KR20160083520A - Long fiber reinforced thermoplastic resin composition with excellent thermal conductivity and EMI shielding effectiveness and article prepared therefrom - Google Patents

Abstract

The present invention relates to a long-fiber reinforced thermoplastic resin composition having excellent heat-radiating properties and electromagnetic wave shielding properties, and to a molded article manufactured therefrom. More specifically, the present invention relates to a long-fiber reinforced thermoplastic resin composition, which can obtain high heat conductivity by using graphite and graphene oxide as a heat-radiant filling material, and relates to a molded article manufactured therefrom. The long-fiber reinforced thermoplastic resin composition has excellent mechanical properties and electromagnetic wave shielding properties by using a long fiber in a polyphenylene sulfide resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a long fiber-reinforced thermoplastic resin composition excellent in heat radiation and electromagnetic wave shielding properties, and a molded article produced therefrom,

The present invention relates to a long-fiber-reinforced thermoplastic resin composition excellent in heat radiation and electromagnetic wave shielding properties and a molded article produced therefrom, and more particularly, to a polyphenylene sulfide resin composition which is excellent in mechanical properties and electromagnetic shielding property Fiber reinforced thermoplastic resin composition capable of simultaneously achieving high thermal conductivity characteristics by using graphite and graphene oxide as heat-radiating fillers, and a molded article produced therefrom.

Electronic devices with heat-generating components Most of the materials used in most of the body, chassis, and heat sinks are metal, which is attributed to the high thermal conductivity of the metal and the property of reflecting most of the electromagnetic waves generated from the inside and the outside of the device do.

The metal material diffuses the thermal energy applied by the surrounding environment at high speed, so that it is possible to protect the heat-sensitive electronic parts locally in a high-temperature environment and also realize high mechanical rigidity. However, As described above, the shielding effect is mainly caused by the reflection action, which is insufficient to realize effective shielding of the electromagnetic wave generated in the device. In order to mass-produce complicated and various designs of products, And it is difficult to realize a lightweight material due to high density.

In order to overcome these disadvantages, various thermally conductive thermoplastic materials have been developed and recently, more heat and electromagnetic waves are generated in the device due to the high integration and high performance of the electronic devices. Especially, as the electronic / information environment continues to develop, the use of the high frequency band increases, and as the electromagnetic wave output by the high density device increases, the electromagnetic interference is generated in a wider frequency range than the conventional one. It is becoming a big issue on the side. For this reason, there is a growing demand for a thermally conductive material that implements electromagnetic wave shielding or a heat dissipation material that quickly dissipates heat and electromagnetic waves generated in the environment around the material, thereby preventing exposure to a thermal environment or blocking electromagnetic waves.

In the development of thermoplastic plastic materials to replace metal materials, the realization of lightweight materials has been an area of continuous interest. Generally, there are two ways to realize the weight reduction of thermoplastic materials. There are two ways of lightweighting the thermoplastic material. One is the addition of various lightweight fillers and the other is applying the small fiber reinforced material . As a method of introducing lightweight filler among the above-mentioned methods, a method of introducing glass bubble, Senosphere, glass beads, low density heterogeneous resin composite material and the like has been continuously carried out. In this case, light weight can be realized by adding a small amount of material, It is thought that it is not suitable for realizing the characteristics of the final product. On the other hand, the development of high strength long fiber reinforced materials has been actively studied in a way that can realize excellent mechanical properties. Development of such a long fiber-reinforced material can be achieved by unwinding a bundle of fibers from a mixed bundle of fiber filaments such as glass fiber, carbon fiber, natural fiber, aramid fiber, rayon fiber, graphite fiber or metal fiber, A method of impregnating, coating or adhering a thermoplastic resin which is dissolved in heat or a solvent in a wet or non-meltable fiber filament has been continuously developed. For example, a melt infiltration method by a pultrusion method, an impregnation method by a powder charging method, a method of impregnating a co-mingle mixed fiber filament, a method of melting a resin by a solvent, , A long fiber-reinforced thermoplastic resin composition in which individual fine filaments are continuously impregnated with a thermoplastic resin is known. The long fiber-reinforced thermoplastic resin produced by such a method can realize excellent rigidity and impact characteristics compared to conventional short fiber reinforced materials, and light weight can be realized because there is no increase in weight.

