hydrogen gas, supplied to the generating furnace, and thermally decomposed at 1300 ° C. to obtain an aggregate of carbon nanotube structures (first intermediate).

(Synthesis Example 2)
An SEM photograph of this first intermediate or a TEM photograph dispersed in toluene and observed after preparing a sample for an electron microscope is shown in FIGS. The synthesized first intermediate was calcined at 900 ° C. in nitrogen, and volatile components such as tar were separated to obtain a second intermediate.

(Synthesis Example 3)
Further, this second intermediate was heat treated at 2600 ° C. in argon at a high temperature to obtain an aggregate of carbon nanotube structures (third intermediate). 3 and 4 show SEM and TEM photographs observed after the third intermediate of the obtained carbon nanotube structure was dispersed in toluene with ultrasonic waves and a sample for an electron microscope was prepared. The third intermediate obtained using New Microcyclomat (MCM-15 type, manufactured by Masuno Seisakusho) was pulverized by airflow pulverization to adjust the particle size. The SEM photograph is shown in FIG. The carbon nanotube of the present invention was prepared.

The fine carbon fiber used in this example is a multi-walled carbon nanotube (CNT) manufactured by two-stage heat treatment by a floating chemical vapor deposition method (manufactured by Nanocarbon Technologies, Inc., trade name: MWNT-7). The carbon fiber has a fiber diameter of 40 to 90 nm, an aspect ratio of 100 or more, and a purity of 99.5% or more. Polycarbonate (PC) resin (Panlite, L-1225, manufactured by Teijin Chemicals Limited), polypropylene (PP) resin (Prime Polymer Co., Prime Polypro, J108M), and polyethylene (PE) resin (Japan) Polyethylene Co., Ltd., High Density Polyethylene (HDPE), Novatec, HJ590N) were each melt-mixed at 300 ° C. (PC) and 250 ° C. (PP and PE) using a biaxial kneader, Three types of CNT / resin (20/80, weight ratio) pellets (particle size about 3-4 mm) master batch (MB) (20% CNT / PC, 20 wt% CNT / PP, and 20 wt% CNT / PE ) Was manufactured.

Heat heated to 200 ° C. between each of the above MB pellets and a metal plate with a polyethylene terephthalate (PET) film (Toyobo Polyester, E5100, manufactured by Toyobo Co., Ltd.) having a thickness of about 0.01 to 0.03 mm. Each MB pellet was melted by heating between two hot plates of a press machine for 2 minutes, and then pressed at about 1 to 10 MPa for 2 minutes while being heated at the same temperature to obtain a molded plate having a thickness of about 1 mm. This plate-like sample was cooled for 2.5 minutes between metal plates cooled to 30 ° C. after heating and pressing. Thereafter, the PET film was peeled off from each MB molded product, and the electrical resistance of the obtained 20 wt% CNT plate-like sample was measured using a surface resistivity meter Loresta GP and Hiresta UP (MCP-T610 type and MCP-HT450 type, Dia Instruments). Measured using a product manufactured by Co., Ltd. The results of measuring the surface resistance of these molded plate samples are shown in Table 1, Table 2 and Table 3 (in the column “before lamination” in each table). The surface resistance of the 20 wt% CNT / PC, PP or PE resin composite was about 10 ² Ω / □.

An HDPE resin (HDPE, Nipolon Hard, # 1000, manufactured by Tosoh Corp.) molded plate not containing CNT having a thickness of about 1 mm prepared in advance is brought into contact with the surface of one side of the above-mentioned CNT / resin molded plate, Bonding was performed at 300 ° C. for 2 minutes between two hot plates of a hot press. At this time, a sample having a shape in which the HDPE plate and the CNT / resin composite are laminated is manufactured, and this operation is called “lamination”. These laminated samples are described below, for example, [HDPE] / [CNT / PC resin]. Further, a PTFE sheet (manufactured by Nitto Denko Corporation) having a thickness of 0.05 mm was used as a release sheet sandwiched between the hot plate and the sample when these samples were produced. After the sample is cooled, the [resin] and [CNT / resin] layers of the laminated sample are peeled off, and the surface of the white [resin] plate on the side in contact with [CNT / resin] is very close to the surface layer. A thin film in which CNTs are transferred is formed in the portion. A schematic diagram of this operation is shown in FIG.

