WO2012026652A1

WO2012026652A1 - High-rigidity electromagnetic shielding composition and molded articles thereof

Info

Publication number: WO2012026652A1
Application number: PCT/KR2010/009244
Authority: WO
Inventors: 임윤숙; 박강열; 신찬균; 박지권; 김두영
Original assignee: 제일모직 주식회사
Priority date: 2010-08-26
Filing date: 2010-12-23
Publication date: 2012-03-01

Abstract

The high-rigidity electromagnetic shielding composition of the present invention comprises: (A) approximately 10-34 wt% of polyamide resin having an aromatic group in the backbone structure; (B) approximately 65-85 wt% of carbon fiber; and (C) approximately 1-20 wt% of metallic filler. The composition has high modulus, electromagnetic shielding effects, and high surface conductance, and can thus be used to replace frames, brackets and the like for electronic devices.

Description

High Rigidity Electromagnetic Shielding Composition and Molded Articles

The present invention relates to a highly rigid electromagnetic wave shielding composition and a molded article thereof. More specifically, the present invention relates to a high-strength electromagnetic shielding composition and a molded article having excellent mechanical strength and EMI shielding properties, which can reduce the production cost by replacing an existing magnesium material, and have excellent processability.

Electromagnetic wave is a noise phenomenon generated by electrostatic discharge, and it is known to not only cause noise and malfunction to surrounding components or devices, but also to have a harmful effect on the human body. Recently, the possibility of electromagnetic wave is rapidly increasing through high-efficiency, high power consumption, and highly integrated electric and electronic products, and the regulation of electromagnetic waves is strengthened not only in advanced countries but also in Korea.

Conventionally, there is a method using a metal material as a method for shielding electromagnetic waves. For example, IT brackets used in portable display products such as mobile phones, laptops, PDAs, and other mobile items protect LCDs, shield electromagnetic waves, and act as frames, requiring high rigidity and EMI shielding. . Recently, metals such as magnesium, aluminum and stainless steel are mainly used as materials for brackets and frames. By the way, in the case of such a metal material has an advantage that can effectively block the electromagnetic wave, it is produced by the die-casting method has a disadvantage of high production cost and high defective rate.

Accordingly, a method of replacing thermoplastics with ease of molding, excellent molding precision, and economical efficiency or productivity has been proposed.

Currently developed metal substitute resin modulus is less than FM 20GPa, electromagnetic shielding effect is about 30dB (@ 1GHz), there is a disadvantage that the rigidity and EMI shielding is significantly lower than the metal. In order to increase the modulus, a method of increasing the fiber content has been proposed, but in the case of a high fiber content, not only the impact strength is low, but also the fluidity is low and the processing is difficult, which makes it difficult to apply practically and the surface resistance is high. There is a problem that the conductivity is too low to use.

In particular, when the polyamide-based resin is applied as a base resin, the product deterioration is accelerated due to low dimensional stability and high moisture absorption rate, and high filler loading is difficult in a low flow base. Recently, products having high modulus and electromagnetic shielding effect of more than 30dB using carbon-based fibers over 50% have been developed, but it is insufficient to replace metals, and there is difficulty in processing. Moreover, there is a problem that the conductivity is low to use such a material as the material of the electronic device. For example, problems such as deterioration of grounding performance and antenna performance have occurred when using a general mobile phone bracket.

In general high stiffness resin, the surface resistance is lowered by conducting plating in order to solve this problem, but it causes a price increase due to the plating process and the subsequent process, and has a disadvantage in that the surface is peeled off when used for a long time.

Therefore, there is a need for the development of a new material that can replace the existing magnesium material with excellent fluidity, impact strength and rigidity, excellent conductivity and shielding performance.

An object of the present invention is to provide a high rigidity electromagnetic shielding composition having excellent mechanical strength and a molded article thereof.

Another object of the present invention is to provide a highly rigid electromagnetic shielding composition suitable for EMI shielding and its molded article having excellent conductivity and low surface resistance.

It is still another object of the present invention to provide a highly rigid electromagnetic shielding composition having excellent flowability and formability and a molded article thereof.

It is still another object of the present invention to provide a high rigidity electromagnetic shielding composition and its molded article which do not require post-processing and are excellent in economy and productivity.

It is still another object of the present invention to provide a highly rigid electromagnetic shielding composition having excellent dimensional stability and a molded article thereof.

