KR102087749B1 - Flame retardant electromagnetic wave shielding and heat radiating carbon-composite composition and molded article manufactured using same - Google Patents

Abstract

The present invention relates to an electromagnetic wave shielding and heat dissipation composite material composition having flame retardancy and a molded article obtained therefrom, and the composite material composition according to the present invention has electrical insulation properties and low thermal conductivity, and has excellent electromagnetic wave shielding efficiency and flame retardant properties However, it has excellent moldability and can be effectively applied to products requiring flame retardancy, electromagnetic wave shielding, and heat dissipation characteristics.

Description

Flame-retardant electromagnetic shielding and heat dissipation carbon composite material composition and molded article manufactured therefrom FLAME RETARDANT ELECTROMAGNETIC WAVE SHIELDING AND HEAT RADIATING CARBON-COMPOSITE COMPOSITION AND MOLDED ARTICLE MANUFACTURED USING SAME}

The present invention relates to an electromagnetic wave shielding and heat dissipation composite material composition having flame retardancy and a molded article obtained therefrom.

Thermoplastic resins, especially high performance plastics with excellent mechanical properties and heat resistance, are used in a variety of applications. For example, polyamide resin or polyester resin is excellent in balance of mechanical properties and toughness, so it is mainly used for various electrical / electronic parts, mechanical parts, automobile parts, etc., mainly for injection molding. Among polyester resins, poly Butylene terephthalate or polyethylene terephthalate is widely used as a material for industrial molded products such as connectors, relays and switches in automobiles and electrical / electronic devices because of its excellent moldability, heat resistance, mechanical properties and chemical resistance. In addition, non-crystalline resins such as polycarbonate resins have excellent transparency and dimensional stability, and are used in various fields, including various optical materials, electrical equipment, OA equipment, and parts such as automobiles.

In general, polymer resins are difficult to apply as electromagnetic shielding and electrical and electronic components due to the properties of electrical insulation and low thermal conductivity. Therefore, in order to implement electromagnetic shielding and thermal conductivity within the polymer, when graphite is used, it has high thermal conductivity. It has low electromagnetic shielding properties. In addition, when carbon fibers are used, they have high electromagnetic shielding properties, but exhibit low thermal conductivity. In addition, in order to impart flame retardancy, when using an organophosphate metal salt flame retardant or a melamine flame retardant, the amount that can be used with a high filler content of existing graphite and carbon fibers is limited. When a large amount of flame retardant (for example, 20 wt% or more) is used, flame retardancy may be realized, but there are limitations in product development due to poor extrusion processability due to low fluidity, and there are difficulties in molding defects during injection processing.

The problem to be solved by the present invention is to provide a carbon composite material composition having good moldability while maintaining physical properties such as flame retardancy and electromagnetic wave shielding.

Another problem to be solved by the present invention is to provide a molded article having improved flame retardancy, electromagnetic wave shielding, and heat dissipation properties obtained from the carbon composite material composition.

The present invention to solve the above problems,

It provides a carbon composite material composition comprising a heat-resistant polymer resin, graphene nanoplates, graphite and carbon fibers.

The graphene nanoplate may have a particle size of 5 to 20 μm and a thickness of 5 to 30 nm.

In addition, the graphene nanoplate may be to include a modified graphene nanoplate treated with phosphorus or fluorine.

In addition, the graphite may be any one or more of natural graphite, artificial graphite and expanded graphite.

In addition, the graphite may be expanded graphite having a particle diameter of 45 to 100 μm.

According to one embodiment, the composition comprises 30 to 70 parts by weight of a heat-resistant polymer resin, 10 to 50 parts by weight of graphene nanoplates, 5 to 30 parts by weight of graphite, and 5 to 30 parts by weight of carbon fiber based on 100 parts by weight of the total May be

In addition, the composition may further include 10 parts by weight or less of a flame retardant.

The flame retardant may be any one or more of melamine-based flame retardants, phosphorus-based flame retardants and organophosphinate metal salt flame retardants.