The SEM photograph which image | photographed the cross section of PE board which CNT transferred to FIG. 3 with changing magnification is shown with the schematic diagram of a cross section in FIG. This photo is a cross section of the vicinity of the surface layer of the [PE] resin peeled from the [HDPE] / [20 wt% CNT / PP] laminate in contact with [20 wt% CNT / PP]. PE resin is shown in the lower half of the majority, and the layer of the CNT / PE composite containing CNT fibers transferred to the surface of the PE resin is shown in the upper part of the figure. A state in which CNTs migrate from the surface layer to a depth of about 10 μm was observed.

The CNT in the composite in FIG. 3 has a polar coordinate system on the assumption that one end of the CNT is the origin, the resin surface is the xy plane, the cross section of the PE resin plate is the zx plane, and the axis perpendicular to the resin surface is the z axis. The coordinates of the other end point can be expressed using two declination angles φ and θ by setting the CNT length to r. Since only CNTs observed along the cross section of the resin are observed in the SEM photograph of FIG. 3, the deflection angle φ on the xy plane is limited to 0 ° or 180 °. Since it is not necessary to distinguish the angles of 0 ° and 180 °, and it is not necessary to distinguish both ends of the CNT, if the declination θ with respect to the z axis is limited to an angle of 0 ° to 90 °, the CNT observed in the cross section is All can be described as CNTs having a declination θ of 0 ° to 90 °. Here, in the lower left figure of the SEM image of FIG. 3, 50 CNTs at arbitrary positions are randomly selected and extracted, and their declination is measured, and CNTs of 0 ° to 45 ° and 45 ° to 90 ° are measured. The following CNTs were classified and counted. As a result, 26 pieces, which is 52% of the total number, were less than 45 °. When the resin plate is peeled from the CNT resin, the CNTs are pulled in the peeling direction, so that it is considered that there is a tendency to be oriented in the direction perpendicular to the resin surface.

Tables 1 and 2 show the measurement results of the surface resistances on the sides that were in contact with each other after the PE sample was peeled from the 20 wt% CNT / resin composite (columns “after lamination” in each table). For example, each value in Table 2 shows the surface resistance before and after peeling of the [HDPE] / [20 wt% CNT / PP] laminated sample in FIG. 3, and the CNT moves to the PE side and a large amount of CNT exists. The surface resistance value of the surface to be processed is shown in the “post lamination” column of the “PE surface” row. The surface resistance of [20 wt% CNT / resin] after lamination shown in Table 1 and Table 2 shows about 10 ² Ω / □ even after lamination with any resin, and almost no change was seen before and after lamination. I couldn't. On the other hand, on the [HDPE] surface after lamination, the surface resistance of the insulator was originally about 10 ¹⁵ Ω / □ or more, but the surface resistance of the PE surface after peeling from [20 wt% CNT / PC] was 10 ^The resistivity decreased to ^{11 to 12} Ω / □, and after peeling with [20 wt% CNT / PP], a lower resistivity of 10 ³ Ω / □ was exhibited. Using these technologies to form a thin film of CNT resin composite that exhibits high electrical conductivity on the surface of the resin plate, a conductive resin composite with a very small amount of CNT added as a whole sample is prepared. Is possible.

Further, the same examination as in Example 4 was performed using PC instead of HDPE. The results are shown in Table 3. Even in the laminate of [PC] / [20 wt% CNT / PE], a CNT / PC thin film having a surface resistance of 10 ¹¹ Ω / □ was formed on the surface of the PC resin plate after peeling.