It is still another object of the present invention to provide a highly rigid electromagnetic shielding composition and its molded article which can replace the existing magnesium material.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the invention relates to a high rigidity electromagnetic shielding composition. The composition comprises (A) about 10 to 34% by weight of a polyamide resin containing an aromatic group in the main chain; (B) about 65 to 85 weight percent of carbon fibers; And (C) about 1 to 20 weight percent of a metal filler.

In embodiments, the (A) polyamide resin may be a wholly aromatic polyamide, a semiaromatic polyamide or a mixture thereof.

The semiaromatic polyamide may be a polymer of aromatic diamine and aliphatic dicarboxylic acid.

In one embodiment, the semiaromatic polyamide may be represented by the following Chemical Formula 1:

[Formula 1]

Ar is an aromatic group, R is a C _4-20 alkylene group, n is an integer of 50 to 500.

In embodiments, the (B) carbon fiber may include a bundle form.

In an embodiment, the metal filler (C) may be metal powder, metal beads, metal fibers, metal flakes, metal coated particles, metal coated fibers, and the like, and these may be used alone or in combination of two or more thereof.

As the metal filler (C), aluminum, stainless steel, iron, chromium, nickel, black nickel, copper, silver, gold, platinum, palladium, tin, cobalt, two or more kinds thereof, and the like may be used. These can be used individually or in mixture of 2 or more types.

The composition may include carbon nanotubes in a range of about 0 to 20 parts by weight or less based on 100 parts by weight of (A) + (B) + (C).

The composition may further comprise a metal coated graphite. The metal-coated graphite may have particles, fibers, flakes, amorphous or a combination thereof.

The metal-coated graphite may have an average particle diameter of about 10 to 200 ㎛.

In embodiments, the metal may be aluminum, stainless steel, iron, chromium, nickel, black nickel, copper, silver, gold, platinum, palladium, tin, cobalt, and the like, and two or more alloys thereof may also be applied.

In embodiments, the composition may further include additives such as flame retardants, plasticizers, coupling agents, thermal stabilizers, light stabilizers, inorganic fillers, mold release agents, dispersants, anti-dropping agents, weather stabilizers. These can be used individually or in mixture of 2 or more types.

In one embodiment the composition has a tensile strength of at least about 40 GPa at a thickness of 3.2 mm by ASTM D638, a flexural modulus of at least 40 GPa at a thickness of 6.4 mm by ASTM D790, EMI D790 at a thickness of 1 GHz, 1 mm. The shielding effect according to the standard is about 50 dB or more, the volume resistance by the four-point probe method is about 0.2 Ω · cm or less for specimens of 1 mm thickness, and 100 pieces are measured after extraction at 550 ℃ / 1hr. The average value of one residual fiber length may be about 2 to 6 mm.

Another aspect of the invention relates to a molded article made from the composition. The molded article may have a structure in which (A) carbon fiber and (C) metal filler are impregnated into a polyamide resin containing an aromatic group in the main chain (A).

In an embodiment the molded article may be an LCD protective bracket of a portable display product.

In an embodiment, the molded article comprises (A) melting a polyamide resin containing an aromatic group in a main chain and (C) a metal filler; Impregnating the melt with (B) carbon fiber and pelletizing it; And it may be prepared including the step of molding the pellets. In embodiments, the pelletization may be pelletized by cutting the impregnated carbon fibers.

The pellet may have a length of about 8 to 20 mm.

In embodiments, the carbon fiber having a length of about 0.5 to 6 mm in the molded article may be at least about 80% by weight of the total carbon fibers in the molded article.

The present invention is suitable for EMI shielding due to its excellent mechanical strength and conductivity, and low surface resistance, excellent fluidity and formability, no post-processing, excellent economy and productivity, excellent dimensional stability, and can replace existing magnesium materials. The high rigidity electromagnetic wave shielding composition and its molded article have the effect of this invention.

The highly rigid electromagnetic wave shielding composition of the present invention comprises (A) a polyamide resin containing an aromatic group in the main chain; (B) carbon fiber; And (C) a metal filler. Hereinafter, each said component is explained in full detail.

(A) polyamide resin

As the polyamide resin (A) that can be used in the present invention, an aromatic polyamide resin containing an aromatic group in the main chain can be used. In embodiments, the (A) polyamide resin may be a wholly aromatic polyamide, a semiaromatic polyamide or a mixture thereof.

As described above, since the aromatic polyamide of the present invention contains an aromatic group in the main chain, it is possible to give higher rigidity and strength.

The wholly aromatic polyamide means a polymer of aromatic diamine and aromatic dicarboxylic acid.