According to one embodiment, the carbon fiber may have a length of 0.01 to 100 mm, and a diameter of 0.1 to 100 μm.

In addition, the heat-resistant polymer resin may be polyamide.

According to one embodiment, the polyamide resin is polycaprolactam (polyamide-6), polyamide-11, polyamide-12, polyamide-4,6, polyamide-4,8, polyamide-4, 10, polyamide-4,12, polyamide-6,6, polyamide-6,9, polyamide-6,10, polyamide-6,12, polyamide-10,10, polyamide-12,12 , Polyamide-6, I, polyamide-6, T, polyamide-6, T / 6,6-copolyamide, polyamide-6, T / 6-copolyamide, polyamide-6 / 6, 6-copolyamide, polyamide-6,6 / 6, T / 6, I-copolyamide, polyamide-6, T / 2-MPMDT-copolyamide, polyamide-9, T, polyamide- 6 / 12-copolyamide, polyamide-6 / 11-copolyamide, polyamide-6,6 / 11-copolyamide, polyamide-6,6 / 12-copolyamide, polyamide-6 / 6,10-copolyamide, polyamide-6,6 / 6,10-copolyamide, polyamide-4,6 / 6-copolyamide, polyamide-6 / 6,6 / 6,10-co Made of polyamide It may be at least one selected from the group true.

In addition, the composition further comprises one or more additives selected from the group consisting of impact modifiers, flame retardant aids, lubricants, plasticizers, heat stabilizers, dripping inhibitors, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives and drip inhibitors It may be included.

In addition, the present invention provides a molded article obtained by processing the composition.

The processing may be by at least one of an extrusion process, an injection process, or an extrusion and injection process.

The molded article may have a thermal conductivity of about 10 to about 30 W / m · K.

In addition, the electromagnetic wave shielding efficiency (EMI SE) may be about 30 dB or more.

The composite composition according to the present invention not only has excellent injection moldability, but also has electromagnetic wave shielding performance, heat dissipation properties, and flame retardancy since it contains an electric / thermal conductivity and a flame retardant filler on a polymer resin base. The composite composition according to the present invention can be used for all components that require electronic vehicle shielding and heat dissipation performance while having flame retardancy such as automotive electronic components, housings for battery electronic components, and battery pack housings.

The present invention can be applied to various conversions and can have various embodiments, and specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention. In the description of the present invention, when it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted.

As used herein, the term “composite material” may be used interchangeably with “composite material” in the present specification, and may be understood to mean a material formed by gathering two or more materials.

Hereinafter, the flame-retardant carbon composite material composition according to the embodiment of the present invention and the molded article obtained therefrom will be described in more detail.

Flame-retardant carbon composite material composition according to the present invention,

It is characterized by including a heat-resistant polymer resin, graphene nanoplates, graphite and carbon fibers.

Hereinafter, each component will be described in more detail.

Heat-resistant polymer

The heat-resistant polymer may be polyamide, but is not limited thereto, and may be used without limitation as long as it is used as a heat-resistant polymer in the related industry.

When considering the moldability of the heat-resistant polymer, it is preferable to use those having a relative viscosity of 1.5 to 5, more preferably 2 to 4.5, measured at a concentration of 1 g / dl at 25 ° C. When the relative viscosity is less than 1.5, since it is a low viscosity, processing after melt kneading becomes difficult, and it may be difficult to obtain desirable physical properties. Moreover, if it is larger than 5, the fluidity at the time of molding processing is poor due to the high viscosity, and it is difficult to make a molded product because a sufficient injection pressure is not applied.

The content of the heat-resistant polymer may be 30 to 70 parts by weight or 40 to 60 parts by weight based on 100 parts by weight of the total composition.