In addition, with the realization of the above-mentioned weight saving characteristics, improvement of the heat dissipation characteristic for replacing metal materials is continuously demanded. This is because of the high density and high integration of the final product, automobile radiator, refrigerator, air conditioner, I.C. This is because application of thermoplastic plastic materials is required in various products such as chips, heat sinks, substrates, housings, electrical connectors, industrial motors, motors for hard disk drives, DVD and CD motors. Compared to metal materials, which are widely used as conventional heat-dissipating materials, thermoplastic materials have been limited in their use because they have a disadvantage in that they have poor thermal conductivity and electrical conductivity and low strength. The thermoplastic resin exhibits 0.2 to 0.3 W / m · K based on the thermal conductivity, while aluminum, which is a typical example of the high heat dissipating metal, exhibits a high heat radiation property of about 200 W / m · K. This is because the high thermal conductivity of the metal allows it to diffuse heat around it more quickly than other materials, thereby protecting the heat sensitive electronic components from localized high temperatures. However, metals are difficult to process in a complicated shape, are difficult to be lighter due to their high density, and have a disadvantage of high unit cost. Therefore, if a metallic material such as aluminum can be replaced with a thermally conductive thermoplastic material that has been used for heat dissipation in existing electronic, electric and automobile parts, the weight of the part can be reduced by about 40%, the cost can be reduced by about 30 to 50% .

Numerous studies have been conducted on thermally-plastic materials having a heat-dissipating property to replace metal materials, and a method of using graphite as a main filler is the most representative. This is because the graphite has a higher thermal conductivity (about 1,000 W / m · K) than other inorganic fillers, but when the graphite is used in a large amount, the mechanical properties of the final product to which the material or the material is applied tend to be significantly reduced And there is a limit in achieving the high level of thermal conductivity required in the final product when using only graphite.

Further, in the development of such a thermoplastic heat-radiating material, the flow characteristics and heat resistance characteristics of the thermoplastic resin are very important factors. This is because the flow characteristics of the resin are closely related to the impregnation rate of the filler capable of realizing heat radiation characteristics. The higher the fluidity of the thermoplastic resin is, the higher the heat dissipation characteristics are obtained because the higher filler can be made to the same filler. In addition, since the heat dissipation material is mainly applied to a region where heat generation is high, a high heat resistance characteristic (that is, high heat distortion temperature and long-term usable temperature) is basically required depending on a long- A resin which can be easily improved in heat resistance with an increase in crystallinity is preferably used. Examples of the general plastic include polystyrene, polyethylene, and polypropylene. Examples of the engineering plastic include nylon resin (nylon 6, nylon 66, nylon 12 and the like), polyester resin (polybutylene terephthalate, polyethylene Terephthalate and the like), polyarylene oxide-based resins such as polyphenylene oxide, and polycarbonate-based resins. Examples of super engineering plastics include polyarylene sulfide-based resins such as polyphenylene sulfide-based resins, A liquid crystal polymer, an aromatic polyamide, a polyarylate, a polysulfone, a polyether sulfone, a polyether imide, a thermotropic liquid crystal polymer resin, and a polyether ketone. The selection of the heat radiating filler can be an important factor for realizing the heat radiation characteristic together with the selection of the thermoplastic resin. The impregnated heat-radiating filler forms a heat conduction path to give a high heat-radiating property. The lower the shape and density of the heat-radiating filler, the more advantageous it is. This is because the filler in the heat-dissipating composite material can occupy a high volume fraction.

 Technological advances in electromagnetic shielding materials have mainly led to increased shielding efficiency in the wide frequency band, development of economical and environmentally friendly materials, and achievement of the objective of wide application in industry. That is, in order to realize effective electromagnetic shielding at the same level as that of a metal or ceramic material, which has been used in the prior art, various functionalities and weight reduction are simultaneously realized. As a general method, a conductive composite material is used, Or a method of coating a conductive resin. In addition, a dry metal film forming method or a metal shielding housing is used. Among these methods, there is a disadvantage that economical efficiency and recyclability are remarkably reduced in case of the wet or dry metal film forming method, and when metal housing is used, very economical efficiency, shielding performance and recyclability can be realized. However, The degree of freedom is remarkably reduced and the conductive resin coating method shows a tendency that the recyclability is remarkably reduced. As a result, the development of conductive composite materials having excellent aspects of economy, shielding performance, light weight, recyclability and design freedom is most active .