The semiaromatic polyamide is meant to include at least one aromatic unit and non-aromatic units between amide bonds. In one embodiment, the semiaromatic polyamide may be a polymer of aromatic diamine and aliphatic dicarboxylic acid.

In a preferred embodiment the semi-aromatic polyamide may comprise a polyamide represented by the following formula (1):

[Formula 1]

Ar in Formula 1 may be a substituted or unsubstituted aromatic group. The aromatic group may be one or more. In addition, R may be a C _4-20 linear or branched alkylene group.

In another embodiment, the semiaromatic polyamide may be a polymer of aliphatic diamine and aromatic dicarboxylic acid, as shown in the following Formula 2.

[Formula 2]

[Revision 17.01.2011 under Rule 26]

Ar is an aromatic group, R is a C _1-20 alkylene group, n is an integer of 50 to 500.

Ar in Formula 1 may be a substituted or unsubstituted aromatic group. The aromatic group may be one or more. In addition, R may be a C _1-20 linear or branched alkylene group.

As the aromatic diamine, p-xylenediamine, m-xylenediamine, etc. may be used, but are not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl 4,4'-dicarboxylic acid, 1,3-phenylenedioxydiacetic acid, and the like. May be used, but is not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

The aliphatic diamine may be 1,2-ethylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, 1,12-dodecylenediamine, piperazine and the like, but is not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

The aliphatic dicarboxylic acid may be adipic acid, sebacic acid, succinic acid, glutaric acid, azelaic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, and the like, but is not limited thereto. These can be used individually or in mixture of 2 or more types.

In one embodiment, the polyamide resin (A) may have a glass transition temperature (Tg) of about 80 to 120 ° C, preferably about 83 to 100 ° C. It is possible to obtain the balance of physical properties of excellent fluidity, rigidity and low moisture absorption in the above range.

Preferably, the polyamide resin (A) includes nylon MXD6, nylon 6T, nylon 9T, nylon 10T, nylon 6I / 6T, and most preferably nylon MXD6. These can be used individually or in mixture of 2 or more types.

In another embodiment, an aliphatic polyamide resin can be further added to the polyamide resin (A). In embodiments, the aliphatic polyamide may be nylon 6, nylon 66, nylon 11, nylon12 or a mixture thereof.

In the present invention, the polyamide resin may be used in about 10 to 34% by weight, preferably about 15 to 30% by weight of the component (A) + (B) + (C). If the (A) polyamide resin exceeds 34% by weight, the modulus and strength are lowered, the volume resistance is increased, and the EMI shielding performance is lowered. On the other hand, when the content of (A) polyamide resin is less than 10% by weight, moldability may be deteriorated.

(B) carbon fiber

Carbon fiber used in the present invention is already well known to those skilled in the art, it is easy to purchase commercially, it can be produced by conventional methods.

In specific embodiments, the carbon fiber may be one prepared from a PAN system or a pitch system.

The average diameter of the carbon fiber may be used that is about 1 to 30 ㎛, preferably about 3 to 20 ㎛, more preferably about 5 to 15 ㎛. Excellent physical properties and conductivity can be obtained in the above range.

In one embodiment, the carbon fiber may be used that has been surface-treated.

In addition, the carbon fiber may use a bundle form. In embodiments, the carbon fiber may be a long carbon fiber in the form of a bundle of about 400 to 3000 TEX, preferably about 800 to 2400 TEX, more preferably about 800 to 1700 TEX. Impregnation can be good in the above range.

The carbon fiber having a bundle form is impregnated in the melt of the polyamide resin (A) to bury the polyamide resin (A) on the surface, and then the carbon fiber having the polyamide resin (A) is squeezed in the pelletizing process. It is cut into 8-20 mm lengths and made into pellets about 8-20 mm long. Since the length is cut along the length of the carbon fiber, the length of the pellet is the same as the length of the cut carbon fiber. That is, a pellet of about 8-20 mm in length will contain carbon fibers of about 8-20 mm in length.

The pellets prepared as described above may be manufactured into a molding through a molding process such as injection, and the final molding has a structure in which carbon fibers are dispersed from each other.

In addition, the carbon fiber is usually cut after the molding, most of the length of the residual fiber in the molded article is about 0.5 to 6mm when the long carbon fiber of about 8 to 20 mm length is applied as in the present invention. Here, the length of the residual fiber refers to the length of the fiber after pelletizing and then forming. The molding process is a common general molding condition. For example, injection conditions with a temperature of about 280 to 320 ° C. and a pressure of about 170 Mpa to 190 Mpa are common. Examples of the molding conditions are merely examples for reference, but are not necessarily limited thereto.