As the polyamide resin, a nylon resin, a nylon copolymer resin, and mixtures thereof can be used. Polyamide-6 (nylon 6) obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecaractam, which are commonly known as nylon resins; Nylon polymers obtainable from amino acids such as aminocapronic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; Ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonanahexamethylenediamine , Metaxylenediamine, paraxylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis ( 4-aminocyclohexane) methane, bis (4-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperidine, etc. Aliphatic, alicyclic or aromatic dicarboxylic acids, such as aliphatic, alicyclic or aromatic diamines of adipic acid, sebacic acid, azelaic acid, terephthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, etc. Nylon polymers obtainable from polymerization of; Copolymers or mixtures of these can be used. As the nylon copolymer, a copolymer of polycaprolactam (nylon 6) and polyhexamethylene sebacamide (nylon 6,10), a copolymer of polycaprolactam (nylon 6) and polyhexamethyleneadipamide (nylon 66), And copolymers of polycaprolactam (nylon 6) and polylaurylactam (nylon 12).

According to one embodiment, the polyamide resin is polycaprolactam (polyamide-6), polyamide-11, polyamide-12, polyamide-4,6, polyamide-4,8, polyamide-4, 10, polyamide-4,12, polyamide-6,6, polyamide-6,9, polyamide-6,10, polyamide-6,12, polyamide-10,10, polyamide-12,12 , Polyamide-6, I, polyamide-6, T, polyamide-6, T / 6,6-copolyamide, polyamide-6, T / 6-copolyamide, polyamide-6 / 6, 6-copolyamide, polyamide-6,6 / 6, T / 6, I-copolyamide, polyamide-6, T / 2-MPMDT-copolyamide, polyamide-9, T, polyamide- 6 / 12-copolyamide, polyamide-6 / 11-copolyamide, polyamide-6,6 / 11-copolyamide, polyamide-6,6 / 12-copolyamide, polyamide-6 / 6,10-copolyamide, polyamide-6,6 / 6,10-copolyamide, polyamide-4,6 / 6-copolyamide, polyamide-6 / 6,6 / 6,10-co Made of polyamide To preferably at least one selected from the group true, and, more preferably, poly caprolactam (PA6).

In addition to the aforementioned heat-resistant resin, various resins may be used in the composite composition or may be added together as necessary. For example, polycarbonate resin, polypropylene resin, aramid resin, aromatic polyester resin, polyolefin resin, polyester carbonate resin, polyphenylene oxide resin, polysulfone resin, polyethersulfone resin, polyarylene resin, cycloolefin series Resin, polyetherimide resin, polyacetal resin, polyvinyl acetal resin, polyketone resin, polyetherketone resin, polyetheretherketone resin, polyarylketone resin, polyethernitrile resin, liquid crystal resin, polybenzimidazole resin, A vinyl-based polymer or copolymer resin obtained by polymerizing or copolymerizing one or more vinyl monomers selected from the group consisting of polyparabanic acid resins, aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters, and vinyl cyanide compounds, diene- Aromatic alkenyl compound copolymer resin, cyan Vinyl-diene-aromatic alkenyl compound copolymer resin, aromatic alkenyl compound-diene-vinyl cyanide-N-phenylmaleimide copolymer resin, vinyl cyanide- (ethylene-diene-propylene (EPDM))-aromatic alkenyl compound At least one selected from the group consisting of copolymer resin, polyolefin, vinyl chloride resin, and chlorinated vinyl chloride resin can be used. The specific types of these resins are well known in the art, and examples that can be used in the composition of the present invention can be appropriately selected by those skilled in the art.

The polyolefin resin may be, for example, polypropylene, polyethylene, polybutylene, and poly (4-methyl-1-pentene), and combinations thereof, but is not limited thereto. In one embodiment, the polyolefin is a polypropylene homopolymer (eg, atactic polypropylene, isotactic polypropylene, and syndiotactic polypropylene), polypropylene copolymer (eg For example, polypropylene random copolymers), and mixtures thereof. Suitable polypropylene copolymers include, but are not limited to, the presence of comonomers selected from the group consisting of ethylene, but-1-ene (ie 1-butene), and hex-1-ene (ie 1-hexene). Random copolymers prepared from the polymerization of propylene underneath. In such polypropylene random copolymers, the comonomer may be present in any suitable amount, but is typically in an amount of about 10 wt% or less (e.g., about 1 to about 7 wt%, or about 1 to about 4.5 wt%). Can exist.

