JP2012229345A - Molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber-reinforced thermoplastic resin composition for obtaining a molded article excellent in electromagnetic wave shielding ability and dynamic characteristics.SOLUTION: The molded article is obtained by molding a molding material comprising (A) a carbon fiber, (B) a metal fiber and (C) a thermoplastic resin, wherein the weight ratio of (A) the carbon fiber and (B) the metal fiber is (B)/(A)=1/5-1/25 and, in the molded article, the weight-average fiber length of (A) the carbon fiber is >0.3 mm and the weight-average fiber length of (A) the carbon fiber/the weight average fiber length of (B) the metal fiber is 1/2-1/6.

Description

  The present invention relates to a molded article, and particularly relates to a molded article excellent in conductivity, electromagnetic shielding properties, weight reduction, and mechanical properties.

  Compositions composed of reinforcing fibers and thermoplastic resins are widely used in sports equipment applications, aerospace applications and general industrial applications because they are lightweight and have excellent mechanical properties. Reinforcing fibers used in these fiber-reinforced thermoplastic resin compositions reinforce molded products in various forms depending on the intended use. Among the reinforcing fibers, carbon fibers are particularly preferable from the viewpoint of the balance of specific strength, specific rigidity, and lightness, and among them, polyacrylonitrile-based carbon fibers are preferably used.

  Thermoplastic material reinforced with carbon fiber becomes a conductive material, but in order to obtain electromagnetic shielding and electrical conductivity equivalent to metal materials, it is necessary to increase the amount of carbon fiber in the thermoplastic material. And not in terms of cost.

  In addition, a thermoplastic material reinforced with metal fibers becomes a highly conductive material, but its specific gravity is heavy and the adhesion between the fibers and the resin is extremely poor, so the mechanical strength is also lowered.

  As a conductive thermoplastic resin composition reinforced with carbon fiber and metal fiber, Patent Document 1 discloses a long fiber reinforced thermoplastic resin composition composed of carbon fiber, metal fiber, and thermoplastic resin. Molded articles composed of the described resin composition have a large amount of metal fibers and are insufficient in weight reduction. Moreover, there is no description about the fiber length of the carbon fiber and metal fiber in a molded object, and the electromagnetic wave shielding property in low specific gravity is inadequate. Patent Document 2 describes a resin composition obtained by melt-kneading carbon fiber, metal fiber, and thermoplastic resin, but the fiber length of the molded product is shortened by melt-kneading, and electromagnetic shielding properties, electrical conductivity Inferior in property and mechanical properties.

  As described above, when the thermoplastic resin is molded as a matrix in the prior art, it is lightweight and does not have both electromagnetic shielding properties, electrical conductivity and mechanical properties, and is lightweight and has electromagnetic shielding properties, electrical conductivity and mechanical properties. Development of an excellent fiber-reinforced molded product has been desired.

JP-A-4-279638 JP 2006-45330 A

  In view of the background of the prior art, an object of the present invention is to provide a molded article that is lightweight and excellent in electromagnetic shielding properties, electrical conductivity, and mechanical properties.

As a result of intensive studies to achieve the above object, the present inventors have found the following molded product that can achieve the above-mentioned problems.
(1) A molded product obtained by molding a molding material containing (A) carbon fiber, (B) metal fiber, and (C) thermoplastic resin, and the weight ratio of (A) carbon fiber to (B) metal fiber (B) / (A) = 1/5 to 1/25, and the weight average fiber length of the (A) carbon fiber in the molded product exceeds 0.3 mm, and (A) the weight average fiber length of the carbon fiber / (B) A molded product, wherein the weight average fiber length of the metal fibers is 1/2 to 1/6.
(2) The molded article according to (1), wherein the molding material is a long fiber pellet obtained by coating (A) carbon fiber and (B) metal fiber with (C) a thermoplastic resin.
(3) Thermoplastic which said molding material mix | blends 0.1-10 weight part of (D) electroconductive fillers other than (A) and (B) with respect to 100 weight part of (C) thermoplastic resin. The molded article according to (2), which is a long fiber pellet coated with a resin composition.
(4) The molded article according to (3), wherein the conductive filler (D) is at least one selected from carbon black, carbon nanotube, and vapor grown carbon fiber.
(5) The molding material is a long fiber pellet coated with a thermoplastic resin composition obtained by blending 1 to 20 parts by weight of (E) an antistatic agent with respect to 100 parts by weight of (C) a thermoplastic resin ( The molded product according to any one of 2) to (4).
(6) The molded article according to (5), wherein (E) the antistatic agent is a polymer type antistatic agent and / or an ionic liquid.
(7) The molded product according to any one of (1) to (6), wherein the molded product is an electrical component storage container.
(8) (A) Carbon fiber and (B) metal fiber in which the weight ratio of (A) carbon fiber and (B) metal fiber is in the range of (B) / (A) = 1/5 to 1/25 (C ) Long fiber pellets coated with thermoplastic resin.

  The molded article of the present invention is a lightweight molded article having excellent electromagnetic shielding properties, electrical conductivity, and mechanical properties. The molded article of the present invention is extremely useful for electrical / electronic equipment, OA equipment, home appliances, housings or parts of automobiles, particularly electric parts storage containers for electric cars.

It is a figure which shows the measuring method of the volume resistance value of a molded article in an Example.

  The carbon fiber (A) used in the present invention is not particularly limited, but high-strength and high-modulus carbon fibers can be used, and these may be used alone or in combination. Among these, PAN-based, pitch-based, rayon-based carbon fibers and the like can be mentioned. From the viewpoint of balance between the electrical conductivity, strength, and elastic modulus of the obtained molded product, PAN-based carbon fibers are more preferable.