On the other hand, when the general chopped fiber is applied, there is a difference in physical properties because the length of the residual fiber is hardly about 0.5 mm or more in the molded article. In an embodiment, after molding the composition of the present invention, the carbon fiber having a length of about 0.5 to 6 mm of residual fiber in the molded article is about 80 wt% or more, and in the embodiment, about 90 wt% or more of the total carbon fibers. In addition, after 1 hour at 550 ℃ for the molded article 100 residual fiber length is extracted by measuring the length in the longitudinal direction, the average value may be about 2mm or more, in embodiments about 3mm or more.

The carbon fiber may be used in about 65 to 85% by weight, preferably about 65 to 80% by weight of the component (A) + (B) + (C). If (B) the carbon fiber is less than 65% by weight, the modulus and flexural modulus are lowered, the volume resistance and the moisture absorption rate are increased, and the EMI shielding performance is lowered. On the other hand, if the content of (B) the carbon fiber exceeds 85% by weight, the fluidity may be lowered and the impact strength and flexural modulus may fall.

(C) metal filler

The metal filler (C) used in the present invention may be used without limitation as long as the filler has conductivity. In specific embodiments, aluminum, stainless, iron, chromium, nickel, black nickel, copper, silver, gold, platinum, palladium, tin, cobalt, two or more alloys thereof, and the like may be used. These can be used individually or in mixture of 2 or more types. In one embodiment it may be an alloy of iron-chromium-nickel.

In other embodiments, metal oxides or metal carbides such as tin oxide, indium oxide, silicon carbide, zirconium carbide, titanium carbide, and the like may also be used.

In another embodiment, a low melting point comprising a main component selected from the group consisting of tin, lead and combinations thereof and a subcomponent selected from the group consisting of copper, aluminum, nickel, silver, germanium, indium, zinc and combinations thereof Metals can be used. The low melting point metal may be used having a melting point of about 300 ° C. or less, preferably about 275 ° C. or less, and more preferably about 250 ° C. or less.

When the low melting point metal is used as described above, the filler-to-pillar network can be easily formed to further improve the electromagnetic shielding efficiency. Such a low melting point metal preferably has a solidus temperature (Solidus temp .: temperature at which solidification ends) lower than the composite process process temperature of the polyamide resin (A). Preferably, the solidus temperature of the low melting point metal is 20 ° C or more lower than the process process temperature of the polyamide resin (A) in terms of the composite manufacturing process and the network formation between the fillers, and the stability is about 100 ° C or more higher than the composite use environment. Good in terms of Preferably, tin / copper (90 to 99/1 to 10 weight ratio) and tin / copper / silver (90 to 96/3 to 8/1 to 3 weight ratio) may be used as the melting point of about 300 ° C. or less.

The metal filler may be formed of metal powder, metal beads, metal fibers, metal flakes, metal coated particles, metal coated fibers, and the like, but are not limited thereto. These can be used individually or in mixture of 2 or more types.

When using the form of the metal filler in the form of metal powder or metal beads, the average particle diameter may be 30 to 300 ㎛. There is an advantage that feeding is good when extrusion in the above range.

When the form of the metal filler is used in the form of a metal fiber, it may have a length of about 50 to 500 mm and a diameter range of about 10 to 100 μm. In addition, the metal fiber may be used having a density of about 0.7 to 6.0 g / ml. It is possible to maintain proper feeding during the extrusion process in the above range.

When the form of the metal filler is used in the form of metal flakes, the average size may be about 50 to 500 μm. There is an advantage in maintaining the proper feeding during the extrusion processing in the above range.

The metal powder, metal beads, metal fibers, etc. may be a single metal or an alloy of two or more kinds, and may have a multilayer structure.

The metal-coated particles and the metal-coated fibers form a core of a resin, ceramic, metal, carbon, and the like, and the core is coated with metal. For example, the resin-based fine particles or fibers may be coated with a metal such as nickel or nickel-copper, and the metal coating may be a single layer or a multilayer.

In embodiments, the metal coated particles may have an average particle diameter of about 30 to 300 ㎛. There is an advantage that feeding is good when extrusion in the above range. In addition, the metal-coated fibers may have an average diameter of about 10 to 100 μm and a length of about 50 to 500 mm. There is an advantage in maintaining the proper feeding during the extrusion processing in the above range.