The polyester resin refers to a homopolyester or a copolymerized polyester which is a polycondensation of a dicarboxylic acid component skeleton and a diol component skeleton. Here, as the homo polyester, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene diphenylate The back is typical. In particular, since polyethylene terephthalate is inexpensive, it can be used for applications that are very versatile and is preferable. In addition, the said copolymer polyester is defined as the polycondensate which consists of at least 3 or more components selected from the component which has a dicarboxylic acid skeleton and a component which has a diol skeleton illustrated next. As a component having a dicarboxylic acid skeleton, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ' And -diphenyldicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexanedicarboxylic acid and their ester derivatives. As a component having a glycol skeleton, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, 2,2-bis ( And 4'-β-hydroxyethoxyphenyl) propane, isosorbate, 1,4-cyclohexanedimethanol, spiroglycol, and the like.

The polycarbonate resin may be prepared by reacting diphenols with phosgene, halogen formate, carbonic acid ester, or a combination thereof. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also referred to as 'bisphenol-A'), 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro -4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) And ethers. Among them, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) Cyclohexane can be used, more preferably 2,2-bis (4-hydroxyphenyl) propane.

The polycarbonate resin may be a mixture of copolymers made from two or more diphenols. In addition, the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.

Examples of the linear polycarbonate resin include bisphenol-A-based polycarbonate resin. Examples of the branched polycarbonate resin include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride and trimellitic acid with diphenols and carbonates. The polyfunctional aromatic compound may be included in 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester carbonate copolymer resin include those produced by reacting a bifunctional carboxylic acid with diphenols and carbonates. At this time, as the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, or the like can be used.

Examples of the cycloolefin-based polymer include norbornene-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Examples of the specific examples include Apel (ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals Co., Ltd.), Atone (norbornene-based polymer manufactured by JSR Corporation), Zeonoa (norbornene-based polymer manufactured by Nippon Zeon), and the like.

The polyphenylene oxide resin is also referred to as polyphenylene ether, and has a structure in which -O- is bonded to a phenylene group as a repeating unit. The phenylene group may have various substituents, for example, methyl group, ethyl group, halogen group, hydroxy group, and the like.

Graphene  Nano plate

Graphene is a two-dimensional carbon allotrope, and the method of manufacturing it is a peeling method that physically separates one layer of graphene from graphite, and a chemical oxidation / reduction method to obtain graphene by chemically reducing graphite by dispersing graphite in a dispersion. , There is a thermal decomposition method to obtain a graphene layer through high-temperature thermal decomposition on a silicon carbide (SiC) substrate, and a chemical vapor deposition method, and among them, a chemical vapor deposition method can be exemplified as a method for synthesizing high-quality graphene.

According to one embodiment, the graphene may have a shape aspect ratio of 0.1 or less, a graphene layer number of 100 or less, and a specific surface area of 300 m ² / g or more. The graphene refers to a single mesh surface of the SP ² bond of carbon (C) in the hcp structure of graphite, and recently, a graphene composite layer having a plurality of layers is also classified as graphene in the broad sense.

According to one embodiment, the graphene nanoplate may have a particle size of 5 to 20 μm and a thickness of 5 to 30 nm having high dispersibility.

In addition, it is also possible to use a modified graphene nanoplate containing phosphorus or fluorine or the like treated with a dispersant containing phosphorus or fluorine.

In particular, when a graphene nanoplate modified with phosphorus is used, it is possible to secure better flame retardancy by blocking the oxygen and forming a protective layer by the phosphoric acid layer, and blocking the char generated by dehydration.