Further, the carbon fiber is preferably a carbon fiber that has been sized from the viewpoint of strength, elastic modulus, and handling properties.
As a sizing treatment, a liquid (sizing solution) containing a sizing agent after drying a water-wet carbon fiber bundle having a moisture content of about 20 to 80% by weight wetted by water in a generally known surface treatment step and water washing step. It is the processing method which attaches.

  As the surface treatment, it is preferable to perform an electric field surface treatment with an acidic or alkaline aqueous solution.

  Although it does not specifically limit as a sizing agent, The compound which has functional groups, such as an epoxy group, a urethane group, an amino group, and a carboxyl group, can be used, These may use 1 type or 2 types or more together.

  The sizing agent adhesion amount is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 2% by mass with respect to the mass of the carbon fiber alone. % Or less is more preferable. If it is 0.01% by mass or less, the effect of improving adhesiveness is hardly exhibited. If it is 10% by mass or more, the physical properties of the molded product may be lowered.

  There are no particular restrictions on the means for applying the sizing agent, but there are, for example, a method of immersing in a sizing liquid through a roller, a method of contacting a roller to which the sizing liquid is adhered, and a method of spraying the sizing liquid in a mist form. . Moreover, although either a batch type or a continuous type may be sufficient, the continuous type which has good productivity and small variations is preferable. At this time, it is preferable to control the sizing solution concentration, temperature, yarn tension, and the like so that the amount of the sizing agent active ingredient attached to the carbon fiber is uniformly attached within an appropriate range. Moreover, it is more preferable to vibrate the carbon fiber with ultrasonic waves when applying the sizing agent.

  Although the drying temperature and drying time should be adjusted according to the amount of the compound attached, the time required for complete removal of the solvent used for applying the sizing agent and drying is shortened, while the thermal deterioration of the sizing agent is prevented, and carbon From the viewpoint of preventing the fiber bundle from becoming hard and deteriorating the spreadability of the bundle, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower. .

  Examples of the solvent used for the sizing agent include water, methanol, ethanol, dimethylformamide, dimethylacetamide, and acetone. Water is preferable from the viewpoint of easy handling and disaster prevention. Accordingly, when a compound insoluble or hardly soluble in water is used as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse in water.

  Moreover, there is no restriction | limiting in particular in the number of single yarns at the time of setting it as a carbon fiber bundle, It can use within the range of 100-350,000, Especially, it uses within the range of 1,000-250,000. It is preferable. Further, from the viewpoint of productivity of carbon fibers, those having a large number of single yarns are preferable, and it is preferable to use them within a range of 20,000 to 100,000.

  The carbon fiber content is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the (C) thermoplastic resin, and if it is less than 5 parts by weight, the electromagnetic shielding properties and mechanical properties are inferior, and if it exceeds 60 parts by weight, the specific gravity becomes heavy. Not good in cost. From the viewpoints of light weight, electromagnetic shielding properties, electrical resistance, and mechanical properties, it is preferably 7 to 50 parts by weight, more preferably 10 to 40 parts by weight.

  (B) Although a metal fiber is not specifically limited, At least 1 sort (s) chosen from a stainless steel fiber, an aluminum fiber, a copper fiber, and a brass fiber can be used, and a stainless steel fiber is especially preferable from the balance of electroconductivity and intensity | strength.

  Furthermore, the fiber diameter of the metal fiber is preferably 1 to 50 μm, more preferably 1 to 20 μm, from the balance between conductivity and mechanical properties.

  As for the content of the metal fiber, the weight ratio of (A) carbon fiber and (B) metal fiber is (B) / (A) = 1/5 to 1/25. Preferably it is 1/5 to 1/10. If the weight ratio is less than 1/25, the electromagnetic shielding properties are inferior, and if it exceeds 1/5, the mechanical properties and the appearance are deteriorated, and the specific gravity becomes heavy.

  (C) The thermoplastic resin is not particularly limited, but polycarbonate, polystyrene, polyester, polyamide, polyolefin, acrylic resin, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, polyphenylene oxide, polybutylene terephthalate, polyether ether ketone, Known thermoplastic resins such as polyphenylenesulfone, liquid crystal polymers, polymers such as fluororesin or copolymers thereof, or polymer alloys thereof may be mentioned. From the viewpoint of weight reduction, polyolefin, polyamide, polycarbonate, polyoxymethylene are preferable. Polybutylene terephthalate, polyphenylene oxide, liquid crystal polyester, and polyphenylene sulfide are preferably used.

  Here, the polyamide is a resin composed of a polymer having an amide bond, and is mainly composed of amino acid, lactam or diamine and dicarboxylic acid. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, penta Methylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylene Diamine, metaxylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane ,Screw Aliphatic and fats such as (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine Cyclic and aromatic diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5 -Aliphatic, alicyclic and aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like. In the present invention, from these raw materials Each derived polyamide homopolymer or copolymer alone Others can be used in the form of mixtures.

  In the present invention, a particularly useful polyamide is a polyamide having a crystal melting temperature of 150 ° C. or higher and excellent in heat resistance and strength. Specific examples include polycaproamide (polyamide 6), polyhexamethylene adipamide. (Polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polypentamethylene sebacamide (polyamide 510), poly Tetramethylene sebamide (polyamide 410), polyhexamethylene dodecane (polyamide 612), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polycaproamide / polyhexamethylene adipamide copolymer (polyamide 6) / 66), Ricaproamide / polyhexamethylene terephthalamide copolymer (polyamide 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (polyamide) 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (polyamide 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), Polyhexamethylene terephthalamide / polydecanamide copolymer (polyamide 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide Polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyxylylene adipamide (polyamide XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (polyamide 6T / M5T), Polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (polyamide 6T / 5T), polypentamethylene terephthalamide / polypentamethylene adipamide copolymer (5T / 56), polynonamethylene terephthalamide (polyamide 9T) and these Examples thereof include mixtures and copolymers.