In the present invention, the metal filler (C) may be used in about 1 to 20% by weight, preferably about 3 to 15% by weight of the component (A) + (B) + (C). If the metal filler (C) is less than 1% by weight, the conductivity is lowered, and when the content of the metal filler (C) is more than 20% by weight, the fluidity may be lowered and the impact strength and the bending modulus may fall.

In one embodiment, the weight ratio between the component (B) and the component (C) may be used as (B) :( C) = 6: 1∼20: 1. Excellent physical property balance can be obtained in the above range.

The composition may further include carbon nanotubes. The carbon nanotubes may be used for any of single walls, double walls, and multiple walls, and a combination thereof may be applied. Preferably it is a multi-walled carbon nanotube. When the carbon nanotubes are contained, the surface resistance is significantly lowered, and thus the electromagnetic wave shielding performance and rigidity may be more excellent. The carbon nanotubes may be included in the range of about 0 to 20 parts by weight or less based on 100 parts by weight of (A) + (B) + (C). It can have excellent fluidity and rigidity and electromagnetic shielding performance in the above range. It is preferably about 1 to 15 parts by weight, more preferably about 1 to 10 parts by weight.

The composition may further include metal coated graphite. The metal coated graphite may have particles, fibers, flakes, amorphous or a combination thereof. When the metal-coated graphite has a fiber shape, it may form a network structure with carbon fibers. When the metal-coated graphite is thus contained, the surface resistance is remarkably reduced, and it may have more excellent electromagnetic shielding performance and rigidity.

The metal-coated graphite may have an average particle diameter of about 10 to 200 ㎛. In addition, when the metal-coated graphite has a fibrous shape, the average diameter is preferably about 10 to 200 μm, and the average length is about 15 to 100 μm. While excellent in electrical conductivity in the above range, there is an advantage that the decrease in mechanical properties by addition.

In embodiments, the metal may be used as long as the metal is conductive. Preferably, aluminum, stainless steel, iron, chromium, nickel, black nickel, copper, silver, gold, platinum, palladium, tin, cobalt and the like may be used, and two or more kinds thereof may also be applied.

In addition, the metal coating may be formed of not only a single layer but also two or more layers.

In embodiments, the metal-coated graphite may be included in the range of about 10 parts by weight or less based on 100 parts by weight of (A) + (B) + (C). Preferably it is about 0.1-7 weight part.

In another embodiment, the metal-coated graphite may be applied together with carbon nanotubes, wherein the metal-coated graphite content is about 0.1 to 3 parts by weight based on 100 parts by weight of (A) + (B) + (C). Can be applied to wealth. It can have excellent fluidity and rigidity and electromagnetic shielding performance in the above range.

In the composition of the present invention, additives such as a flame retardant, a plasticizer, a coupling agent, a thermal stabilizer, a light stabilizer, an inorganic filler, a mold release agent, a dispersant, an antidropping agent, a carbon filler, and a weathering stabilizer may be added in a conventional range. These can be used individually or in mixture of 2 or more types. As the carbon filler, various carbon fillers except for the carbon fiber (B) may be applied. Specific examples may include graphite, carbon nanotubes, carbon black, and the like, and metal coatings thereof may also be included. For example, the metal-coated graphite described above may also be included.

In one embodiment the composition has a tensile strength of at least about 40 GPa at 3.2 mm thickness according to ASTM D638, a flexural modulus of at least about 40 GPa at 6.4 mm thickness according to ASTM D790, EMI at 1 GHz, 1 mm thickness The shielding effect according to D790 standard is about 50 dB or more, the volume resistivity by the 4-point probe method is about 0.2 Ω · cm or less for specimens of 1 mm thickness, and 100 pieces are extracted after 550 ℃ / 1hr. The average value of the measured residual fiber length may be about 2 to 6 mm.

In another embodiment the composition has a tensile strength of about 315-420 MPa at a thickness of 3.2 mm by ASTM D638, a flexural modulus of about 40-55 GPa at a thickness of 6.4 mm by ASTM D790, and a thickness of 1 GHz, 1 mm. The shielding effect according to the EMI D790 standard is about 53 ~ 85 dB, the volume resistance by the 4-point probe method is about 0.05 ~ 0.18 Ω · cm for 1 mm thick specimens, and 100 pieces after 550 ℃ / 1hr for the molded product. The average value of the residual fiber length measured by extracting may be about 3.0 to 6 mm.

Another aspect of the invention relates to a molded article made from the composition. In an embodiment, the molded article may have a structure in which (B) carbon fibers and (C) metal filler are dispersed in a polyamide resin (A) containing an aromatic group in a main chain.