The influence of the CNT migration phenomenon on the processing temperature was tested at different temperatures. The test conditions were [PC] / [20 wt% CNT / PP] and [HDPE] / [20 wt% CNT / PP], with temperatures of 200 ° C. and 300 ° C., respectively, and a heating time of 2 minutes. Tested. The details of the experimental method are the same as in Example 4. In order to quantify the amount of CNT transferred at this time, the thickness of the CNT layer was measured using an SEM photograph of the cross section of the transferred thin film. 4 shows [PC] / [20 wt% CNT / PP] (200 ° C.), FIG. 5 shows [PC] / [20 wt% CNT / PP] (300 ° C.), and FIG. 6 shows [HDPE] / [20 wt% CNT / PP] (200 ° C.) and FIG. 7 shows a cross-sectional SEM photograph of each transferred thin film of [HDPE] / [20 wt% CNT / PP] (300 ° C.). Table 4 shows the thickness of each CNT layer. From these results, it was confirmed that the heating temperature of 300 ° C. has a larger CNT layer thickness. It was also confirmed that the HDPE resin substrate had a larger CNT layer thickness than PC. This is probably due to the difference in temperature characteristics of the viscosity of HDPE and PC.

In this CNT transfer phenomenon, how the CNT transfer amount changes when the heating time is changed was tested in a [PC] / [20 wt% CNT / PP] system. The details of the experimental method are the same as in Example 4. In the same manner as in Example 6, the method of quantifying the amount of transferred CNT was measured by using the SEM photograph of the cross section of the transferred thin film to measure the thickness of the CNT layer. SEM photographs of cross-sections of transferred PP thin film of [PC] / [20 wt% CNT / PP] produced at heating times of 2, 5, 10, 15, 20, 25, and 30 minutes. Are shown in FIGS. 8, 9, 10, 11, 12, 13, and 14, respectively. Table 5 shows the thickness of each CNT layer. From these results, it was revealed that the longer the heating time, the greater the thickness of the CNT layer. This phenomenon is considered to occur due to the driving force for transferring the CNT in the PP resin into the PC resin at the interface with the PC resin.

Whether the above-described CNT migration phenomenon occurs also with other resins was tested using the following resins. First, MB prepared by the same manufacturing method as the master batch (MB) of the CNT-resin composite shown in Example 2 was prepared. The raw material resins of MB are general-purpose resins, general-purpose engineering plastics and special engineering plastics, such as polystyrene resin (PS, PSJ-GPPS, manufactured by PS Japan Co., Ltd., 679), polyacetal resin (POM, Duracon manufactured by Polyplastics Co., Ltd.). , M90-44), polymethyl methacrylate resin (PMMA, Delpet 560F manufactured by Asahi Kasei Chemicals Corporation), acrylonitrile-butadiene-styrene copolymer resin (ABS, Stylak manufactured by Asahi Kasei Chemicals Co., 191F), and It is a polyether ether ketone resin (PEEK, manufactured by Victrex, 150P). The MB of each CNT-resin composite was kneaded using a biaxial kneader in the same manner as shown in Example 2 so that the CNT concentration was 10 wt%. The kneading temperatures were 230 ° C. (PS), 200 ° C. (POM) 240 ° C. (PMMA), 200 ° C. (ABS), and 380 ° C. (PEEK), and other conditions were appropriately adjusted according to each resin.

Using each of these types of resins and MB, a CNT-free plate and a 10 wt% CNT-resin composite plate having a size of about 150 mm square × thickness of about 4 mm were produced by injection molding. The production conditions for each injection-molded plate are as follows. First, resin and MB pellets were dried at 80 ° C. for 2 hours or longer (PEEK only at 150 ° C. for 12 hours or longer). The injection molding machine uses an apparatus manufactured by Crocner, and the heating cylinder temperature is 180 to 200 ° C. (PS), 180 to 200 ° C. (POM), 190 to 210 ° C. (PMMA), 210 to 230 for each resin. The mold temperature is set to 40 to 50 ° C. (PS), 80 to 90 ° C. (POM), 60 to 70 ° C. (PMMA), 50 to 50 ° C. for each resin. It was set as 60 degreeC (ABS) and 170-180 degreeC (PEEK). Other conditions were appropriately adjusted according to each resin.