  Particularly preferred are polyamide 6, polyamide 66, polyamide 56, polyamide 610, polyamide 510, polyamide 410, polyamide 612, polyamide 11, polyamide 12, polyamide 6/66, polyamide 66 / 6T, polyamide 6T / 6I, polyamide 66. Examples include / 6I / 6, polyamide 6T / 5T, and the like. Furthermore, it is also practically preferable to use these polyamides as a mixture depending on required properties such as moldability, heat resistance, toughness, and surface properties. Among these, polyamide 6, polyamide 66, polyamide 610, polyamide 11, Polyamide 12 and polyamide 66 / 6T are most preferred.

  The terminal group concentration of these polyamides is not particularly limited, but those having a terminal amino group concentration of 3 × 10 −5 mol / g or more have a resin (B) having a reactive functional group or a reactive functional group. It is preferable in terms of reactivity with the compound (D). The terminal amino group concentration here can be measured by dissolving a sample in an 85% phenol-ethanol solution, using thymol blue as an indicator, and titrating with an aqueous hydrochloric acid solution.

  The degree of polymerization of these polyamides is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is preferably in the range of 1.5 to 7.0, particularly 1 A polyamide resin in the range of .8 to 6.0 is preferred. When the relative viscosity is less than 1.5, it is difficult to develop the impact resistance and impact absorption characteristics of the thermoplastic resin composition of the present invention, and when the relative viscosity is more than 7.0, the thermoplastic resin composition This is not preferable because the melt viscosity of the product is remarkably increased and it becomes difficult to form a molded article.

  The polycarbonate is selected from bisphenol A, that is, 2,2′-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylalkane, 4,4′-dihydroxydiphenylsulfone, and 4,4′-dihydroxydiphenyl ether. Preferred are those using one or more selected dihydroxy compounds as the main raw material. Among these, bisphenol A, that is, a product produced using 2,2'-bis (4-hydroxyphenyl) propane as a main raw material is preferable. Specifically, polycarbonate obtained by the transesterification method or the phosgene method using the above bisphenol A or the like as a dihydroxy component is preferable. Further, the dihydroxy compound such as bisphenol A may be other dihydroxy compounds copolymerizable therewith, such as 4,4′-dihydroxydiphenylalkane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenyl ether, and the like. They can be used in combination, and the amount of other dihydroxy compounds used is preferably 10 mol% or less based on the total amount of dihydroxy compounds.

  The polycarbonate has a specific viscosity of 0.1 to 2.0, particularly 0.5 when measured at 20 ° C. by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride from the viewpoint of excellent impact resistance and moldability. Those in the range of -1.5 are preferred, and those in the range of 0.8-1.5 are most preferred.

  Polyolefin is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Modified polyolefin resin modified with an unmodified olefin resin obtained by polymerizing or copolymerizing olefins such as hexadecene and 1-octadecene, and an unsaturated carboxylic acid or an acid anhydride or derivative thereof. Is preferred.

  Specific examples include homopolymers such as polyethylene resin, polypropylene resin, poly 1-butene resin, poly 1-pentene resin, poly 4-methyl-1-pentene resin, or 1,4-hexadiene, dicyclo Copolymer obtained by copolymerizing one or more non-conjugated diene monomers such as pentadiene, 2,5-norbornadiene, 5-ethylidenenorbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene Examples include coalescence.

  In the present invention, a polyethylene resin, a polypropylene resin, and a poly-4-methyl-1-pentene resin are preferable in that the phase structure is easily controlled and heat resistance or impact resistance is improved. From the viewpoint of heat resistance, polypropylene is preferable. A resin is more preferable, and a polyethylene resin is more preferable in terms of toughness.

  By using the modified polyolefin resin, a composition with improved mechanical properties can be obtained. Examples of compounds selected from unsaturated carboxylic acids, acid anhydrides or derivatives thereof used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid , Methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Hydroxyethyl, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2, 2 1) -5-heptene-2,3-dicarboxylic acid, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferable, and maleic acid, 5-norbornene-2,3-dicarboxylic acid or acid anhydrides thereof are particularly preferable.

  In addition, there is no particular limitation on the method for introducing a compound selected from these unsaturated carboxylic acids, acid anhydrides or derivatives thereof into the polyolefin resin, and the polyolefin resin and the unsaturated carboxylic acid, which are the main components, and acid anhydrides thereof are preliminarily used. Or a compound selected from the group consisting of derivatives thereof and graft-introducing into an unmodified polyolefin resin using a compound selected from unsaturated carboxylic acid, acid anhydride or derivative thereof and a radical initiator. Can be used. The amount of the modifier component introduced is preferably 0.001 to 40 mol%, more preferably 0.01 to 35 mol%, based on the entire olefin monomer in the modified polyolefin resin.

  In the present invention, as will be described later, (A) carbon fibers and (B) metal fibers are formed into long fiber pellets made of (C) thermoplastic resin, and the long fiber pellets are molded as a molding material. In this case, the thermoplastic resin (C) may contain other elastomers, fillers and additives as long as the object of the present invention is not impaired.

