KR20130046154A - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition is provided to remove flow mark and weld line and to have excellent appearance with metal texture. CONSTITUTION: A thermoplastic resin molded product comprises a thermoplastic resin, planar metal particles with an average particle diameter of 8-25 micron, and metal spheres. The flop index of the thermoplastic resin is 6.5 or more. The thermoplastic resin composition comprises a thermoplastic resin, plate-like metal particles with an average particle diameter of 8-25 micron, and the metal spheres. The flop index of the molded product is 6.5 or more. When the average particle diameter of the plate-like metal particles is L1 and the average particle diameter of the metal particles is L2, the average particle diameter of the metal spheres is 0<L2<=L1.

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 injection appearance 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 Laid-Open Nos. 2001-262003 and 2007-137963, but the metal texture does not appear in the actual experiment, and there is a problem that a flow mark or a 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.

In one embodiment of the invention, (A) a thermoplastic resin, (B1) comprises a plate-shaped metal particles having an average particle diameter of 8 to 25 ㎛, and (C) spherical metal particles, the flop index (FI) is 6.5 The thermoplastic resin molded article characterized by the above is provided.

In another embodiment of the present invention, (A) a thermoplastic resin, (B1) comprising a plate-shaped metal particles having an average particle diameter of 8 to 25㎛, and (C) spherical metal particles, characterized in that the flop index of the molded article is 6.5 or more It provides a thermoplastic resin composition.

When the average particle diameter of the plate-shaped metal particles (B1) is referred to as L ₁ , and the average particle diameter of the particles of the spherical metal particles (C) is referred to as L ₂ , the average particle diameter of the particles of the spherical metal particles is 0 <L ₂ ≤ L ₁ may be.

Thickness ratio (thickness / average particle diameter) with respect to the average particle diameter of the said plate-shaped metal particle (B1) may be 1/400 to 1/2.

The composition may further comprise a plate-shaped metal particles (B2) having an average particle diameter of 40 to 65㎛.

The particle average particle diameter of the spherical metal particles (C) may be 1 to 32㎛.

The weight ratio of the plate-shaped metal particles (B1) and the spherical metal particles (C) may be 1: 3 to 3: 1.

The thermoplastic resin (A) may include a polycarbonate resin, a rubber modified vinyl copolymer resin, a polyester resin, a polyalkyl (meth) acrylate resin, a polystyrene resin, a polyolefin resin, or a combination thereof.

The thermoplastic resin (A) is a mixture of polycarbonate, acrylonitrile-butadiene-styrene graft resin (ABS) and styrene-acrylonitrile copolymer resin (SAN); Or a mixture of polycarbonate, acrylate-styrene-acrylonitrile graft resin (ASA) and styrene-acrylonitrile copolymer resin (SAN).

The plate-shaped metal particles (B1) and the spherical metal particles (C) may be made of a material selected from aluminum, copper, gold and combinations thereof.

The total amount of the plate-shaped metal particles (B1) + (B2) and the spherical metal particles (C) may be included in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin (A).

The thermoplastic resin composition may further include an inorganic particle (D) including one selected from glass particles, mica, graphite, pearl particles, and a combination thereof.

The inorganic particles (D) may be included in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the thermoplastic resin (A).

Other specific details of embodiments of the present invention are included in the following detailed description.

The thermoplastic resin composition has little 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 otherwise specified herein, "average particle diameter" of the plate-shaped particles means "long diameter", "long diameter" means the longest length of a line connecting two points in a closed curve, In this case, the "closed curve" means a curve in which a point on the curve moves in one direction and returns to the starting point.

In one embodiment of the present invention provides a composition and its molded article to provide a metal texture without separate painting (painting), and used a flop index as an indicator of the performance of the molded article. The flop index is an index indicating the surface metal texture, and the luminance (L) of each reflected light at 15 °, 45 °, and 110 ° is usually measured and obtained according to the following definition. L (x˚) means luminance measured at x˚.

The flop index of the non-metallic surface is 0, the flop index of the metal is about 15 to about 17, and the flop index of the metallic coating used for automobile body coating is about 11, The flop index is about 6.5 or more.

In order to realize the metallic texture, the average particle diameter, particle size distribution, surface roughness, and combination of various particles of the metallic particles to be added should be well matched, and the present invention provides an optimal composition for forming such physical properties and molded articles thereof.

According to one embodiment of the invention, (A) comprises a thermoplastic resin, (B1) a plate-shaped metal particles having an average particle diameter of 8 to 25㎛, and (C) spherical metal particles, characterized in that the flop index of the molded article is 6.5 or more A thermoplastic resin composition and its molded article are provided.

According to another embodiment of the invention, (A) thermoplastic resin, (B1) plate-shaped metal particles having an average particle diameter of 8 to 25 ㎛, (B2) plate-shaped metal particles having an average particle diameter of 40 ~ 65 ㎛ and (C) spherical metal A thermoplastic resin composition comprising particles and having a flop index of 6.5 or more is provided, and a molded article thereof.

Since the thermoplastic resin composition has almost no appearance of flow marks and weld lines, and has an excellent appearance with a metal texture of flop index 6.5 or more, a molded article having an excellent appearance without a separate coating process, in particular, It can be usefully applied to plastic exterior products such as electric and electronic parts, automobile parts. 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 use a weight average molecular weight of 10,000 to 200,000 g / mol, specifically may be used 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. In addition, the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.

Bisphenol-A type | system | group polycarbonate resin etc. are mentioned as said linear polycarbonate resin. Examples of the branched polycarbonate resins include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates. The polyfunctional aromatic compound may be included 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. In this case, as the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, or the like may be used.

