KR20130066942A - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition is provided to have excellent impact resistance and to have excellent metal texture-feeling exterior. CONSTITUTION: A thermoplastic resin composition includes 100.0 parts by weight of a thermoplastic resin, 0.01-10 parts by weight of a plate-like or spherical metal particle, and 0.5-15 parts by weight of a thermoexpandable microparticle. The thermoplastic expandable particle is a polymer particle including a hydrocarbon foam compound. The plate-like metal particle has a thickness ratio with regard to long diameter of 1/80-1/1. The thermal expandable microparticle includes a polymer with a glass transition temperature of 30-120 °C.

Description

Thermoplastic resin composition and molded article using the same {THERMOPLASTIC RESIN COMPOSITION AND MOLDED PRODUCT USING THE SAME}

The present invention relates to a thermoplastic resin composition having an excellent metal texture and a molded article using the same.

In recent years, plastic exterior products in which various colors are implemented in electric / electronic parts and automobile parts are becoming popular, and plastic exterior products capable of feeling a more advanced texture are increasingly being launched.

These plastic exterior products mainly exhibit a metal texture on the exterior of the resin by adding metal to the plastic resin. This is disclosed in Japanese Patent Application Laid-Open Nos. 2001-262003 and 2007-137963, but the metal texture does not appear during the actual experiment, and there is a problem in that a flow mark or weld line occurs during injection. In addition, Japanese Patent Laid-Open Publication No. 1995-196901 shows a metal texture obtained by punching a plastic resin and adding a metal microplate having a gloss having an average shape ratio (thickness / average particle diameter) of 1/100 to 1/8. There is a limit such as the generation of lines.

One embodiment of the present invention is to provide a thermoplastic resin composition having almost no flow mark and weld line generation and having an excellent metallic texture appearance.

Another embodiment of the present invention is to provide a molded article using the thermoplastic resin composition.

According to one embodiment of the present invention, the thermoplastic resin composition comprising a thermoplastic resin, a plate-shaped or spherical metal particles, and thermally expandable fine particles, wherein the thermally expandable fine particles are polymer particles containing a hydrocarbon-like foamable compound. Is provided.

The thermoplastic resin may include 0.01 kPa to 10 kPa of the metal particles and 0.5 kPa to 15 kPa of the thermally expandable fine particles, based on 100 parts by weight of the thermoplastic resin.

The plate-shaped metal particles may be particles having a flat surface having a thickness ratio of about 1/80 to about 1/1 of a long diameter.

The metal particles may have a plate shape having a long diameter of about 5 mm to about 100 μm of a flat surface, or a spherical shape having a particle diameter of about 5 μm to about 100 μm.

The metal particles may be made of a material containing aluminum, copper, gold, or a combination thereof.

The thermally expandable fine particles may include a thermoplastic resin having a glass transition temperature of about 30 ° C. to about 120 ° C.

The thermally expandable fine particles may have a maximum expansion temperature of about 150 Pa to about 280 ° C.

The thermally expandable fine particles may have an average particle diameter of about 5 kPa to about 60 µm before foaming, and may be about 10 to about 100 times by volume at the maximum expansion temperature.

The thermoplastic resin may be one selected from polycarbonate resin, rubber modified vinyl copolymer resin, polyester resin, polyalkyl (meth) acrylate resin, polystyrene resin, polyolefin resin and combinations thereof.

The thermoplastic resin composition may further include one selected from glass particles, mica, graphite, pearl particles, and combinations thereof.

In another embodiment of the present invention, a molded article manufactured using the thermoplastic resin composition is provided.

Other aspects of the present invention are included in the following detailed description.

The thermoplastic resin composition has excellent impact resistance, hardly generates flow marks and weld lines, and has an excellent appearance with a metallic texture.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

As used herein, unless otherwise specified, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible. "(Meth) acrylic acid ester" means that both "acrylic acid alkyl ester" and "methacrylic acid alkyl ester" can be used. It means that it is possible.

Unless stated otherwise in the present specification, "long diameter" means the longest length of a line connecting two points in a closed curve, and "closed curve" means that one point on the curve moves in one direction again. It means a curve returning to the starting point.