Researches on thermoplastic resins, especially polyphenylene sulfide resins, for the above-mentioned various industrial issues and heat dissipation materials have been continuously carried out. For example, Korean Patent Laid-Open Publication No. 10-2002-0096356 discloses a method of producing a thermally conductive thermoplastic resin by introducing less than 25% by volume of a ceramic solid as a heat-radiating filler into a thermoplastic resin. However, when such a ceramic filler is used, The conductivity is remarkably lowered and the improvement of the thermal conductivity of the injection product is insufficient.

Korean Patent Publication No. 2007-0135608 discloses a resin composition in which graphite, a ceramic filler, and a fibrous inorganic filler are mixed with a thermoplastic resin. However, this technique has a disadvantage in that it is difficult to impart high thermal conductivity characteristics because of using a mixture of a carbon-based filler and a ceramic in order to impart an insulating property, and thus it is difficult to apply to parts requiring high thermal conductivity. In addition, there is a disadvantage in terms of material recycling as compared with a single system of a heat-radiating filler.

Korean Patent Laid-Open Publication No. 2012-0078256 discloses a high thermal conductive resin composition using graphite as a heat-radiating filler and a glass fiber and a carbon fiber as a fibrous inorganic filler. However, since inorganic fillers are mixed and used, There is a drawback in that the improvement of the city performance is insufficient.

Japanese Laid-Open Patent Publication No. 2002-146187 discloses a thermally conductive resin composition excellent in fluidity by using alumina as a heat-radiating filler. However, since alumina having a small heat radiation effect is used, the thermal conductivity of the heat- , The advantage of heat dissipation characteristics is insufficient, and the price of alumina is high, which causes a disadvantage that the cost of plastic injection products is increased.

Japanese Patent Application Laid-Open No. 2003-336956 discloses a resin composition comprising a thermoplastic resin mixed with a silane-based compound and graphite as a heat-radiating filler. However, this technique has a disadvantage in that the thermal conductivity is lowered to 4 W / m · K by reducing the amount of the heat-radiating filler in order to maintain high mechanical strength.

Therefore, development of a thermoplastic resin composition that realizes high thermal conductivity and electromagnetic wave shielding property and at the same time implements mechanical properties is still required.

Disclosure of Invention Technical Problem [8] The present invention has been made to overcome the problems of the prior art described above, and it is an object of the present invention to provide a composite material capable of achieving excellent mechanical properties and electromagnetic wave shielding characteristics and using graphite and graphene oxide as heat- A thermoplastic resin composition and a molded article produced therefrom.

(A) 30 to 85% by weight of a polyphenylene sulfide resin, (B) 3 to 15% by weight of graphite, (C) 0.05 to 1% by weight of graphene oxide, and (D) Fiber reinforced thermoplastic resin composition comprising 10 to 55% by weight of fibers.

According to another aspect of the present invention, there is provided a molded article produced from the long fiber-reinforced thermoplastic resin composition.

The long fiber-reinforced thermoplastic resin composition according to the present invention exhibits excellent pressure / injection moldability and mechanical properties together with high thermal conductivity and electromagnetic wave shielding property and is also low in manufacturing cost. Therefore, the pressure / The molded article can be manufactured at a low cost, and such a molded article can be utilized in various fields such as automobile, electric, electronic parts, and LED lighting in particular.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The long fiber-reinforced thermoplastic resin of the present invention means a fiber having a long fiber bundled through a draw-molding apparatus and passing through a dipping bath in which the resin is melted to "cover" So that the long fibers are reinforced parallel to the longitudinal direction of the pellets and can be produced in a length of 5 to 30 mm depending on the length of the pellets.

(A) 30 to 85% by weight of a polyphenylene sulfide resin, (B) 3 to 15% by weight of graphite, (C) 0.05 to 1% by weight of graphene oxide, and (D) 10 to 55% by weight.