Moreover, MB produced with the manufacturing method similar to the masterbatch (MB) of the CNT-PC resin composite shown in Example 2 was prepared. The raw material PC resin of MB is a polycarbonate (PC) resin (Panlite, L-1225LL, manufactured by Teijin Chemicals Ltd.). The MB of the CNT-PC resin composite was kneaded using a biaxial kneader in the same manner as in Example 2 so that the CNT concentration was 10 wt%.

Using this PC resin and MB of CNT-PC resin, a plate not containing CNT having a thickness of about 3 to 5 mm and a plate of 10 wt% CNT-resin composite were produced by injection molding. Molding was performed at a heating cylinder temperature of 260 to 280 ° C and a mold temperature of about 85 ° C.

First, it is determined whether or not CNT migration occurs in the same manner as the method shown in Example 4 by combining various resin plates formed with general-purpose resins and the like and a 10 wt% CNT-PC resin plate. Tested. The detailed method is as follows. A molded plate of 10 wt% CNT-PC resin composite having a thickness of about 4-5 mm is cut into a 20 mm square, and further, PS, POM, PMMA, ABS or PEEK resin not containing CNT of about 4 mm thickness A 20 mm square plate cut out from the injection molded piece was placed in contact with each other, and heated and bonded at a heating temperature of 280 ° C. to 300 ° C. between two hot plates of a hot press machine at a heating temperature of 280 ° C. to 300 ° C. for lamination. These laminated samples are described below as [(type of resin)] / [CNT / PC resin]. Further, a PTFE sheet having a thickness of 2 mm (Valflon, No. 7000 manufactured by Nippon Valqua Industries, Ltd.) was used as a release sheet sandwiched between the hot plate and the sample at the time of preparation of these samples. After cooling the sample to near room temperature, it was confirmed whether the [resin] and [CNT / resin] layers of the laminated sample could be peeled off.

Table 6 shows the results of the migration test in this [general-purpose resin] / [10 wt% CNT-PC] system. In each of PS, POM, PMMA, and ABS resins, although the resins melt, the CNT-PC resin has higher viscosity. The resin could not be peeled off. Or it is thought that it was impossible to peel off because the compatibility of each resin was good. In order to make 10 wt% CNT-PC resin a viscosity suitable for the transfer method, it is necessary to heat at around 300 ° C. At these temperatures, it is considered that the resin to be transferred is also decomposed. Therefore, in the vicinity of 280 ° C., the combination of these [general-purpose resin] / [CNT-resin] does not cause CNT transfer. It is thought that there was not. In addition, in the system where the resin to be transferred is PEEK, PEEK itself is not sufficiently melted at around 300 ° C., so it can be said that CNT transfer was difficult. In order to cause CNT migration in the [PEEK] / [CNT-PC] system, it is necessary to heat the PEEK to a melting temperature near 330 to 380 ° C., and at that temperature, the decomposition of the PC resin of [CNT-PC resin] It is assumed that the transition is difficult.

Subsequently, each [10 wt% CNT-general purpose resin] molded plate and [PC resin plate] were combined to test whether or not CNT migration occurred in the same manner as the method shown in Example 4. The detailed method is as follows. A molded plate of a composite of 10 wt% CNT-general-purpose resin or the like (PS, POM, PMMA, ABS and PEEK) having a thickness of about 4 mm is cut into a 20 mm square, and an injection-molded piece of a PC resin having a thickness of about 4 mm is formed thereon. A 20 mm square plate cut out from the plate was placed in contact with each other, heated and bonded at a heating temperature of 270 ° C. to 280 ° C. for two minutes between two hot plates of a hot press machine, and laminated. These laminated samples are described below as [PC] / [10 wt% CNT / resin type (general-purpose resin, etc.)]. Other methods were heat-treated by sandwiching a sample with a PTFE sheet in the same manner as in the system of [General-purpose resin] / [10 wt% CNT-PC]. After cooling the sample to near room temperature, it was confirmed whether each layer of [resin] and [CNT / resin] of the laminated sample could be peeled. For those that were peelable, a thin film in which CNTs migrated was formed on the surface of the white [resin] plate that was in contact with [CNT / resin] on the very near surface layer surface. Was measured.