The content of the graphene nanoplate to obtain this effect may be 10 to 50 parts by weight or 20 to 40 parts by weight based on 100 parts by weight of the total composition.

black smoke

The graphite may be any one or more of natural graphite, artificial graphite and expanded graphite.

Synthetic (artificial) graphite and expanded graphite can be used without limitation as long as they are used as thermally conductive / electrically conductive fillers in the related industry.

For example, the expanded graphite is one that is heated and expanded from the interlayer compound through chemical treatment with sulfuric acid or the like on the flaky graphite. For example, after treating natural scale-like graphite with a mixed acid of concentrated sulfuric acid and concentrated acetic acid, washing and dewatering is performed to expand to 800 ° C to 1200 ° C to obtain expanded graphite expanded 10 to 200 times the volume of the raw material graphite. have. As graphite, natural scaly graphite, artificial graphite, or the like can be used. As the acid treatment system for graphite, fuming nitric acid, concentrated sulfuric acid-potassium permanganate, concentrated sulfuric acid, ammonium persulfate and the like can be used.

According to one embodiment, expanded graphite is preferred, and in particular, a particle size of 45 to 100 μm can realize high thermal conductivity by forming an optimal thermal path in the polymer resin together with the graphene nanoplate described above. have.

The content of graphite for obtaining the above effect may be 5 to 30 parts by weight or 10 to 30 parts by weight based on 100 parts by weight of the total composition.

Carbon fiber

Carbon fiber has a high specific surface area, excellent electrical conductivity, adsorption, and the like, and can be obtained by growing a carbon material produced by decomposing and growing a gaseous compound containing carbon at a high temperature in the form of a fiber in a metal catalyst prepared in advance. The thermally decomposed carbons can be formed in a graphene layer through a step of adsorption, decomposition, absorption, diffusion, and precipitation on a specific metal catalyst surface of a few nanometers in size to form carbon fibers with excellent crystallinity and purity. have. Carbon fibers formed on catalyst particles of transition metals, such as nickel, iron, and cobalt, grow to a nano-scale size, which is 100 times thinner than that of other types of general-purpose carbon fibers, which is 100 times thinner. It is more useful because it has a specific surface area and is excellent in electrical conductivity, adsorption and mechanical properties.

The carbon fiber synthesis method mainly includes an electric discharge method, a laser deposition method, a plasma chemical vapor deposition method, and a chemical vapor deposition (CVD) method. Factors influencing the growth of carbon fiber include temperature, carbon source, catalyst, and substrate type. Among these, the diffusion action of the substrate and the catalyst particles and the difference in interfacial interaction between them affect the shape and microstructure of the synthesized carbon fiber.

According to one embodiment, it is possible to improve the degree of reflection and absorption of electromagnetic waves through graphene nanoplates and carbon fibers having high dispersibility.

Carbon fiber for obtaining such an effect may have a length of 0.01 to 100 mm, a diameter of 0.1 to 100 μm, preferably a length of 1 to 50 mm, a diameter of 0.1 to 10 μm, and the content is based on 100 parts by weight of the total composition It may be 5 to 30 parts by weight or 5 to 20 parts by weight.

Other additives

The composite composition may further include one or more additives selected from the group consisting of flame retardants, flame retardants, lubricants, plasticizers, heat stabilizers, anti-dropping agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives, and drip inhibitors. And the content may be used in an amount of 10 parts by weight or less based on 100 parts by weight of the composition. The specific types of these additives are well known in the art, and examples that can be used in the composition of the present invention can be appropriately selected by those skilled in the art.

According to one embodiment, the flame retardant may be any one or more of a melamine-based flame retardant, phosphorus-based flame retardant and organophosphinate metal salt flame retardant.

Manufacturing and processing methods

According to one embodiment, the method for preparing the composite composition is not particularly limited, but is supplied to a conventionally known melt mixer such as a single or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll to supply approximately 100 to 500 ° C. Or a method of kneading at a temperature of 200 to 400 ° C, for example.