  Examples of other elastomers include unmodified olefin elastomers, styrene elastomers, urethane elastomers, ester elastomers, and amide elastomers. Specific examples of olefin elastomers include ethylene-α-olefin copolymers. And ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-ethylidene norbornene copolymer and ethylene-propylene-hexadiene copolymer. Specific examples of styrene elastomers include styrene-butadiene, styrene-isoprene-styrene, styrene-butadiene-styrene, styrene-ethylene-butadiene-styrene, styrene-ethylene-propylene-styrene random copolymers, and blocks. Examples thereof include a copolymer, a hydrogenated product of the block copolymer, and an acrylonitrile-butadiene-styrene copolymer.

  Fillers and additives include dispersants, flame retardants, crystal nucleating agents, UV absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, heat stabilizers, release agents , Plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, or coupling agents. These elastomers, fillers, and additives can be used alone or in combination of two or more.

  In this invention, you may mix | blend (D) electroconductive fillers other than (A) and (B) in (C) thermoplastic resin further. Examples of the conductive filler (D) include carbon black, vapor grown carbon fiber, and carbon nanotube.

  Examples of carbon black include furnace black, acetylene black, thermal black, channel black, and ketjen black.

  The vapor grown carbon fiber is a fine carbon fiber having an average fiber diameter of 10 to 200 nm obtained by a production method in which a hydrocarbon such as benzene or toluene is vaporized to grow crystals in a high temperature furnace. Examples of the growth carbon fiber include VGCF manufactured by Showa Denko KK.

  Examples of the carbon nanotubes include single-walled nanotubes and multi-walled nanotubes having an average diameter of 0.4 to 50 nm obtained by, for example, a vapor deposition method, an arc discharge method, a laser evaporation method, and the like. It can take any form such as a tubular form.

  When mix | blending these (D) electroconductive fillers, the compounding quantity has the preferable inside of the range of 0.1-10 weight part with respect to 100 weight part of (C) thermoplastic resins. If it is less than 0.1 part by weight, sufficient conductivity cannot be obtained, and if it exceeds 10 parts by weight, moldability may be reduced due to thickening of the resin composition.

  In the present invention, (E) an antistatic agent may be further added to (C) the thermoplastic resin. Examples of (E) antistatic agents include polymer antistatic agents and ionic liquids. As the polymer type antistatic agent, a polymer in which conductive units such as polyether, quaternary ammonium salt, sulfonate and the like are incorporated in a block or randomly, a polymer charge transfer type conjugate, or the like can be used.

  Among these, polyether antistatic agents are preferable from the viewpoint of dispersibility with the matrix resin. Specifically, polyethylene oxide, polyether ester amide, polyether amide imide, ethylene oxide-epihalohydrin copolymer, methoxy polyethylene glycol Examples include (meth) acrylate copolymers, copolymers of polyolefin blocks and hydrophilic polymer blocks described in JP-A-2001-278985, and the like. From the viewpoint of dispersibility with polyolefin resins, polyolefin blocks and hydrophilic A block copolymer of a conductive polymer is more preferable.

  The number average molecular weight of the polymer antistatic agent used in the present invention is preferably 2,000 to 1,000,000 from the viewpoint of resin physical properties and antistatic properties.

  Here, the number average molecular weight is a value determined by gel permeation chromatography (GPC).

  Commercially available antistatic agents of the present invention can be used as they are. For example, Pelestat 300 (polymer antistatic agent: manufactured by Sanyo Kasei Co., Ltd.), Pelestat 230 (polymer antistatic agent: manufactured by Sanyo Kasei Co., Ltd.) ) And the like.

  As the ionic liquid, organic compound salts such as imidazolium salts, pyridinium salts, ammonium salts and phosphonium salts which are liquid at room temperature, which are liquid at room temperature, are preferably used.

  Examples of ionic liquids that are imidazolium salts include 1,3-dimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, and 1-ethyl-3- Methylimidazolium bis (trifluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium nitrate, Ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium hexafluorophosphate 1-ethyl-3-methyl Imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tosylate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-n-butyl-3-methylimidazolium trifluoromethanesulfone Narate, 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-butyl-3 -Methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium 2- (2-methoxyethoxy) ethyl sulfate, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl- 3-Methylimidazolium Tet Fluoroborate, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-methyl- 3-octylimidazolium chloride, 1-methyl-3-octylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propyloctylimidazolium tris (trifluoromethylsulfonyl) methide, 1-butyl-2 , 3-dimethylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-methyl-3- ( 3,3,4,4,5,5,6,6,7,7 , 8,8,8-tridecafluorooctyl) imidazolium hexafluorophosphate, and 1-butyl-3- (3,3,4,4,5,5,6,6,7,7,8, 8,8-tridecafluorooctyl) imidazolium hexafluorophosphate and the like.

  Examples of the ionic liquid that is a pyridinium salt include 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide, 1- Propyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium trifluoromethanesulfonate Examples include butyl-4-methylpyridinium hexafluorophosphate and 1-butyl-4-methylpyridinium tetrafluoroborate.

  Examples of ionic liquids that are ammonium salts include tetrabutylammonium heptadecafluorooctane sulfonate, tetrabutylammonium nonafluorobutane sulfonate, tetrapentylammonium methanesulfonate, tetrapentylammonium thiocyanate, and methyl- Examples include tri-n-butylammonium methylsulfate.

  Examples of ionic liquids that are phosphonium salts include tetrabutylphosphonium methanesulfonate, tetrabutylphosphoniumnium p-toluenesulfonate, trihexyltetradecylphosphonium bis (trifluoroethylsulfonyl) imide, and trihexyltetradecyl. Phosphonium bis (2,4,4-trimethylpentyl) phosphinate, trihexyl tetradecyl phosphonium bromide, trihexyl tetradecyl phosphonium chloride, trihexyl tetradecyl phosphonium decanoate, trihexyl tetradecyl phosphonium hexafluorophosphinate , Triethyltetradecylphosphonium tetrafluoroborate, tributylmethylphosphonium tosylate, and the like.