Table 7 shows the results of the migration test in this [PC] / [10 wt% CNT-general purpose resin] system. [PC] / [10 wt% CNT-PMMA and ABS] Each resin melts each other, but CNT-general-purpose resin has higher viscosity. Therefore, CNT-general-purpose resin toward PC resin The resin could not be peeled off. Or it is thought that it was impossible to peel off because the compatibility of each resin was good. In the [PC] / [10 wt% CNT-PEEK] system, it can be said that CNT migration was difficult because 10 wt% CNT-PEEK itself was not sufficiently melted at around 280 ° C. in the first place. In the [PC] / [10 wt% CNT-POM] system, the CNT thin film / PC could be removed from the CNT-POM plate, but a homogeneous film surface sample could not be obtained, and the conductivity was measured. It was impossible and a high resistance film.

On the other hand, in the [PC] / [10 wt% CNT-PS] system, a detachable CNT thin film / PC could be produced. The thickness of the PC is about 0.5 to 1.0 mm, and the thickness of the CNT layer is non-uniform, but is estimated to be about 0.01 to 0.1 mm in cross-sectional observation with an optical microscope. . The conductivity of this film was 5 × 10 ⁴ Ω / □ as shown in Table 7. When the reproducibility of the [PC] / [10 wt% CNT-PS] system was confirmed with each 40 mm plate sample, a 1 × 10 ⁴ Ω / □ CNT thin film / PC that could be easily peeled was obtained. This system may be considered a system suitable for CNT migration. Further, the surface resistance of the 10 wt% CNT / PS plate after peeling was several Ω / □ to about 10 Ω / □, and high conductivity was maintained. From the comparison with [PC] / [10 wt% CNT-POM], it can be inferred that there is no compatibility and that a highly conductive film cannot be obtained only by being peelable. The fact that the viscosities of the resins at the same temperature almost coincide with each other suggests that this is a condition for CNT transfer.

Moreover, about the transfer method as described above, it was confirmed whether the same CNT transfer occurred repeatedly using the same CNT-resin sample plate. The sample was produced by heat treatment at 300 ° C. for 2 minutes in the same [PC] / [20 wt% CNT-PP] laminated system as in Example 7. After peeling to obtain a CNT thin film / PC, another new PC plate was stacked on the same 20 wt% CNT-PP plate, and the same lamination and heat treatment was repeated four times. In any of the four PC plates, the PC surface was clearly black and CNT migration could be confirmed, and the surface resistance was measured. As shown in Table 8, the surface resistance was 10 ³ to 10 ⁴ Ω. / □. In addition, the surface resistance of the CNT / PP plate after the transfer treatment was also maintained at several Ω / □. From this result, the possibility of repeated use of the 20 wt% CNT-PP plate used for the transfer method was shown.

When the slope and number of CNTs in the composite obtained by transferring CNTs were measured by the same method as in Example 4, CNTs of 0 ° or more and less than 45 ° were all antistatic. The number of fine carbon fibers having an inclination of 0 degree or more and less than 45 degrees with respect to the axis perpendicular to the layer surface was 20 to 60% by mass of the total number of fine carbon fibers.

By using the composite material manufacturing technique of the present invention, a composite material having high conductivity can be obtained even when a low concentration of conductive filler is added. Therefore, it can be applied to the field of electronic equipment that does not like static electricity, the antistatic film in a clean room, the heat-dissipating resin material, the radio wave shielding material, and the like.

Claims (17)