In addition, the mixing order of the raw materials is not particularly limited, and after blending the above-mentioned heat-resistant polymer resin, graphene nanoplate, graphite, carbon fiber, and additives as necessary in advance, the melting point of the heat-resistant polymer resin is shortened, or A method of uniformly melt-kneading with a twin-screw or more multi-screw extruder, a method of removing a solvent after mixing in a solution, and the like are used. Among them, from the viewpoint of productivity, a method of uniformly melt-kneading with a single-screw or a twin-screw multi-screw extruder is preferable, and a method of uniformly melt-kneading at a melting point or higher of a heat-resistant polymer resin using a multi-screw twin-screw extruder is preferred Is used.

As a kneading method, a method of collectively kneading components such as a heat-resistant polymer resin, graphene nanoplate, graphite, and carbon fiber, and a resin composition containing a high concentration of graphene nanoplate, graphite, carbon fiber, etc. in a heat-resistant polymer resin ( Master pellets), and then, by adding the heat-resistant polymer resin, graphene nanoplates, graphite, carbon fibers, etc. so as to have a specified concentration, a method of melt-kneading (master pellet method), etc. can be exemplified, and any kneading method You may use

As another method, a method of preparing a composite material composition by supplying a heat-resistant polymer resin and other necessary additives from the extruder side and supplying graphene nanoplates, graphite or carbon fibers to the extruder using a side feeder It can be preferably used.

Through the kneading method, a composite composition having a form such as pellets may be prepared.

The electric component housing, battery electronic component housing, battery housing, etc. using the resin composition can be molded by any method such as injection molding, extrusion molding, blow molding, press molding, spinning, etc., which are generally known. It may be an extrusion process, an injection process, or an extrusion and injection process, and since such a molding method is widely known, a detailed description is omitted.

The molded article prepared using the composition according to the present invention may have an in-plane of 10 to 30 W / mK. Thermal conductivity is a property value indicating the size of thermal conductivity, and is expressed as the ratio of the flow rate of heat energy (heat amount passing through a unit cross-sectional area during a unit time) Q and the temperature gradient grad T. That is, the thermal conductivity K can be expressed as "K = Q / grad T".

In addition, the molding may have an electromagnetic wave shielding efficiency of 30 dB or more (@ 1 GHz, thickness 2 mm), and more preferably 30 to 60 dB.

The composite material obtained through the above method is not only easy to mold, but also has excellent electromagnetic wave shielding performance and heat dissipation characteristics, so it can be used for various applications requiring electromagnetic wave shielding and heat dissipation characteristics, in particular, various parts such as automobile parts, electric and electronic parts, and building members. You can. Specific applications include: air flow meters, air pumps, thermostat housings, engine mounts, ignition bobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuums Pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, top and bottom of radiator tank, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap , Oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various Automobile under hood parts such as clips, various valves, and various pipes, torque control level , Seat belt parts, register blades, washer levers, wind regulator handles, knobs on wind regulator handles, passing light levers, sun visor brackets, various interior parts for automobiles, roof rails, fenders, garnishes, etc. Automotive exterior parts such as bumper, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, grille apron cover frame, lamp reflector, lamp bezel, door handle, wire harness connector, SMJ connector-, PCB Various automotive connectors such as connectors, door grommet connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, notebook PC housings and internal parts, LED display housings and internal parts, printer housings and internal parts, mobile phones , Mobile PC, portable terminal housings and internal parts such as portable mobiles, recording media (CD, DVD, PD, FDD, etc.) drives There may be mentioned electric and electronic parts typified by the housing and internal components, a housing and inner parts of copying machine, facsimile housings and internal parts of the parabolic antenna and the like.

In addition, VTR parts, television parts, irons, hair dryers, rice cooker parts, microwave oven parts, sound parts, video camera parts such as video cameras, projectors, laser disks (registered trademark), compact disks (CDs), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray Disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processors Examples are parts of household and office electrical products, such as parts.