Thermoplastic resin composition according to one embodiment is a thermoplastic resin, plate-shaped or spherical metal particles; And thermally expandable fine particles. Since the thermoplastic resin composition has almost no appearance of flow marks and weld lines, and has an excellent appearance with a metallic texture, molded articles having an excellent appearance even without a coating process, in particular, electrical and electronic parts and automobile parts It can be usefully applied to plastic exterior products such as. Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

(A) a thermoplastic resin

The thermoplastic resin known as the thermoplastic resin can be used without limitation, and for example, polycarbonate resin, rubber modified vinyl-based graft copolymer resin, polyester resin, polyalkyl (meth) acrylate resin, polystyrene resin, polyolefin Resin or a combination thereof can be used. The thermoplastic resin may impart basic physical properties such as impact resistance, heat resistance, bending characteristics, and tensile properties.

The polycarbonate resin may be prepared by reacting a diphenol with phosgene, a halogen formate, a carbonic 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- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether, and the like. Of these, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1- Cyclohexane may be used, and more preferably 2,2-bis (4-hydroxyphenyl) propane may be used.

The polycarbonate resin may have a weight average molecular weight of 10,000 to 200,000 g / mol, specifically 15,000 to 80,000 g / mol, but is not limited thereto.

The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin.

Examples of the linear polycarbonate resin include a bisphenol-A polycarbonate resin and the like. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride, trimellitic acid and the like with a diphenol and a carbonate. The polyfunctional aromatic compound may be contained in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester carbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. As the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate and the like can be used.

The rubber-modified vinyl graft copolymer resin may be a copolymer in which 5 to 95 wt% of the vinyl polymer is grafted to 5 to 95 wt% of the rubbery polymer.

The rubbery polymer may be at least one selected from the group consisting of butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane / polyalkyl (Meth) acrylate rubber composite or a combination thereof.

Wherein the vinyl polymer comprises 50 to 95% by weight of a first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And 5 to 50% by weight of a second vinyl monomer of an unsaturated nitrile monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof.

As the aromatic vinyl monomer, styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene, or a combination thereof may be used. Specific examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

As the acrylic monomer, alkyl (meth) acrylate, (meth) acrylic acid ester, or a combination thereof may be used. Wherein said alkyl means C1 to C10 alkyl. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Methacrylate may be used. Specific examples of the (meth) acrylic acid esters include (meth) acrylates.

As the heterocyclic monomers, maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof may be used.

As the unsaturated nitrile monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, or a combination thereof may be used.

In preparing the rubber-modified vinyl-based graft copolymer, the particle diameter of the rubber particles may be about 0.05 to about 4 μm in order to improve impact resistance and surface properties of the molded product. Rubber particles having a particle size in the above range have excellent impact strength. It can be secured.

The rubber modified vinyl graft copolymer may be used alone or in the form of a mixture of two or more thereof.

Specific examples of the rubber-modified vinyl graft copolymers include graft copolymerization of styrene, acrylonitrile and optionally methyl (meth) acrylate in the form of a mixture of butadiene rubber, acrylic rubber or styrene / butadiene rubber. have.

Specific examples of the rubber-modified vinyl-based graft copolymer include graft-copolymerized methyl (meth) acrylate with butadiene rubber, acrylic rubber or styrene / butadiene rubber.

More specific examples of the rubber-modified graft copolymers include acrylonitrile-butadiene-styrene graft copolymers, methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymers, and the like.

The method for producing the rubber-modified vinyl-based graft copolymer is well known to those skilled in the art, and any of emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be used, For example, the aforementioned aromatic vinyl monomer may be added in the presence of a rubbery polymer and emulsion polymerization or bulk polymerization may be carried out using a polymerization initiator.

The polyester resin may be an aromatic polyester resin, which is obtained by condensation polymerization of a terephthalic acid or terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms by melt polymerization. Wherein said alkyl means C1 to C10 alkyl.

Specific examples of the aromatic polyester resin include polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexanedimethylene terephthalate resin, or a part of these resins Among them, a polyethylene terephthalate resin, a polytrimethylene terephthalate resin, a polybutylene terephthalate resin and an amorphous polyethylene terephthalate resin can be used. And more preferably, polybutylene terephthalate resin and polyethylene terephthalate resin can be used.