  As the ionic liquid of the present invention, a commercially available product can be used as it is. For example, CIL-313 (1-butyl-3-methylpyridine-1-ium trifluoromethanesulfonate: manufactured by Nippon Carlit Co., Ltd.), CIL-312 (N-butyl-3-methylpyridinium / bistrifluoromethanesulfonylimide: manufactured by Nippon Carlit Co., Ltd.).

  The blending amount of these antistatic agents is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the (C) thermoplastic resin. In the case of an ionic liquid, it is more preferably within a range of 0.1 to 5 parts by weight. If it is less than 0.1 part by weight, sufficient conductivity cannot be obtained, and if it exceeds 20 parts by weight, the mechanical properties and heat resistance of the molded article may be lowered.

  In the present invention, the weight average fiber length of the carbon fibers in the molded product exceeds 0.3 mm, and (A) the weight average fiber length of the carbon fibers / (B) the weight average fiber length of the metal fibers is 1/2 to 1 / 6 is important, and in order to obtain such a molded product, it is preferable to use the following molding material. For example, (A) carbon fiber roving is led to (C) an impregnation die filled with a resin composition obtained by melt-kneading a thermoplastic resin, and the resin composition is uniformly impregnated between carbon fiber filaments, and then a nozzle And then solidified by cooling and pelletizing to a predetermined length, and carbon fiber-containing long fiber pellets and (B) metal fiber rovings are filled with (C) a resin composition obtained by melting and kneading a thermoplastic resin. Then, the resin composition is uniformly impregnated between the filaments of the metal fibers, then pulled out through a nozzle, cooled and solidified, pelletized to a predetermined length, and dry blended with metal fiber-containing long fiber pellets (A) and In this method, the ratio of (B) is obtained within the range. Here, the long fiber pellet is such that, as shown in Japanese Patent Publication No. 63-37694, conductive fiber bundles are arranged substantially parallel to the longitudinal direction of the pellet, and the length of the conductive fiber bundle in the pellet is the pellet. It refers to what is substantially the same as the length.

  Further, the roving composed of (A) carbon fiber and (B) metal fiber is led to an impregnation die filled with a resin composition obtained by melt-kneading (C) a thermoplastic resin, and the resin composition is placed between carbon fiber filaments. Long fiber pellets containing both carbon fibers and metal fibers may be used after being uniformly impregnated, drawn through a nozzle, pelletized to a predetermined length after cooling and solidification.

  More preferably, using a crosshead die, (A) a carbon fiber roving is impregnated with a resin composition obtained by melt kneading (C) a thermoplastic resin, and then cooled, solidified, and pelletized to a predetermined length The composition and (B) roving of metal fibers are impregnated with (C) a resin composition obtained by kneading and kneading a thermoplastic resin, then solidified by cooling and dry blended into pellets of long fibers. How to get.

  In addition, (A) roving made of carbon fiber and (B) roving made of metal fiber are dispersed in the fiber before impregnating with (C) thermoplastic resin in order to improve fiber dispersibility during molding. It may be impregnated.

  Although the length of a long fiber pellet does not have a restriction | limiting in particular, Usually, it is the range of 3-15 mm. If the pellet length is too short, the fibers may be shortened and the electromagnetic shielding properties, electrical conductivity, strength, impact, and electromagnetic shielding properties may be reduced.If the pellet length is too long, a biting failure may occur in the molding machine. is there. The pellet length is preferably 3 to 12 mm, and more preferably 5 to 10 mm.

  The molded article of the present invention can be obtained from such long fiber pellets using a generally known injection molding machine such as an in-line screw type or a pre-plunger type. In particular, injection press molding in which a predetermined amount of the mold is opened in advance and the mold clamping is completed after the resin is filled in the mold is preferable from the viewpoints of reducing the filling pressure, preventing fiber breakage, and reducing warpage. In the injection press molding, the mold clamping may be started simultaneously with the start of resin filling, or the mold clamping may be started in the middle of resin filling.

The weight average fiber length of the carbon fiber and metal fiber in the molded product was determined by ashing the molded product at 500 ° C. for 2 hours, taking out the carbon fiber and metal fiber in the sample, and removing the carbon fiber and metal fiber from the sample 3 Place in a beaker with water of liter, use an ultrasonic cleaner to uniformly disperse the carbon fiber and metal fiber in water, suck 1 cc of the aqueous solution in which the carbon fiber and metal fiber are uniformly dispersed with a syringe having a tip diameter of 8 mm, 10 × It is a value obtained by sampling the sample after having been sampled on a petri dish having a depression of 10 mm, taking a picture of carbon fibers and metal fibers in the petri dish, measuring the length of about 1000 pieces, and calculating by the following formula.
Weight average fiber length = Σ (Mi ² × Ni) / Σ (Mi × Ni)
Mi: Fiber length (mm)
Ni: Number.

  In the present invention, the weight average fiber length of (A) carbon fibers in the molded product exceeds 0.3 mm, and (A) the weight average fiber length of carbon fibers / (B) the weight average fiber length of metal fibers is 1/2. It is important that it is ˜1 / 6, and by setting it within this range, it is possible to obtain a molded article having good electromagnetic shielding properties and mechanical properties. The weight average fiber length of the (A) carbon fiber in the molded product is preferably 0.3 to 5 mm, more preferably 0.3 to 3 mm, and still more preferably 0.3 to 2 mm.