(A) polyphenylene Sulfide  Suzy

Examples of the method for producing the polyphenylene sulfide resin include the reaction of a halogen-substituted aromatic compound with an alkali sulfide disclosed in U.S. Patent No. 2513188 and Japanese Patent Publication (Tokukai) No. 44-27671, U.S. Patent No. 3274165 Condensation reaction of thiophenols under air-conditioning with an alkali catalyst or a copper salt, or condensation reaction of an aromatic compound with sulfuric acid under Lewis acid catalyst disclosed in Japanese Patent Publication (Kokoku) No. 46-27255. Generally, commercially available polyphenylene sulfide resin can be used in the market. There is no particular limitation on the structure, and both linear and cross-linkable types are applicable.

The resin composition of the present invention comprises a polyphenylene sulfide resin as a base resin component. In the present invention, the polyphenylene sulfide resin is preferably a linear polyphenylene sulfide resin containing a repeating unit having a structure represented by the following formula (1), more preferably at least 70 mol%

[Chemical Formula 1]

In the above, n is preferably an integer of 1000 to 20,000.

The bulk density of the polyphenylene sulfide resin is preferably 0.3 to 1.5 g / cm < ³ > to be. When the bulk density of the polyphenylene sulfide resin is 0.3 g / cm < ³ > , Phase transfer is difficult due to the free fall from the fixed feeder to the extruder inlet, and when it exceeds 1.5 g / cm < ³ >, phase separation occurs during agitation with graphite having a relatively low bulk density, It may be difficult to inject the solution into the reactor.

Further, the flow index of the polyphenylene sulfide resin is preferably 20 to 100 g / 10 min at 300 캜 under a load of 1.2 kg. When the flow index of the polyphenylene sulfide resin is less than 30 g / 10 min, the strength of the molded article becomes very low. When the flow index of the polyphenylene sulfide resin exceeds 100 g / 10 min, it becomes difficult to highly fill the heat dissipation and reinforcing filler.

The polyphenylene sulfide resin is contained in an amount of 30 to 85% by weight, preferably 35 to 80% by weight, and more preferably 40 to 60% by weight within 100% by weight of the resin composition of the present invention. If the content of the polyphenylene sulfide resin in the composition is less than 30% by weight, it becomes difficult to highly fill the heat-radiating and reinforcing filler, and the fluidity and the injection-moldability of the resin composition deteriorate. If the content of the polyphenylene sulfide resin exceeds 85% by weight, the flow increases and the injection moldability and thermal conductivity decrease.

(B) Graphite

In the present invention, graphite and graphene oxide may be used in combination as a heat-radiating filler. However, this does not exclude the possibility of using other heat-radiating fillers, and other carbon-based heat-radiating fillers such as carbon fibers, carbon nanotubes and the like may be further used within the scope of achieving the object of the present invention.

The graphite used in the composition of the present invention forms a continuous plate-like layer of graphene, and three electrons formed on the planar surface form a strong covalent bond, and the remaining one electron is bonded to the upper and lower layers. The height of one layer on the hexagonal plate is 3.40 ANGSTROM, and the distance between the closest carbons in the hexagonal ring is 1.42 ANGSTROM. The distance between the upper and lower layers of the platelets is much larger than the center distance of the two carbon atoms (the radius of the carbon atom is 0.77 Å and the carbon ion is tetravalent, 0.16 Å). For this reason, graphite has good electrical conductivity because the electrons above the hexagonal plate can move somewhat freely.

In the present invention, the fixed carbon content of graphite is preferably 95% or more, and more preferably 98% or more. The crystallization ratio of graphite is preferably 80% or more, more preferably 90% or more. The bulk density of graphite is preferably 0.5 to 2 g / cm < ^{3 &} gt ;. When the bulk density of graphite is less than 0.5 g / cm ^3, it is too light and bulky to be difficult to be injected into the extruder in a fixed amount, and when exceeding 2 g / cm ³ , the molded product becomes heavy and lightweight becomes difficult.

The particle diameter of the graphite used in the present invention is preferably 10 to 500 占 퐉, more preferably 20 to 200 占 퐉. The thermal conductivity of graphite is preferably 100 W / m · K or more. If graphite whose thermal conductivity is not sufficiently secured is used, the heat dissipation property of the molded article is deteriorated.

Within 100 wt% of the resin composition of the present invention, the graphite is contained in an amount of 3 to 15 wt%. If the graphite content in the composition is less than 3% by weight, the thermal conductivity is lowered and the flow is increased to make it difficult to secure stable extrusion and injection molding properties. If the graphite content exceeds 15% by weight, the input amount of the long fiber reinforcing agent is limited, Can not be achieved.