The polybutylene terephthalate resin is a polymer polycondensed by direct esterification or transesterification of a 1,4-butanediol monomer and a terephthalic acid or dimethyl terephthalate monomer.

In order to increase the impact strength of the polybutylene terephthalate resin, the polybutylene terephthalate resin may be selected from polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), low molecular weight aliphatic polyester or aliphatic poly. It may be used in the form of a modified polybutylene terephthalate resin copolymerized with an amide or blended with an impact improving component.

The polybutylene terephthalate resin may have an intrinsic viscosity [η] of about 0.35 kPa to about 1.5 mW / g as measured by about 25 ° C. of o-chlorophenol, and specifically about 0.5 kPa to about 1.3 mW / g. . When the intrinsic viscosity of the polybutylene terephthalate resin is within the above range, the mechanical strength, the moldability, and the like are excellent.

The polyalkyl (meth) acrylate resin can be obtained by polymerizing a starting monomer containing an alkyl (meth) acrylate by a known polymerization method such as suspension polymerization, bulk polymerization and emulsion polymerization.

The alkyl (meth) acrylate has an alkyl group of C1 to C10, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (Meth) acrylate etc. are mentioned.

At this time, the alkyl (meth) acrylate may be included in more than 50% by weight relative to the total amount of polyalkyl (meth) acrylate.

The polyalkyl (meth) acrylate may have a weight average molecular weight in the range of about 10,000 to about 200,000 g / mol, specifically, about 15,000 to about 150,000 g / mol. When the weight average molecular weight of the polyalkyl (meth) acrylate is within the above range, the hydrolysis resistance, scratch resistance and processability are excellent.

As the polystyrene resin, for example, rubber-modified polystyrene resin (HIPS) reinforced with impact strength may be used.

The polyolefin resin may be a polyethylene resin (PE), a polypropylene resin (PP), a resin in a copolymerized form thereof, or the like.

The thermoplastic resin may be used in the form of an alloy mixed with two or more kinds, and examples thereof include polycarbonate, acrylonitrile-butadiene-styrene graft resin (ABS), and styrene-acrylonitrile copolymer resin (SAN). It may be the case when using a mixture or a mixture of polycarbonate, acrylate-styrene-acrylonitrile graft resin (ASA) and styrene-acrylonitrile copolymer resin (SAN).

(B) metal particles

The thermoplastic resin may be provided with a metal texture by including the metal particles. The metal particles may be plate-shaped or spherical.

The metal particles may be a kind of sparkling particles, and when the metal particles are plate-shaped, they have a flat surface that reflects light. At this time, the flat surface means a flat surface to the extent that the particles glisten with the naked eye, and means, for example, the surface of the plate glass, or the metal surface finished by polishing.

The metal particles may be made of a material containing aluminum, copper, gold, or a combination thereof, for example, may be made of aluminum.

The metal particles may be included in an amount of about 0.01 kPa to about 10 kPa parts, specifically about 0.5 kPa to about 3 kPa parts, relative to 100 parts by weight of the thermoplastic resin. When the thermoplastic resin comprises metal particles in the above range of contents, a predetermined metal texture is imparted.

When the metal particles have a plate shape, the thickness ratio of the plate to the long diameter of the flat surface may be 1/80 to 1/1, for example, may be 1/40 mm to 1/5 mm. The long diameter means the longest diameter. When the metal particles having the size range are included, there is almost no generation of flow marks and weld lines, and a molded article having an excellent metal texture can be obtained.

When the metal particles are plate-shaped, the long diameter of the flat surface may be about 5 to about 100 μm. For example, the cross-sectional area of the flat surface is about ² to about 100㎛ 22,500㎛ may be ^two days. For example, the plate-shaped thickness of the plate-shaped metal particles may be about 0.05 to about 20 μm, more specifically about 0.1 to about 5 μm.

When the metal particles are spherical, the particle diameter may be about 5 kPa to about 100 mPa.

(C) Thermal expansion  Particulate

The thermally expandable fine particles are polymer particles containing a hydrocarbons foamable compound. Above a certain temperature, the hydrocarbon-like expandable compound generates a gas while being vaporized or decomposed by heat to form a hollow in the thermally expandable fine particles, and the polymer expands to form a shell. At this time, since the polymer is very soft and excellent in elasticity, it does not rupture. When the thermally expansible fine particles rupture upon expansion, the foaming pressure increases during molding of the thermoplastic resin composition, thereby deteriorating the surface properties. Since the polymer does not rupture, it is possible to obtain excellent surface properties.