  As for the weight average fiber length of a metal fiber, 0.6-30 mm is preferable, More preferably, it is 0.6-18 mm, More preferably, it is 0.6-12 mm.

  As a molded article, it is suitable for automobile parts such as various modules such as an instrument panel, a door beam, an under cover, a lamp housing, a pedal housing, a radiator support, a spare tire cover, and a front end. Furthermore, home and office electrical product parts such as telephones, facsimiles, VTRs, copiers, televisions, microwave ovens, audio equipment, toiletries, laser discs, refrigerators, and air conditioners are also included. Further, there are a housing used for a personal computer, a mobile phone and the like, and a member for electric / electronic equipment represented by a keyboard support which is a member for supporting a keyboard inside the personal computer. The molded product of the present invention is excellent in balance between lightness, mechanical strength characteristics, electrical conductivity, and electromagnetic wave shielding properties. Therefore, the container for portable electrical / electronic equipment parts and electrical parts for electric vehicles such as battery cases, inverters, etc. It is particularly suitable for use as a case or ECU case.

  Hereinafter, the present invention will be described in more detail with reference to examples. The evaluation method of the molded product in the examples and comparative examples is as follows.

[Bending elastic modulus and bending strength]
A parallel part of the ISO type test piece was cut out, and a bending test was carried out in accordance with ISO178 in the 5566 type test manufactured by Instron, and bending elastic modulus (GPa) and bending strength (MPa) were obtained.

[Charpy impact test]
A parallel part of an ISO type test piece is cut out, and a Charpy impact test without a V notch is performed according to ISO 179 using a C1-4-01 type tester manufactured by Tokyo Tester Co., Ltd. to calculate an impact value (kJ / m ² ). did.

[Volume resistivity]
An ISO type tensile test piece was cut into a size of 80 × 10 mm (4 mmt) with a band saw, and the cut surface was smoothed with sand paper having a roughness of No. 400 to obtain a test piece for measuring volume resistivity. In accordance with JIS K 6271, volume low efficiency (Ω · cm) was measured by a four-terminal method shown in FIG. 1 using an ohmmeter HIOKI3541.

[Electromagnetic shielding]
Using an evaluation apparatus manufactured by Microwave Factory, the average shielding effect (dB) was measured in the region of the near electric field of 10 (MHz) to 1 (GHz) according to the KEC method. The shielding effect was calculated by the following formula (1). A 150 × 150 mm (3 mmt) square plate was used as the test piece.
_{SE = 20 × log10E 0 / E} X (1)
SE: Shielding effect (dB)
E ₀ : Spatial electric field strength when there is no shield material E _X : Spatial electric field strength when there is a shield material.

[appearance]
Using 150 × 150 mm (3 mmt) square plates molded for electromagnetic wave shielding, 10 molded products were visually observed and judged according to the following criteria.
◎: There is surface gloss and there is no warpage of the molded product ○: There is little surface gloss, but there is no warpage of the molded product ×: There are irregularities on the surface, but there is no warpage of the molded product XX: Warpage of the molded product Has occurred.

[Weight average fiber length]
The center part of the ISO type tensile dumbbell test piece (4 mmt) was cut into 20 × 10 mm (4 mmt), and ashed at 500 ° C. for 2 hours, and the carbon fiber and metal fiber in the sample were taken out. The taken-out carbon fiber and metal fiber were put into a beaker together with 3 liters of water, and the carbon fiber and metal fiber were uniformly dispersed in water using an ultrasonic cleaner. 1 cc of an aqueous solution in which carbon fibers and metal fibers were uniformly dispersed was sucked with a dropper having a tip diameter of 8 mm, sampled in a petri dish having a 10 × 10 mm depression, and then dried. The average fiber length was calculated by taking pictures of carbon fibers and metal fibers in the petri dish, measuring the length of about 1000 fibers. The calculation formula is as follows.
Weight average fiber length = Σ (Mi ² × Ni) / Σ (Mi × Ni)
Mi: Fiber length (mm)
Ni: Number.

[Example 1]
First, the carbon fiber bundle which is the component (A) is opened while being heated to 200 ° C., and the gear pump is attached so that 5 parts by weight of the melted dispersant (terpene resin) is attached to 100 parts by weight of the carbon fiber bundle. And weighed with a curtain coater. Next, the carbon fiber bundle is sufficiently impregnated with the terpene resin by passing through a plurality of squeeze bars in an atmosphere heated to a temperature 50 ° C. higher than the melting temperature of the terpene resin, and the continuous carbon fiber bundle and the terpene resin And obtained a composite (impregnation process)
Next, the component (C) is put into a hopper of an extruder and extruded into a coating die in a melt-kneaded state, and at the same time, the coated composite is continuously fed into the coating die, The composite was coated, and the discharge amount of the extruder and the supply amount of the composite were adjusted to obtain a continuous carbon fiber reinforced resin strand having a CF content of 40 wt% (coating step).

  Then, the continuous carbon fiber reinforced resin group strand was cooled and solidified to 100 ° C. or lower, and cut to 6.0 mm length using a cutter to obtain a long fiber pellet made of core-sheath carbon fiber.

  Next, the metal fiber bundle as the component (B) is opened while being heated to 200 ° C., and 5 parts by weight of the molten dispersant (terpene resin) is attached to 100 parts by weight of the metal fiber bundle. Weighed with a gear pump and applied with a curtain coater. Next, the metal fiber bundle is sufficiently impregnated with the terpene resin by passing through a plurality of squeeze bars in an atmosphere heated to a temperature 50 ° C. higher than the melting temperature of the terpene resin, and the continuous metal fiber bundle and the terpene resin To obtain a composite (impregnation step).