(C) Grapina Oxide

Graphene has a unique structure in which two carbon atoms have a double bond and a sigma bond directly connecting the carbon atoms, and a pivalent bond with a p orbital protruding above and below the carbon atom. When the double bond of the carbon atom is extended, the overlap of the p orbital also expands. The hexagonal net carbon atoms that make up the graphene are also connected to the pi-orbitals by overlapping pie bonds, just like benzene. Graphene has very good electrical conductivity because free electrons can migrate from p orbits that are superposed between adjacent carbon atoms.

As a synthesis method of graphene, a mechanical peeling method (top-down method) in which single-layer graphene is separated from graphite by using a scotch tape, a chemical peeling method in which graphene oxide is reduced or reduced by heat treatment, A bottom-up method in which a transition metal that is well adsorbed by nitrogen is used as a catalyst layer to grow from carbon atoms; a method in which carbon atoms adsorbed or contained in crystals at high temperatures are grown to graphene along the surface An epitaxial synthesis method, and the like are widely known. The graphene synthesized by the conventional method as described above has a low yield and is obtained in the form of a thin film film, so that it is difficult to apply it to a resin composition. Therefore, in the present invention, graphene oxide which can maintain a stable yield and shape to such an extent that it can be fed into an extruder is used. According to a preferred embodiment of the present invention, graphene oxide is produced using solvent thermo-synthesis. According to the solvent thermo-synthetic method in this specific example, sodium and ethanol are first charged into a reaction vessel at a particle ratio of 1: 1, and the mixture is put into a furnace and reacted at 220 ° C for 72 hours. Treated for a short time, rinsed with distilled water, and dried in a vacuum oven at 100 ° C. for 24 hours to obtain graphene oxide.

Graphene oxide has an excellent thermal conductivity, but it is difficult to mass-synthesize it, the production cost is high, the bulk density is too low, and the interfacial van der Waals force lowers the feedability to the extruder. Therefore, in the present invention, by using a small amount of graphene oxide in combination with graphite without using graphene oxide alone, it is possible to prevent the loss during the introduction into the extruder and to facilitate the introduction of the graphene oxide, Thereby enabling extrusion.

In the present invention, the grain size of graphene oxide is preferably 1 to 10 mu m, and the thermal conductivity is usually 4500 to 5500 W / mK.

The graphene oxide is contained in an amount of 0.05 to 1% by weight, preferably 0.1 to 1% by weight, more preferably 0.5 to 1% by weight in 100% by weight of the resin composition of the present invention. If the content of graphene oxide in the composition is less than 0.05% by weight, the effect of improving the thermal conductivity is insignificant. If the content is more than 1% by weight, the volume of the extruded strand becomes lighter and the continuous process becomes difficult.

(D) Long fiber

The length of the long fibers contained in the long fiber-reinforced thermoplastic resin composition of the present invention may have a length of 5 to 30 mm, preferably 10 to 25 mm, more preferably 15 to 20 mm, The length can be variously used.

As the long fibers, inorganic fibers and organic fibers can be used. Since they have inherent advantages and functions, they are appropriately selected according to the use of the final molded product. Preferable long fibers in terms of cost or performance include glass fibers, carbon fibers, metal fibers, aramid fibers, Ultra High Molecular Weight Polyethylene (PE) fibers, polyacrylonitrile (PAN) Fibers, polyether ether ketone (PEEK) fibers, rayon fibers, mixtures thereof, and the like, and it is preferable to use natural fibers in the environment. The long fibers may be surface-treated. As the surface treatment agent, silane-based or titanate-based low molecular weight or high molecular weight polymers generally used can be used. At least one of the surface treatment agents is compatible with the thermoplastic resin A good surface treatment agent is preferably used and can be impregnated continuously with the thermoplastic resin by various known methods such as melt infiltration method and powder charging method.

Although not limited in particular, it is possible to prepare long fiber-reinforced thermoplastic resin pellets by using a pultrusion method in consideration of mass productivity and efficiency among various known methods in the present invention. The thermoplastic resin is injected into a resin injection portion of a pultrusion apparatus and is impregnated with a long fiber reinforcing agent in the form of a lobe through a pulling and squeezing process while passing the resin through a die and pulling the strands of the continuous phase in the impregnated state pelletized, cooled and cut into pellets to produce long fiber-reinforced thermoplastic resin pellets.