The thermally expandable fine particles are heated to expand during molding of the thermoplastic resin composition, and a molded article molded from the thermoplastic resin composition including the thermally expandable fine particles may be formed as a foam.

The expansion start temperature (Tstart) and the maximum expansion temperature (Tmax) may be determined according to the boiling point of the foamable compound of the hydrocarbons and the glass transition temperature (Tg) of the polymer forming the shell upon foaming. In addition, it is possible to adjust the maximum expansion displacement (Dmax) according to the content of the foaming compound of hydrocarbons and the gas barrier property of the polymer. For example, the glass transition temperature (Tg) of the polymer forming the shell upon foaming may be from about 30 Pa to about 120 ° C, so that the thermally expandable fine particles are prepared so that foaming can be started from about 110 Pa to about 180 ° C. Can be.

The polymer forming the shell upon foaming is basically possible as long as it is a thermoplastic resin that can be softened to enable foaming of the internal gas at the foaming start temperature. Specifically, acrylic resin, vinylidene chloride resin, acrylonitrile resin, ABS resin, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, vinyl chloride resin, acetal resin, cellulose ester, cellulose acetate, fluorine resin, methylpentene A polymer or a thermoplastic polymer made by mixing them may be used, but is not limited thereto. For example, acrylonitrile, methacrylonitrile, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethyl Hexyl acrylate, n-octyl acrylate, lauryl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, polyethylene glycol acrylate, methoxypolyethylene glycol acrylate, glycidyl acrylate, dimethylaminoethyl acrylic Rate, diethylaminoethyl acrylate, vinylidene chloride, butadiene, styrene, p- or m-methylstyrene, p- or m-ethylstyrene, p- or m-chlorostyrene, p- or m-chloromethylstyrene, Styrenesulfonic acid, p- or m-t-butoxystyrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ether, It may be, but is not limited to, a polymer or copolymer comprising at least one of allyl butyl ether, allyl glycidyl ether, unsaturated carboxylic acid including (meth) acrylic acid or maleic acid, and alkyl (meth) acrylamide, and the like. . Such a polymer can be selected according to the desired use such as its softening temperature, heat resistance and chemical resistance. For example, copolymers containing vinylidene chloride have excellent gas barrier properties, and copolymers containing about 80% by weight or more of nitrile monomers have excellent heat resistance and chemical resistance.

The hydrocarbon-type expandable compound contained in the thermally expandable fine particles is characterized by a boiling point of about 100 ° C. or lower, without dissolving the polymer forming the shell upon foaming. Low boiling liquid phase materials, commonly referred to as volatile swelling agents, are used, but solid phase materials that decompose by heat to produce gas may also be used. Specifically, butane, pentane, hexane, heptane, halide of methane, tetra alkyl silane, hydrofluoro ether, azobisisobutyronitrile (AIBN), which is pyrolyzed by heating and becomes gaseous, may be used. It doesn't work.

The inclusion rate of the hydrocarbon-like foamable compound contained in the thermally expandable microparticles may be different depending on the application, but is not particularly limited. For example, it is about 0.5 kPa to about 15 kW% by weight, preferably based on the total weight of the thermally expandable microparticles. About 1 to about 10 weight percent.

Thermally expandable microparticles | fine-particles are generally manufactured by the suspension polymerization method which polymerizes monomer residue in the state which mechanically disperse | polymerized the polymerizable monomer mixture containing a polymerizable monomer, a blowing agent, etc. in incompatible liquids, such as water.

The thermally expandable fine particles having excellent foaming properties and uniform particle sizes of the present invention may have an average particle diameter of about 5 kPa to about 60 m before foaming, for example, about 10 kPa to about 50 m, and other examples of about 20 to about It is about 35 micrometers. In the case of thermally expandable fine particles having an average particle diameter of about 5 kPa to about 60 µm, the thermal expansion behavior is accelerated by flattening the shell of a suitable thickness without rupturing upon expansion.