  Next, the component (C) is put into a hopper of an extruder and extruded into a coating die in a melt-kneaded state, and at the same time, the coated composite is continuously fed into the coating die, The composite was coated, and the discharge amount of the extruder and the supply amount of the composite were adjusted to obtain a continuous metal fiber reinforced resin strand having a metal fiber content of 20 wt% (coating process).

  Thereafter, the continuous metal fiber reinforced resin group strand was cooled and solidified to 100 ° C. or less, and was cut into a length of 6.0 mm using a cutter to obtain a long fiber pellet made of a core-sheath type metal fiber.

  Next, the obtained long fiber pellet made of carbon fiber, long fiber pellet made of metal fiber, and (C) were dry blended so as to have the ratio shown in Table 1, and then an injection molding machine (J110AD manufactured by Nippon Steel Works). , A test piece for characteristic evaluation (molded product) was molded at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained molded product was evaluated according to the evaluation method described above. The evaluation results are collectively shown in Table 1.

  As shown in Table 1, the evaluation results of this molded product were excellent in electromagnetic shielding properties, electrical conductivity, and mechanical properties.

[Examples 2 to 5]
The obtained long fiber pellets made of carbon fibers, long fiber pellets made of metal fibers, and (C) were molded and evaluated in the same manner as in Example 1 except that they were dry blended so as to have the ratio shown in Table 1. It was. The evaluation results of this molded product are shown in Table 1.

[Example 6]
Table 1 shows the long fiber pellets made of carbon fibers, the long fiber pellets made of metal fibers, and (C-2), where (C-2) is the component (C) charged into the hopper of the extruder. After dry blending to a ratio, a characteristic evaluation test piece (molded product) was molded using the injection molding machine at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. The obtained test piece was subjected to a characteristic evaluation test after drying for 8 hours in a vacuum dryer at a temperature of 80 ° C. and a vacuum degree of 1013 hPa. Next, the obtained molded product was evaluated according to the evaluation method described above.

[Example 7]
Table 1 shows the long fiber pellets made of carbon fibers, the long fiber pellets made of metal fibers, and (C-3), where (C-3) is the component (C) charged into the hopper of the extruder. After dry blending to a ratio, a characteristic evaluation test piece (molded product) was molded at a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. using the injection molding machine. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained molded product was evaluated according to the evaluation method described above.

[Examples 8 and 9]
The component (C) is supplied from the main hopper of the extruder, then (D-1) is supplied from the downstream side hopper, kneaded sufficiently at a barrel temperature of 220 ° C., and further degassed from the downstream vacuum vent. A long fiber pellet made of carbon fiber coated with a mixture of (C-1) and (D-1) and a long fiber pellet made of metal fiber coated with a mixture of (C-1) and (D-1). Obtained.

  Next, it was carried out except that the obtained long fiber pellet made of carbon fiber, the long fiber pellet made of metal fiber, and the mixture of (C-1) and (D-1) were dry blended so as to have the ratio shown in Table 1. Molding was performed in the same manner as in Example 1, and evaluation was performed.

[Example 10]
Except that the component (C) was a mixture of (C-1) and (E-1) and the ratio shown in Table 1 was used, a long fiber pellet was obtained, molded and evaluated in the same manner as in Example 1. .

[Example 11]
Except that the component (C) was a mixture of (C-1) and (E-2) and the ratios shown in Table 1 were used, long fiber pellets were obtained, molded and evaluated in the same manner as in Example 1. .

[Example 12]
A mixture of components (C-1) and (E-2) is supplied from the main hopper of the extruder, and then (D-1) is supplied from the side hopper downstream of the mixture, and kneaded sufficiently at a barrel temperature of 220 ° C. Further, degassing is further performed from a downstream vacuum vent, and (C-1), (D), and (C-1), (D) and (C-1), (D), and (C-1), (D-1), and (E-2) coated with a mixture of -1) and long fiber pellets made of metal fibers coated with a mixture of (E-2) were obtained.

  Next, the obtained long fiber pellets made of carbon fibers, long fiber pellets made of metal fibers, and a mixture of (C-1), (D-1) and (E-2) so as to have the ratio shown in Table 1. Except for dry blending, it was molded and evaluated in the same manner as in Example 1.

[Example 13]
A component (A) carbon fiber bundle and (B) metal fiber bundle are made into a composite fiber bundle so as to have the ratio shown in Table 1, and the dispersion agent (terpene-based resin) which is opened and melted while being heated to 200 ° C. ) Was measured with a gear pump so that 5 parts by weight was attached to 100 parts by weight of the composite fiber bundle, and applied with a curtain coater. Next, the composite fiber bundle is sufficiently impregnated into the composite fiber bundle by passing through a plurality of squeeze bars in an atmosphere heated to a temperature 50 ° C. higher than the melting temperature of the terpene resin, and the continuous composite fiber bundle and the terpene resin are obtained. A complex with was obtained.

  Next, the component (C) is put into a hopper of an extruder and extruded into a coating die in a melt-kneaded state, and at the same time, the coated composite is continuously fed into the coating die, The composite was coated, and a continuous composite fiber reinforced resin strand was obtained so as to have the ratio shown in Table 1 by adjusting the discharge amount of the extruder and the supply amount of the composite.

  Thereafter, the continuous composite fiber reinforced resin strand was cooled and solidified to 100 ° C. or lower, and was cut into a length of 6.0 mm using a cutter to obtain long fiber pellets composed of core-sheath carbon fibers and metal fibers.