The content of the long fiber reinforcing agent may be varied depending on impact characteristics, workability and flexural rigidity of the desired product, and preferably 10 to 55% by weight based on the total composition. If the content of the heat-radiating filler is more than 55% by weight, the amount of the heat-radiating filler is limited, and the heat conduction effect is deteriorated. In addition, the processability is deteriorated, This is because derivation of the reinforcing agent on the surface of the thermoplastic resin and dispersion of the reinforcing agent in the molded article may not be uniform.

(E) Any other additional component

The composition of the present invention may contain, in addition to the above-described components, various additives commonly used in thermoplastic resin compositions, such as compatibilizers, heat stabilizers, antioxidants, lubricants, etc., Or more. The amount of the additive to be used is not particularly limited and may be further added in an amount of up to about 5% by weight, preferably about 0.2 to 5% by weight based on 100% by weight of the total resin composition, depending on the intended use and application.

According to another aspect of the present invention, there is provided a molded article produced from the long fiber-reinforced thermoplastic resin composition. The long fiber-reinforced thermoplastic resin composition of the present invention thus obtained exhibits remarkably high thermal conductivity, excellent mechanical strength, and pressure / injection moldability at the same time. Therefore, it is possible to provide a molded article exhibiting remarkably excellent heat- Automotive parts, electrical products, electronics, LED lighting products (eg housings, heat sinks) are available.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[ Example  And Comparative Example ]

The components used in this embodiment and the comparative examples are as follows.

(A) polyphenylene Sulfide

Linear polyphenylene sulfide resin: HATON Hbo Linear (SCDY)

(Bulk density: 0.4 g / cm 3, flow index: 300 to 1000 at 315 ° C @ 5 kg)

(B) Graphite

SDK-S (Showa Denko) (bulk density: 0.9 g / cm ³ , particle diameter: 200 탆 on average)

(C) Grapina Oxide

Manufactured by Samyang Corp. (solvent thermo-synthetic method) (particle size: 1 to 10 탆, thermal conductivity: 4840 to 5300 W / m 占))

(D-1) Long fiber  Reinforcing agent

PAN-based carbon fiber tows having a diameter of 5 to 10 탆 and a length of 15 to 20 mm and being collected by urethane resin and having a filament number of 15,000 were used as the carbon fiber reinforcers (D-1A and D-1B) .

(D-2) Short fiber reinforcing agent

PAN-based short carbon fiber roving having a diameter of 5 to 10 탆 and a length of 3 to 6 mm, a urethane resin-concentrated filament number 24,000 was used as the carbon short stiffener (D-2A) used in the comparative example .

As the glass short-fiber reinforcement (D-2B) used in the comparison, a glass short fiber roving having a diameter of 10 to 14 mu m, a length of 2 to 4 mm and a filament number of 3,500 was used.

The polyphenylene sulfide resin, graphite and graphene oxide were melt-kneaded at a melt temperature of 275 to 295 ° C and 150 rpm in a biaxial melt-kneading extruder having L / D = 48 and Φ = 25 mm as components and contents of the examples and comparative examples shown in the following Table 1 Extruded under the conditions of a screw rotation speed of about 600 mmHg, a first vent pressure of 20 kg / h, and a self-feed rate of 20 kg / h. The graphite was fed side through a point in the middle of the extruder and the extruded strand was cooled in water and then cut with a rotary cutter to prepare a master batch.

Then, the polyphenylene sulfide resin was injected into the resin injection part of the pultrusion equipment in the components and contents of the examples and comparative examples shown in the following Table 1, and the long fiber reinforcing agent in the form of lobes was pulled Impregnated through a squeezing process, pultruded from the continuous strands in the impregnated state, cooled and cut into pellets having a length of 30 mm to prepare long-fiber reinforced polyphenylene sulfide pellets.

The prepared masterbatches and polyphenylene sulfide pellets were dry blended with the components and contents of Table 1 (except that Comparative Example 5 was extruded without dry blending), and after hot air drying at 110 to 120 ° C for 4 hours, The specimens were prepared by injection molding at a cylinder temperature of 300 ~ 350 ° C and a mold temperature of 150 ° C. The properties of each specimen were measured by the method described below. The results are shown in Table 2.