The thermally expandable fine particles may have a maximum expansion temperature of about 150 to about 280 ° C., for example, about 180 ° C. to about 270 ° C., and may be appropriately adjusted according to a required use. For example, a thermoplastic resin composition can be comprised so that the difference of the maximum expansion temperature between the said thermally expansible microparticles may be 20 degrees C or less. The thermoplastic resin composition configured as described above may expand and expand the thermally expandable fine particles only in a narrow temperature range, thereby facilitating control of the molding process.

The thermally expandable fine particles may increase by about 10 times to about 100 times in volume at the maximum expansion temperature, for example, about 30 times to about 60 times. When the thermoplastic resin composition including the thermally expandable fine particles is molded by injection or the like, the thermally expandable fine particles are expanded, and the manufactured article includes the thermally expandable fine particles in the expanded state. In the molded article, the thermally expandable fine particles may be in a state of about 1.05 times to about 20 times increased in volume compared to before expansion, for example, about 2 times to about 15 times increased.

The thermally expandable fine particles may be included in the thermoplastic resin composition together with the metal particles described above to improve the orientation of the metal particles. In the case of the plate-shaped metal particles, when the thin plate-shaped thin portion, that is, the edge portion is directed toward the surface of the molded article, the metal texture is shaken, and the portion is dark. Therefore, when forming the edge portion of the plate-shaped metal particles (b1) to be well aligned in a certain direction so as not to face the surface it can be higher metal texture. Mixing the thermally expandable fine particles with the plate-shaped metal particles causes the edge portions of the plate-shaped metal particles to be well aligned so as not to face the surface due to the presence of the spherically expanded thermally expandable fine particles during molding. In other words, the thermally expandable fine particles can be positioned between the plates of the plate-shaped metal particles to help the arrangement of the particles to be uniformly arranged. As a result, the thermoplastic resin composition including both the thermally expandable fine particles and the plate-shaped metal particles has a very good metal texture, and because the plate-shaped metal particles are well aligned, the flow mark and the weld line in the molded article are line) to reduce the occurrence.

The thermally expandable fine particles may be included in an amount of about 0.5 kPa to about 5 kPa parts, for example, about 1 kPa to about 3 kPa parts relative to 100 parts by weight of the thermoplastic resin. When the thermoplastic resin includes the thermally expandable fine particles in the above range, the glossiness can be maintained while improving the metal texture by improving the orientation of the metal particles.

(D) inorganic particles

The thermoplastic resin composition may further include the inorganic particles.

The inorganic particles may be another kind of sparkling particles having a flat surface that reflects light. In this case, the description of the flat surface is as described above.

As the inorganic particles, glass particles, mica, graphite, pearl particles, or a combination thereof may be used, and among these, glass particles may be used.

The glass particles have a plate-like structure, and thus are different from glass fibers having a mainly cylindrical shape. Cylindrical glass fibers do not reflect light and are difficult to exhibit metal texture. The cross section of the glass particles may have a shape such as a circular, elliptical, amorphous form.

The inorganic particles may have a long diameter of about 10 to about 200 μm, a thickness of about 0.5 to about 10 μm, and a cross-sectional area of about 80 to about 32,000 μm ² . When the inorganic particles have a long diameter, a thickness, and a cross-sectional area in the above range, a molded article having an excellent metal texture can be obtained with little generation of flow marks and weld lines.

The inorganic particles may be included in an amount of about 0.05 to about 10 parts by weight based on 100 parts by weight of the thermoplastic resin, and more specifically, about 0.2 to about 3 parts by weight. When the inorganic particles are used in the content range, the impact strength is excellent, flow marks and weld lines are hardly generated, and it is advantageous to manufacture molded articles having excellent metal texture.

The metal particles (B) and the inorganic particles (C) obtained by the punching are in a weight ratio of about 1: 5 to about 5: 1, specifically, in the weight ratio of about 1: 2 to about 2: 1. Can be mixed within. When mixed in the ratio range, the impact strength is excellent, there is little flow mark and weld line generation, and it is advantageous to manufacture a molded article having an excellent metal texture.

(D) Other additives

The thermoplastic resin composition may include an antibacterial agent, a heat stabilizer, an antioxidant, a release agent, a light stabilizer, a surfactant, a coupling agent, a plasticizer, a admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, a colorant, a flame retardant, a weatherproof agent, a ultraviolet absorber, a sunscreen, It may further include an additive of a nucleating agent, an adhesion aid, an adhesive, or a combination thereof.