In addition, housings or internal parts such as electronic instruments, home game machines, and portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, and variable capacitors Case, optical pickup, oscillator, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motors It is particularly useful as an electrical / electronic component such as a brush holder, a transformer member, a coil bobbin, or various automotive connectors such as a wire harness connector, SMJ connector, PCB connector, and door grommet connector.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains may easily practice. However, the present invention may be implemented in various different forms, and is not limited to the embodiments described herein.

< Example  1 to 7 and Comparative example  1 to 5> Preparation of carbon composite material composition

Carbon composite material compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were prepared with the composition shown in Table 1 below.

Pellet having a size of 0.2mm X 0.3mm X 0.4mm by adding components of the contents as shown in Table 1 to a twin-screw extruder (L / D = 42, Φ = 40mm) and melt extrusion while raising the temperature profile to 280 ° C. Was prepared. The prepared pellets were injected under the conditions of a flat profile with an injection temperature of 280 ° C in an injection machine to prepare specimens of 3.2 mm in thickness, 12.7 mm in length, and dog-bone type.

Comparative example Example One 2 3 4 5 One 2 3 4 5 6 7 Polycaprolactam
(Parts by weight) 55 35 45 30 25 55 55 50 50 45 40 40 Artificial graphite
(Parts by weight) 10 10 10 15 10 15 - - - - - - Expanded graphite
(Parts by weight) 35 35 35 20 20 - 15 20 20 20 20 20 Carbon fiber
(Parts by weight) - - - 10 20 10 10 10 10 10 10 20 Graphene nanoplate
(Parts by weight) - - - - - 20 20 20 - - - - Graphene nanoplate containing phosphorus
(Parts by weight) - - - - - - - - 20 20 30 30 Organophosphinate metal salt flame retardant
(Parts by weight) - 20 - 20 20 - - - - - - - Melamine flame retardant
(Parts by weight) - - 10 - - - - - - - - - Phosphorous flame retardant
(Parts by weight) - - - 5 5 - - - - 5 - -

The ingredients used in Table 1 are as follows.

-Polyamide resin: Poly caprolactam (PA6) with a relative viscosity of KP chemical 2.5

-Artificial graphite: TIMCAL, average particle size 45 ~ 100 ㎛

-Expanded graphite: Nippon graphite, purity 98% or more, average particle size 70 ~ 150 ㎛

-Carbon fiber: Zoltec, length 6 mm, diameter 7.5 μm, purity 95% or more

-Graphene nanoplate: LG Chem, 5 ~ 20 ㎛, thickness 5 ~ 30 nm graphene

-Graphene nano-plate containing phosphorus: used as phosphorus in the manufacturing process

-Flame retardant: Clariant, Exolit OP-1230, organophosphinate metal salt flame retardant; Melamine cyanurate 99% or more melamine-based flame retardant; Daihachi's PX-200 phosphorus flame retardant.

< Experimental example > Characterization of carbon composite material moldings

Standards for thermal conductivity, electromagnetic interference shielding efficiency (EMI SE), flame retardant properties and formability of the carbon composite material specimens of Examples 1 to 7 and Comparative Examples 1 to 5 having the composition shown in Table 1 above. It was analyzed using the test method and the results are shown in Table 2.

-Thermal conductivity: ASTM E1461 standard test method, unit W / mK

-Electromagnetic shielding efficiency: ASTM D4936 standard test method, 1GHz, 2mm thickness, unit dB

-Flame retardant properties: UL94V test method for vertical burning test

-Formability: According to the degree of molding of the specimen, it was evaluated as 5 points, 5 points, 4 points, 3 points, 2 points, and 1 point, very bad.