A resin molded body in which an antistatic layer is accumulated on at least one surface of the resin molded body, the antistatic layer including fine carbon fibers, and an axis perpendicular to the surface of the antistatic layer in the arrangement state of the fine carbon fibers A resin molded product, wherein the number of fine carbon fibers having an inclination of 0 degree or more and less than 45 degrees is 20 to 60% of the number of whole fine carbon fibers. The resin molding according to claim 1, wherein the fine carbon fibers are randomly arranged in a three-dimensional direction. The resin molded body according to claim 1 or 2, wherein a plurality of fine carbon fibers are in electrical contact with each other at a surface layer portion of the antistatic layer of the resin molded body. The resin molded body according to any one of claims 1 to 3, wherein the resin molded body has a surface resistivity of 10 ¹ to 10 ¹² Ω / □. The resin molded body according to any one of claims 1 to 4, wherein in the resin molded body, a resin constituting the molded body is a thermoplastic resin. The thermoplastic resin is cellulose acetate, ethyl cellulose, polydimethylsiloxane, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl pyrrolidine, sucrose octaacetate, polycarbonate (PC), polyethylene (PE), polypropylene (PP ), Polystyrene (PS), acrylotolyl / butanediene / styrene resin (ABS), polyvinyl chloride (PVC), acrylonitrile / styrene resin (AS), methacrylic resin (PMMA), vinyl chloride (PVC), polyamide (PA), polyacetal (POM), modified polyphenylene ether (m-PPE), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), ultra-high polymer Polyethylene (UHPE), polyphenylene sulfide (PPS), polyimide (PI), polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyethersulfone (PES), polyetheretherketone (PEEK), liquid crystal The resin constituting the resin molded body containing at least one selected from a polymer (LCP), polytetrafluoroethylene (PTFE), and polyurethane (PU) is one kind of thermoplastic resin. The resin molded product according to claim 5. The resin molded body according to any one of claims 1 to 6, wherein the fine carbon fiber has an outer diameter of 0.5 to 800 nm. The resin molded body according to claim 7, wherein the fine carbon fibers are single-layer fine carbon fibers, double-layer fine carbon fibers, or multilayer fine carbon fibers. The fine carbon fiber is a network-like carbon fiber structure composed of carbon fibers having an outer diameter of 15 to 100 nm, and the carbon fiber structure is formed in a form in which a plurality of the fine carbon fibers are extended. It has a granular part that binds carbon fibers to each other, and the granular part is formed during the growth process of the fine carbon fiber, and is 1.3 times larger than the outer diameter of the fine carbon fiber. The resin molded product according to claim 7 or 8, wherein the resin molded product has the following. A resin plate containing another fine carbon fiber is brought into contact with the target resin plate on which the antistatic layer is to be accumulated on the surface, and is heated at 100 to 400 ° C., and kept in a heated state for 1 to 60 minutes. A method for producing a resin molded body, wherein the antistatic layer is accumulated by transferring the fine carbon fibers to the surface layer of the target resin plate by peeling the two resin plates from each other. The method for producing the resin molded body, wherein a resin plate containing fine carbon fibers having a viscosity at 100 to 400 ° C higher than a viscosity of the target resin plate at 100 to 400 ° C is used. A method for producing a resin molded article. In the method for producing a resin molded body, the resin material for the resin plate containing fine carbon fibers is a resin material having no compatibility. In the method for producing a resin molded body, the absolute value of the difference between the surface tension of the target resin plate and the surface tension of the fine carbon fiber is T1, and the surface tension of the resin plate containing the fine carbon fiber and the carbon fiber The resin plate containing fine carbon fibers is selected so that T1 <T2 when the absolute value of the difference from the surface tension of T2 is T2, and is brought into contact with the target resin plate. Item 13. A method for producing a resin molded article according to any one of Items 12 to 12. In the method for producing a resin molded body, a release sheet for easily peeling the target resin plate from the hot plate is polytetrafluoroethylene (PTFE), polyether ether ketone (PEEK), polysulfone (PSF), polyphenylene. The method for producing a resin molded body according to claim 13, wherein any one of sulfide (PPS), polyetherimide (PEI), polyethersulfone (PES), and polyimide (PI) is used. A method for improving the conductivity of a resin molded body having a surface resistivity of 10 ¹² Ω / □ or less using the method for producing the resin molded body until the surface resistivity is 10 ¹² Ω / □ or less. The method for producing a resin molded body according to any one of claims 10 to 14, wherein in the method for producing the resin molded body, the heated resin molded body is cooled stepwise. . A method of using the resin molded body as a conductive material, an electromagnetic wave shield, an electromagnetic wave absorber, an infrared shield, or a heating element.

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