The antioxidant may be a phenol, phosphite, thioether or amine antioxidant, the release agent is a fluorine-containing polymer, silicone oil, metal salt of stearic acid, montanic acid Metal salts, montanic acid ester waxes or polyethylene waxes may be used. Further, benzophenone type or amine type endurance agent can be used as the weathering agent, and a dye or pigment can be used as the coloring agent. Titanium dioxide (TiO ₂ ) or carbon black can be used as the ultraviolet ray blocking agent. As the nucleating agent, talc or clay may be used.

The additive may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, specifically, may be included in about 40 parts by weight or less based on 100 parts by weight of the thermoplastic resin composition, more specifically about 0.1 to About 30 parts by weight.

The above-mentioned thermoplastic resin composition can be manufactured by a well-known method of manufacturing resin composition. For example, after mixing the components and other additives according to the embodiments at the same time, it can be melt-extruded in an extruder and produced in pellet form.

According to another embodiment of the present invention, a molded article manufactured by molding the aforementioned thermoplastic resin composition is provided. That is, a molded article can be manufactured by various processes, such as injection molding, blow molding, extrusion molding, and thermoforming, using the said thermoplastic resin composition. In particular, there is little flow mark and weld line generation, and can be usefully applied to molded articles having a metallic texture appearance, in particular, plastic exterior products such as electric and electronic parts and automobile parts. In addition, the molded article is manufactured from a thermoplastic resin composition including metal particles, so that the metal texture is excellently expressed, and thus, an additional coating process for imparting a metal texture is not required.

The molded article may be prepared by adjusting the density of the thermally expandable fine particles and the foaming temperature thereof, and the degree of metal texture may be determined according to the content of the metal particles. Since the molded article is controlled in the orientation of the metal particles, a higher metal texture may be expressed when the molded article includes the same amount of metal particles than when the orientation is not controlled. For example, in order to manufacture a molded article having excellent metal texture, the density may be about 0.1 kPa to about 3.0 kPa, and the content of the metal particles may be about 0.2 kPa to about 3 kPa in 100% by weight of the molded article. As another example for producing a molded article having a good metal texture, the molded article may include about 0.002 kPa to about 0.03 kg metal particles per cm 3 of unit volume.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

Example

Each component used for manufacture of the thermoplastic resin composition of the following Example is as follows.

(A) a thermoplastic resin

MABS® Resin (MABS Resin SF-0950 of Cheil Industries)

(B) amorphous Plate  Metal particles

(B-1) Amorphous having a cross-sectional area of 1,200 μm ² , long diameter of 20 μm, and thickness of 1 μm

Plate-shaped aluminum particles

(B-2) Amorphous having a cross section of 1,200 μm ² , 80 μm in long diameter, and 1 μm in thickness

Plate-shaped aluminum particles

(C) Thermal expansion  Particulate

MATSUMOTO Corporation Microsphere F-260D

Average particle diameter 30㎛ Maximum expansion temperature 260 ℃

(D) foaming agent

Geumyang CELLCOM-EMS Series

Example  1 to 5 and Comparative example  1 to 5

The thermoplastic resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 5 were prepared using the above-mentioned components and the compositions shown in Table 1 below, followed by extrusion at a temperature range of 230 ° C. in a conventional twin screw extruder. The extrudate was then prepared in pellet form.

After the pellets prepared according to Examples 1 to 5 and Comparative Examples 1 to 5 were dried at 80 ° C for 4 hours, an injection molding machine having an injection capacity of 6 Oz was used, and the cylinder temperature was 240 ° C and the mold temperature was 80 ° C. The cycle time was set to 30 seconds, and the physical properties were measured according to the following physical property measurement criteria and are shown in Table 1.

(Physical measurement standard)

The prepared physical specimens were measured for physical properties by the following method and the results are shown in Table 2 below.

1) Metal Texture:

X-rite's MA98 Multi-Angle Spectrophotometer was measured and evaluated by the flop index (Flop Index, FI), the values are shown in Table 1 below.

The flop index FI is an index indicating the surface metal texture, and the luminance L of each reflected light is measured at 15 °, 45 °, and 110 °, and is calculated according to the definition of Equation 1 below. L (x˚) means luminance measured at x˚.