(1) Bulk density: ASTM B527

(2) Through-Plane: ASTM E1461 (Laser flash method)

Specimen length 10 x 10 mm, thickness: 2 mm, thickness direction measurement

(3) Thermal conductivity In (In-Plane): ASTM E1461 (Laser flash method)

Specimen length 10 x 10 mm, thickness: 2 mm, length direction of specimen

(4) Electromagnetic wave shielding: ASTM D4935

(5) Tensile strength and elongation: ASTM D638

(6) Flexural strength and elastic modulus: ASTM D790

(7) Extrusion processability: Relative comparison is made according to the degree of breaking of the strand in the masterbatch according to the following criteria

As can be seen from Table 2, the resin composition according to the embodiment of the present invention has improved thermal conductivity compared to the resin composition of Comparative Examples, and has improved mechanical properties such as tensile strength, flexural strength and flexural modulus, Are well balanced. Except for Example 2 in which the content of the long-fiber carbon reinforcing agent is particularly limited, excellent thermal conductivity of 3 W / m · K or more and excellent electromagnetic wave shielding efficiency of 40 dB level were achieved in all the compositions.

On the other hand, in the case of Comparative Example 2, the graphite content is high and the mechanical properties are greatly deteriorated. Comparative Examples 1 and 3 exhibit very low thermal conductivity characteristics and are insufficient to be applied as a heat dissipation material. Extrusion processing was impossible because it was difficult to quantitatively inject the excess amount of pin oxide. Comparative Example 5 showed the same composition as in Example 1, but in the case of extrusion processing without dry blending. All properties were lowered than in Example 1, continuous extrusion operation was impossible, and it was not suitable for mass production It is considered that there will be many difficulties in implementing the final product by applying this. In Comparative Example 6, a short-fiber carbon reinforcing agent was used, and in Comparative Example 7, a short-fiber glass carbon reinforcing agent was used, and it was found that all properties were lowered compared to Comparative Example 1 in which a long-fiber carbon reinforcing agent was used.

Claims (14)

(A) 30 to 85% by weight of a polyphenylene sulfide resin, (B) 3 to 15% by weight of graphite, (C) 0.05 to 1% by weight of graphene oxide and 10 to 55% Fiber reinforced thermoplastic resin composition. The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein (A) the polyphenylene sulfide resin is a linear polyphenylene sulfide resin containing a repeating unit having a structure represented by the following formula (1)
[Chemical Formula 1]

(Wherein n is an integer from 1,000 to 20,000). The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein (A) the polyphenylene sulfide resin has a bulk density of 0.3 to 1.5 g / cm ³ . The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein the polyphenylene sulfide resin (A) has a flow index of 20 to 100 g / 10 min (300 ° C under a load of 1.2 kg). The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein the (B) graphite has a bulk density of 0.5 to 2 g / cm ³ . The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein the (B) graphite has a particle diameter of 10 to 500 μm. The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein (C) the graphene oxide has a particle diameter of 1 to 10 μm. The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein the (C) graphene oxide has a thermal conductivity of 4500 to 5500 W / mK. The nonwoven fabric according to claim 1, wherein the (D) long fiber is at least one selected from the group consisting of glass fiber, carbon fiber, metal fiber, aramid fiber, ultra high molecular weight polyethylene fiber, polyacrylonitrile fiber, arylate fiber, polyetherketone fiber, And mixtures thereof. The long fiber-reinforced thermoplastic resin composition according to claim 1, The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein (D) the long fiber is surface-treated with a silane-based or titanate-based polymer. The long-fiber-reinforced thermoplastic resin composition according to claim 1, further comprising an additive selected from the group consisting of compatibilizers, heat stabilizers, antioxidants, lubricants, and mixtures thereof. The long-fiber-reinforced thermoplastic resin composition according to claim 1, wherein the (D) long fibers are arranged parallel to the longitudinal direction of the pellets, and the length of the long fibers and the length of the pellets are 5 to 30 mm. A molded article produced from the long fiber-reinforced thermoplastic resin composition according to any one of claims 1 to 12. The molded article according to claim 13, which is an automobile part, an electric product, an electronic product or an LED lighting article.