Comparative example Example One 2 3 4 5 One 2 3 4 5 6 7 Thermal conductivity
(W / mK) 10 8 9 7 6 10 13 15 15 15 25 20 EMI SE
(dB) 10 10 10 15 25 30 35 35 35 35 45 55 Flame retardant properties NG V-1 NG V-0 V-0 V-1 V-1 V-1 V-1 V-0 V-0 V-0 Formability 5 3 3 One 0 5 5 5 5 5 5 5

From the results of Table 2, it can be seen that the carbon composite material compositions according to Examples 1 to 7 were provided with electromagnetic wave shielding, heat dissipation, and flame retardancy together, and were excellent in moldability.

Since the specific parts of the present invention have been described in detail above, it is obvious to those skilled in the art that this specific technique is only a preferred embodiment, and the scope of the present invention is not limited thereby. something to do. Therefore, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (16)

As a carbon composite material composition comprising a heat-resistant polymer resin, graphene nanoplate, graphite and carbon fiber,
The composition is a carbon composite material composition comprising 40 to 55 parts by weight of heat-resistant polymer resin, 20 to 30 parts by weight of graphene nanoplates, 15 to 20 parts by weight of graphite, and 10 to 20 parts by weight of carbon fibers relative to 100 parts by weight . According to claim 1,
The graphene nanoplate is a carbon composite material composition having a particle diameter of 5 to 20 μm and a thickness of 5 to 30 nm. According to claim 1,
The graphene nanoplate is a carbon composite material composition comprising a modified graphene nanoplate treated with phosphorus or fluorine. According to claim 1,
The graphite is a carbon composite material composition of at least one of natural graphite, artificial graphite and expanded graphite. According to claim 1,
The graphite is a carbon composite material composition of the expanded graphite having a particle diameter of 45 to 100 μm. delete According to claim 1,
A carbon composite material composition further comprising 10 parts by weight or less of a flame retardant. The method of claim 7,
The flame retardant is a melamine-based flame retardant, phosphorus-based flame retardant and organophosphinate metal salt flame retardant at least one or more carbon composite material composition. According to claim 1,
The carbon fiber is a carbon composite material composition having a length of 0.01 to 100 mm, and a diameter of 0.1 to 100 μm. According to claim 1,
Carbon composite material composition wherein the heat-resistant polymer resin is polyamide. The method of claim 10,
The polyamide resin is polycaprolactam (polyamide-6), polyamide-11, polyamide-12, polyamide-4,6, polyamide-4,8, polyamide-4,10, polyamide-4 , 12, polyamide-6,6, polyamide-6,9, polyamide-6,10, polyamide-6,12, polyamide-10,10, polyamide-12,12, polyamide-6, I, polyamide-6, T, polyamide-6, T / 6,6-copolyamide, polyamide-6, T / 6-copolyamide, polyamide-6 / 6,6-copolyamide, Polyamide-6,6 / 6, T / 6, I-copolyamide, polyamide-6, T / 2-MPMDT-copolyamide, polyamide-9, T, polyamide-6 / 12-copolyamide Amide, polyamide-6 / 11-copolyamide, polyamide-6,6 / 11-copolyamide, polyamide-6,6 / 12-copolyamide, polyamide-6 / 6,10-copolyamide In the group consisting of amide, polyamide-6,6 / 6,10-copolyamide, polyamide-4,6 / 6-copolyamide, polyamide-6 / 6,6 / 6,10-copolyamide Selected ha Carbon composite material composition of I or more. According to claim 1,
The composition further comprises one or more additives selected from the group consisting of impact modifiers, flame retardant aids, lubricants, plasticizers, heat stabilizers, dripping inhibitors, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives and drip inhibitors The carbon composite material composition. A molded article obtained by processing the carbon composite material composition according to any one of claims 1 to 5 and 7 to 12. The method of claim 13,
The processing is a molded article by one or more of the extrusion process, injection process or extrusion and injection process. The method of claim 13,
Molded article with a thermal conductivity of 10 to 30 W / m · K. The method of claim 13,
Molded articles with electromagnetic shielding efficiency (EMI SE) of 30 dB or more.