[Equation 1]

FI = 2.69 × (L (15 °)-L (110 °)) ^1.11 / (L (45 °)) ^0.86

2) Injection appearance: A weld line may occur since the injection molding is performed using a mold having two gates. The appearance of the injection molding was visually observed, and the results determined according to the following evaluation criteria are shown in Table 2 below.

(Double-circle): The state / metal texture which there is no flow mark and the weld line exotic color is very excellent.

(Circle): There is no flow mark, but the state of the weld line with a little discoloration / metal texture is excellent.

(Triangle | delta): There exists a state / metal texture in which a flow mark and a weld line discoloration appear.

X: There is almost no state / metal texture in which a flow mark and the weld line discoloration show severely.

Item Example Comparative example One 2 3 4 5 6 7 8 9 One 2 3 4 5 6 (A) thermoplastic resin
(Parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 (B)
Amorphous plate-shaped metal particles (B-1)
(Parts by weight) 0.5 One 0.5 One - - - - 0.5 0.5 One - - 0.5 One (B-2)
(Parts by weight) - - - - 0.5 One 0.5 One - - - 0.5 One 0.5 - (C) thermal expansion
Particulate 3 3 5 5 3 3 5 5 One - - - - - - (D) foaming agent - - - - - - - - - - - - - - 3 Injection appearance Metal texture 13 14 11 12 9 10 8 9 14 14 14 12 12 14 3 Flow mark ○ ○ ◎ ◎ ○ ○ ◎ ◎ ○ x x x x x ○ Weld line ○ ○ ◎ ○ ○ ○ ○ ○ ○ x x x x x ○ Injection weight per unit volume
(g / cm3) 60.8 61.2 57.3 58.1 60.5 62.3 56.9 57.5 74.3 81.6 81.7 81.3 81.4 80.8 60.8

Through the above Table 1, the molded article prepared from the thermoplastic resin composition of Examples 1 to 9 was excellent in the metal texture, it was confirmed that the excellent results in terms of flow mark and weld line reduction. On the other hand, (C) Comparative Examples 1 to 5 that do not include thermally expandable fine particles did not reduce the flow mark and weld lines, and (C) Comparative Example 6 including the (D) foaming agent instead of thermally expandable fine particles showed flow marks and weld lines. Although excellent in terms of reduction, the metal texture dropped significantly.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (11)

Thermoplastic resin;
Plate-shaped or spherical metal particles; And
Thermally expandable particulates
Lt; / RTI >
The thermally expandable fine particles are thermoplastic particles comprising a hydrocarbon-like expandable compound. The method of claim 1,
The thermoplastic resin may include 0.01 to 10 parts by weight of the metal particles and 0.5 to 15 parts by weight of the thermally expandable fine particles, based on 100 parts by weight of the thermoplastic resin. The method of claim 1,
The plate-shaped metal particle is a thermoplastic resin composition is a particle having a flat surface having a thickness ratio of about 1/80 to about 1/1 of the thickness of the long diameter. The method of claim 1,
The metal particles are in the form of a plate having a long diameter of 5 to 100 μm in a flat surface, or a spherical thermoplastic resin composition having a particle diameter of 5 to 100 μm. The method of claim 1,
The metal particle is a thermoplastic resin composition consisting of a material containing aluminum, copper, gold or a combination thereof. The method of claim 1,
The thermally expandable fine particles are thermoplastic resin composition comprising a polymer having a glass transition temperature of 30 to 120 ℃. The method of claim 1,
The thermally expandable fine particles have a maximum expansion temperature of 150 to 280 ° C. The method of claim 1,
The thermally expandable fine particles have a mean particle diameter of 5 to 60 µm before foaming, and have a volume of 10 to 100 times by volume at the maximum expansion temperature. The method of claim 1,
The thermoplastic resin is a thermoplastic resin composition comprising one selected from polycarbonate resin, rubber modified vinyl copolymer resin, polyester resin, polyalkyl (meth) acrylate resin, polystyrene resin, polyolefin resin and combinations thereof. The method of claim 1,
The thermoplastic resin composition further comprises one selected from glass particles, mica, graphite, pearl particles, and combinations thereof. The molded article manufactured using the thermoplastic resin composition of any one of Claims 1-10.