In an embodiment, the molded article comprises (A) melting a polyamide resin containing an aromatic group in a main chain and (C) a metal filler; (B) impregnated by passing the carbon fiber through the melt and then cut and pelletized; And it may be prepared including the step of molding the pellets. In embodiments, the pelletization may be pelletized by cutting the impregnated carbon fibers. The melting is a temperature at which the polyamide resin can be melted. Therefore, the metal filler may be dispersed in the polyamide in the melt.

The carbon fiber may have a bundle form.

In the specific example, the polyamide resin (A) and the metal filler (C) containing an aromatic group in the main chain may be first introduced into the extruder and melted, and then carbon fiber (B) may be added and impregnated.

In a preferred embodiment, the molded article is (A) polyamide resin containing an aromatic group in the main chain and (C) a metal filler in an extruder and the first pelletized to produce a composite resin pellet; Melting the composite resin pellets; (B) impregnating the composite resin pellets by passing carbon fibers and then pelletizing them; And it may be prepared including the step of molding the carbon pellet impregnated secondary pellets.

The impregnated mixture may be extruded in the form of long fibers and then cut into pellets to pelletize. In embodiments it may be pelletized by cutting to a length of about 8 to 20 mm, preferably about 10 to 15 mm. The shape of the carbon fiber of the long fiber is maintained in the above range can be obtained excellent shielding properties and strength.

The prepared pellets may be manufactured in various forms through injection molding, compression molding, casting molding, and the like.

Through such a molding process, the carbon fibers having a bundle shape may be dispersed with each other so that the fibers may be dispersed in a network shape in the final molded product. Here, the network shape refers to a form in which the fibers form a plurality of contact points and are connected to each other.

The carbon fiber may be partially cut after the molding. In an embodiment, the carbon fiber having a length of about 0.5 to 6 mm may be dispersed in a network shape in the molded article. The carbon fiber having a length of about 0.5 to 6 mm is at least about 80% by weight, in embodiments at least about 90% by weight of the total carbon fiber. In addition, after 1 hour at 550 ℃ for the molded article 100 residual fiber length is extracted to measure the length in the longitudinal direction may have an average value of about 2mm or more.

In the exemplary embodiment, the molded article has excellent electromagnetic shielding properties, conductivity, mechanical properties, and moldability, and thus may be preferably applied to the LCD protective bracket of a portable display product.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

실시예 Example

The specifications of each component used in the following Examples and Comparative Examples are as follows:

(A) Polyamide resin: Toyobo T-600, a nylon-MXD6 manufactured by Toyobo, was used.

(A ′) polyamide resin: PA 11 made from ARKEMA was used.

(B) Carbon fiber: Toray TORAYCA T700S 50C, 1650TEX manufactured by Toray was used.

(B ′) Carbon fiber: A chopped carbon fiber manufactured by Zoltek having an average diameter of 7 μm and a length of 6 mm was used.

(C) metal filler

(C1) micro stainless steel fiber: MSF150 (short metal fiber with 65-15-10 Fe-Cr-Ni) manufactured by Mirae Materials Co., Ltd. was used.

(C2) Low melting point 300 ℃ or less metal powder: 97C (97% Sn, 2.5% Cu as powder type tin-copper alloys) manufactured by Warton Metals Limited was used.

(D) Metal-coated graphite: Sulzer 2805 (Ni: 75 wt%, graphite: 25 wt%) was used as Ni-coated graphite.

(E) Carbon Nano Tube: NC7000 (multi-wall CNT) manufactured by Nanocyl was used.

실시예 1~8Examples 1-8

Polyamide resin, metal filler, and other additives shown in Table 1 were mixed in a conventional mixer and extruded using a twin screw extruder having L / D = 35 and Φ = 45 mm, and then the extrudate was prepared in pellet form. The pellets were melted using a long-screw extruder, and impregnated with carbon fibers (B) by a pultrusion method, and cut into long pellets having a length of 12 mm to prepare a carbon fiber having a length of 12 mm. Specimens for measuring physical properties and evaluating applications such as EMI and resistance at the injection temperature of 270 ° C were prepared using a long fiber injection machine. After the specimens were allowed to stand for 48 hours at 23 ° C. and 50% relative humidity, the physical properties were evaluated by the following method, and the results are shown in Table 1.

Evaluation method :

(1) Tensile strength: evaluated by ASTM D638 at 5 mm / min conditions, the unit is MPa.

(2) Flexural modulus: evaluated at 1.27 mm / min by ASTM D790, and the unit is GPa.