  Next, the obtained long fiber pellets made of carbon fiber and metal fiber were molded in the same manner as in Example 1 using the injection molding machine described above, and evaluated.

[Comparative Examples 1-3]
The obtained long fiber pellets made of carbon fibers, long fiber pellets made of metal fibers, and (C-1) were molded and evaluated in the same manner as in Example 1 except that they were dry blended so as to have the ratios shown in Table 2. Went. The evaluation results of this molded product are shown in Table 2. Comparative Example 1 was inferior in electromagnetic shielding properties and electrical conductivity, and Comparative Examples 2 and 3 were inferior in mechanical properties, surface irregularities were visually observed, and appearance was inferior.

[Comparative Example 4]
Components (A) and (B) were cut to ¼ inch with a cartridge cutter. Next, Nippon Steel Corporation TEX-30α type twin screw extruder (screw diameter 30 mm, L / D = 32) was used to supply the component (C-1) from the main hopper, (A) and (B) cut as described above were supplied from the side hopper, kneaded sufficiently at a barrel temperature of 220 ° C. and a rotation speed of 150 rpm, and further deaerated from a downstream vacuum vent. The feed was adjusted to the ratio shown in Table 2 using a weight feeder. The molten resin was discharged from a die port (diameter 5 mm), and the obtained strand was cooled and then cut with a cutter to obtain short fiber pellets.

  Next, the obtained short fiber pellet was molded in the same manner as in Example 1 and evaluated. The evaluation results of this molded product are shown in Table 2.

  The comparative example was inferior in electromagnetic shielding properties, electrical conductivity, and mechanical properties, warped in the molded product, and inferior in appearance.

[Comparative Example 5]
The component (C-2) was molded from the main hopper, and molded and evaluated in the same manner as in Comparative Example 4 except that the barrel temperature was 260 ° C. The comparative example was inferior in electromagnetic shielding properties, electrical conductivity, and mechanical properties, warped in the molded product, and inferior in appearance.

  This example was superior in electromagnetic wave shielding properties, electrical conductivity, and mechanical properties as compared with Comparative Examples 1-5.

The carbon fibers (A) used in the examples and comparative examples are as follows.
(A): Diameter 7μ, carbon fiber (“Torayca” T700SC manufactured by Toray Industries, Inc.)
Similarly, (B) metal fiber is as follows.
(B): Diameter 12μ, metal fiber (“NASSON FILAMENT YARN” manufactured by Nippon Seisen Co., Ltd.)
Similarly, (C) the thermoplastic resin is as follows.
(C-1): Polypropylene ("Prime Polypro" J137 manufactured by Prime Polymer Co., Ltd.)
(C-2): Polyamide (“Amilan” CM3001, melting point 265 ° C., manufactured by Toray Industries, Inc.)
(C-3): Polycarbonate (“Taflon” A2200 manufactured by Idemitsu Kosan Co., Ltd.)
Similarly, (D) the conductive filler is as follows.
(D-1): Furnace Black (“Mitsubishi Carbon Black” MA100 manufactured by Mitsubishi Chemical Corporation)
Similarly, (E) antistatic agent is as follows.
(E-1): Polymer type antistatic agent (Pelestat 300 manufactured by Sanyo Kasei Co., Ltd.)
(E-1): Ionic liquid (CIL-313 manufactured by Nippon Carlit Co., Ltd.)
Similarly, the dispersant is as follows.
Terpene resin having a softening point of 150 ° C. (“Mighty Ace G” 150 manufactured by Yasuhara Chemical Co., Ltd.).

  The molded article of the present invention is a molded article capable of producing a molded article having excellent electromagnetic shielding properties and mechanical properties, and is suitable for electrical / electronic equipment, OA equipment, home appliances or automobile parts, internal members, and housings. Used.

1. Test piece 2. Electrode 3. 3. Ammeter voltmeter

Claims (8)

(A) A molded product obtained by molding a molding material containing carbon fiber, (B) metal fiber, and (C) thermoplastic resin, wherein the weight ratio of (A) carbon fiber to (B) metal fiber is (B ) / (A) = 1/5 to 1/25, and the weight average fiber length of the (A) carbon fiber in the molded product exceeds 0.3 mm, and (A) the weight average fiber length of the carbon fiber / (B). A molded product, wherein the weight average fiber length of the metal fibers is 1/2 to 1/6. The molded article according to claim 1, wherein the molding material is a long fiber pellet obtained by coating (A) carbon fiber and (B) metal fiber with (C) a thermoplastic resin. A thermoplastic resin composition in which the molding material in the previous period is composed of 0.1 to 10 parts by weight of (D) conductive filler other than (A) and (B) with respect to 100 parts by weight of (C) thermoplastic resin. The molded article according to claim 2, which is a long fiber pellet coated with. The molded article according to claim 3, wherein the conductive filler (D) is at least one selected from carbon black, carbon nanotube, and vapor grown carbon fiber. The first molding material is a long fiber pellet coated with a thermoplastic resin composition obtained by blending 1 to 20 parts by weight of (E) an antistatic agent with respect to 100 parts by weight of (C) a thermoplastic resin. 4. The molded article according to any one of 4. 6. The molded article according to claim 5, wherein (E) the antistatic agent is a polymer type antistatic agent and / or an ionic liquid. The molded article according to any one of claims 1 to 6, wherein the molded article is an electrical component storage container. (A) Carbon fiber and (B) Metal fiber is in the range of (B) / (A) = 1/5 to 1/25 (A) Carbon fiber and (B) Metal fiber (C) Thermoplastic Long fiber pellets coated with resin.

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