(3) EMI shielding (dB): After leaving the sample for 48 hours at 23 ° C., 50% relative humidity, the electromagnetic shielding performance of the 1 mm thick sample (6 × 6) at 1 GHz was measured according to EMI D790.

(4) Volume resistance: It was evaluated by the 4-point probe method (Ωcm).

(5) Residual fiber length (mm) after ignition loss: 100 residual fiber lengths were extracted after 550 ° C./1hr, and the length was measured in the longitudinal direction to be an arithmetic mean value for the length.

비교예 1~5Comparative Examples 1 to 5

Comparative Examples 1 to 3 were carried out in the same manner as in Example 1 except for changing the composition of each component as shown in Table 2 below.

Comparative Example 4 was carried out in the same manner as in Example 1 except that the length of the carbon fiber to 6mm by cutting the pellet length to 6mm after impregnating the carbon fiber by the pultrusion method.

In Comparative Example 5, polyamide resin, chopped carbon fiber (B ') and metal filler were mixed in a conventional mixer with the contents shown in Table 1 below, and extruded using a twin screw extruder having L / D = 35 and Φ = 45 mm to pellet After the preparation in the form, the physical properties were evaluated in the same manner as in Example 1 except that a specimen for measuring the physical properties and the evaluation of the application, such as EMI and resistance at the injection temperature of 270 ℃.

Table 1

		Example
		One	2	3	4	5	6	7	8
(A) PA		30	25	30	20	15	20	20	20
(A ') PA		-	-	-	-	-	-	-	-
(B) carbon fiber		65	65	65	75	80	75	75	75
(B ') chopped carbon fiber		-	-	-	-	-	-	-	-
(C) metal filler	C1	5	10	-	5	5	5	5	5
(C) metal filler	C2	-	-	5	-	-	-	-	-
(D) metal coated graphite		-	-	-	-	-	3	-	3
(E) CNT		-	-	-	-	-	-	One	One
Pellet length (mm)		12	12	12	12	12	12	12	12
The tensile strength		318	320	319	343	381	352	345	352
Flexural Modulus		45	42	41	43	41	44	43	44
EMI shielding (dB)		53	59	54	65	71	67	66	68
Resistance (Ωcm)		0.15	0.12	0.17	0.16	0.14	0.12	0.12	0.10
importance		1.48	1.48	1.48	1.49	1.49	1.50	1.49	1.50
Length of residual fiber after ignition loss (mm)		3.4	3.3	3.1	3.6	3.5	3.5	3.6	3.4

TABLE 2

		Comparative example
		One	2	3	4	5
(A) PA		35	-	55	30	30
(A ') PA		-	30	-	-	-
(B) carbon fiber		65	65	40	65	-
(B ') chopped carbon fiber		-	-	-	-	65
(C) metal filler	C1	-	5	5	5	5
(C) metal filler	C2	-	-	-	-	-
(D) metal coated graphite		-	-	-	-	-
(E) CNT		-	-	-	-	-
Pellet length (mm)		12	12	12	6	6
The tensile strength		319	290	270	291	280
Flexural Modulus		47	35	31	35	33
EMI shielding (dB)		54	51	38	41	35
Resistance (Ωcm)		0.31	0.14	0.20	0.25	0.23
importance		1.48	1.43	1.47	1.48	1.47
Length of residual fiber after ignition loss (mm)		3.3	3.3	3.2	1.4	0.8

Comparing Examples 1, 4 and 5 as shown in Table 1, it can be seen that the use of a high content of carbon fiber has a flexural modulus of 40 GPa or more and an EMI shielding effect of 50 dB or more and increases as the content of the carbon fiber increases. have. This can be seen that the content of the carbon fiber is much higher than the comparative example 3. In addition, when the aromatic polyamide is not as in Comparative Example 2, it can be seen that the tensile strength and modulus are significantly reduced.

In Examples 1 to 8, the metal filler was used to have a high modulus and a high EMI shielding effect, as well as a low volume resistivity of 0.2 Ω · cm or less, whereas Comparative Example 1 without the metal filler had a modulus and EMI shielding effect. It is similar but the resistance is high.

In Examples 1 to 5, a long fiber reinforced thermoplastic resin having a pellet length of 12 mm extruded by pultrusion method, overall performance such as modulus, EMI shielding effect, and resistance was higher than that of Comparative Example 4 using 6 mm carbon fiber extruded in the same method. In particular, it can be seen that the comparative example 4, in particular, the length of the fibers (ash) remaining after the loss of ignition is also shortened so that there is a significant difference in EMI shielding and electrical resistance, which is important for networking in the injection molding. In addition, Comparative Example 5 using a 6mm general chopped CF also showed a significant decrease in modulus, EMI shielding effect and resistance.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains has the technical idea of the present invention. However, it will be understood that other specific forms may be practiced without changing the essential features. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

(A) about 10 to 34% by weight of a polyamide resin containing an aromatic group in the main chain;

(B) about 65 to 85 weight percent of carbon fibers; And

(C) about 1 to 20 weight percent of a metal filler;

High-rigidity electromagnetic shielding composition comprising a.
The highly rigid electromagnetic shielding composition according to claim 1, wherein the polyamide resin (A) is a wholly aromatic polyamide, a semi-aromatic polyamide or a mixture thereof.
3. The highly rigid electromagnetic shielding composition of claim 2, wherein the semiaromatic polyamide is a polymer of aromatic diamine and aliphatic dicarboxylic acid.
According to claim 3, The semi-aromatic polyamide is a highly rigid electromagnetic shielding composition, characterized in that represented by the formula

<Formula 1>

Ar is an aromatic group, R is a C 4-20 alkylene group, n is an integer of 50 to 500.
The high stiffness electromagnetic shielding composition according to claim 1, wherein the carbon fiber (B) comprises a bundle form.
The highly rigid electromagnetic shielding of claim 1, wherein the metal filler (C) comprises at least one selected from the group consisting of metal powder, metal beads, metal fibers, metal flakes, metal coated particles, and metal coated fibers. Composition.
The metal filler of claim 1, wherein the metal filler (C) is selected from the group consisting of aluminum, stainless steel, iron, chromium, nickel, black nickel, copper, silver, gold, platinum, palladium, tin, cobalt and two or more alloys thereof. Highly rigid electromagnetic shielding composition, characterized in that at least one selected.
According to claim 1, wherein the composition (A) + (B) + high rigidity electromagnetic shielding further comprises a carbon nanotube in the range of about 0 to 20 parts by weight or less based on 100 parts by weight Composition.
The high stiffness electromagnetic shielding composition of claim 8, wherein the composition further comprises metal-coated graphite.
10. The highly rigid electromagnetic shielding composition of claim 9, wherein the metal-coated graphite has particles, fibers, flakes, amorphous, or a combination thereof.
The highly rigid electromagnetic shielding composition of claim 10, wherein the metal-coated graphite has an average particle diameter of about 10 to 200 μm.
The method of claim 9, wherein the metal is at least one selected from the group consisting of aluminum, stainless, iron, chromium, nickel, black nickel, copper, silver, gold, platinum, palladium, tin, cobalt and two or more alloys thereof. Highly rigid electromagnetic shielding composition, characterized in that.
The method of claim 1, wherein the composition further comprises at least one additive selected from the group consisting of flame retardants, plasticizers, coupling agents, thermal stabilizers, light stabilizers, inorganic fillers, mold release agents, dispersants, anti-drip agents, carbon fillers and weather stabilizers. High-strength electromagnetic shielding composition characterized in that.
The composition of claim 1 wherein the composition has a tensile strength of at least about 40 GPa at a thickness of 3.2 mm by ASTM D638, a flexural modulus of at least 40 GPa at a thickness of 6.4 mm by ASTM D790, and EMI at 1 GHz, 1 mm thick. The shielding effect according to D790 standard is about 50 dB or more, the volume resistance by the 4-point probe method is about 0.2 0.2 · cm or less for specimens of 1 mm thickness, and 100 pieces are extracted after 550 ℃ / 1hr. The high rigidity electromagnetic shielding composition, characterized in that the measured residual fiber length is about 2 to 6 mm.
A molded article prepared from the composition according to any one of claims 1 to 14, wherein the molded article has a structure in which (A) carbon fibers and (C) metal filler are dispersed in a polyamide resin containing (A) an aromatic group in its main chain.
The molded article of claim 15, wherein the molded article is an LCD protective bracket of a portable display product.
The molded article according to claim 15, wherein the molded article comprises: (A) melting a polyamide resin containing an aromatic group in a main chain and (C) a metal filler; (B) impregnated by passing the carbon fiber through the melt and then cut and pelletized; And molding the pellets.
18. The molded article of claim 17, wherein the pellets have a length of about 8 to 20 mm.
16. The molded article of claim 15, wherein the molded article is at least about 80 wt% of the total carbon fibers in the molded article with carbon fibers having a residual fiber length of about 0.5 to 6 mm.