The rubber-modified vinyl-based graft copolymer resin is 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 polymers include 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 composites or a combination thereof can be used.

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.

The rubber particle diameter of the rubber-modified vinyl graft copolymer may be 0.05 to 4 μm in order to improve impact resistance and surface properties of the molded product. When the rubber particle is 0.05 to 4 μm, the impact strength is excellent. 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.

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 0.35 kPa to 1.5 kPa / g as measured by 25 ° C. of o-chlorophenol, and specifically, may be 0.5 kPa to 1.3 kPa / 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 10,000 to 200,000 g / mol, specifically, may have a range of 15,000 to 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). mixture; Or when using a mixture of polycarbonate, acrylate-styrene-acrylonitrile graft resin (ASA) and styrene-acrylonitrile copolymer resin (SAN).

(B1) and (B2) Plate type  Metal Particles / (C) Spherical Metal Particles

The thermoplastic resin may be provided with a metal texture by including the plate-shaped metal particles and the spherical metal particles. The thermoplastic resin essentially includes plate-shaped metal particles (B1) and spherical metal particles (C) having an average particle diameter of 8 to 25 μm, and may further include plate-shaped metal particles (B2) having an average particle diameter of 40 μm to 65 μm. Can be.

The total amount of the plate-shaped metal particles (B1) + (B2) and the spherical metal particles (C) may be included in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin.

Below, plate-shaped metal particles ((B1) and (B2)) and spherical metal particles (C) will be described in detail.

1.Platformed metal particles (B1) having an average particle diameter of 8 to 25 µm.

The plate-shaped metal particles may be a kind of sparkling particles having 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 plate-shaped metal particles (B1) may be made of a material containing aluminum, copper, gold or a combination thereof, preferably made of aluminum.

The plate-shaped metal particles (B1) may have a ratio of the thickness to the average particle diameter of 1/400 to 1/2, for example, may be 1/80 kPa to 1/20. When the range includes the plate-shaped metal particles (B1) having a ratio of the thickness to the average particle diameter, there is almost no flow mark and weld lines, and a molded article having an excellent metal texture can be obtained. .

2. Spherical Metal Particles (C)

When using only the plate-shaped metal particles (B1) alone, 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 manufacturing the molded article, the edge portion of the plate-shaped metal particles (B1) to be well aligned in a certain direction so that the surface does not face the metal texture may appear well. When the spherical metal particles (C) are mixed with the plate-shaped metal particles (B1), due to the presence of the spherical metal particles (C) during molding, the edge portions of the plate-shaped metal particles (B1) are well aligned so that they do not face the surface. The generation of flow marks and weld lines can be reduced.

When the average particle diameter of the plate-shaped metal particles (B1) is L ₁ and the average particle diameter of the particles of the spherical metal particles (C) is L ₂ , 0 <L ₂ ≤L ₁ may be used. as it may be a relationship between L ₁ / 5≤L ₂ ≤L _1. When the relationship between the average particle diameter of the two particles satisfies the numerical range 0 <L ₂ ≤ L ₁ , the alignment state of the plate-shaped metal particles B1 may be arranged in a more constant direction.

The average particle diameter (L ₁ ) of the plate-shaped metal particles (B1) may be 5 to 100㎛. When the plate-shaped metal particles B1 of the above size are used together with the spherical metal particles C, there is little flow mark and weld line generation, and a molded article having excellent metal texture can be obtained. For example, the cross-sectional area of the plate-shaped metal particles (B1) may be 5 to 10,000㎛ ² . For example, the thickness of the plate-shaped metal particles (B1) may be 0.25 to 2.5㎛, more specifically 0.5 to 2.2㎛.

The particle average particle diameter (L ₂ ) of the spherical metal particles (C) may be 1 to 32㎛. When the spherical metal particles (C) in the above size range are used together with the plate-shaped metal particles (B1), there is little flow mark and weld line generation, and a molded article having excellent metal texture can be obtained.

The weight ratio of the plate-shaped metal particles (B1) and the spherical metal particles (C) may be 1: 3 kPa to 3: 1 kPa, for example, 1: 1: 2 kPa to 2: 2 kPa. When the plate-shaped metal particles (B1) and the spherical metal particles (C) are included in the thermoplastic resin composition at the weight ratio, there is little flow mark and weld lines, and a molded article having excellent metal texture is obtained.

The weight ratio of the plate-shaped metal particles (B1) and the spherical metal particles (C) can be obtained by inversely calculated by calculation in the molded article. For example, the plate-shaped metal particles (B1) in three angles perpendicular to each other are explained. After measuring the area ratio of and the spherical metal particles (C), the content ratio of these can be calculated by obtaining the volume ratio occupied by the plate-shaped metal particles (B1) and the spherical metal particles. At this time, the area ratio of the plate-shaped metal particles (B1) and the spherical metal particles (C) on one surface is the ratio of the sum of the area of the plate-shaped metal particles (B1) shown on one surface and the sum of the areas of the spherical metal particles (C) on the one surface. It is measured as

3. Plate-shaped metal particles (B2) having an average particle diameter of 40 to 65 µm

In another embodiment of the present invention includes two types of plate-shaped metal particles (B1) and spherical metal particles (C) having an average particle diameter of 8 to 25 ㎛ and at the same time 40 to 65 ㎛ having a larger average particle diameter than (B1) By selectively using the plate-shaped metal particles (B2), the metal texture can be further improved. The average particle diameter and thickness ratio of the plate-shaped metal particle (B2) whose average particle diameter is 40-65 micrometers may be the same range as described in description of (B1), or may differ from that of the metal particle of (B1).

The weight ratio of the plate-shaped metal particles (B1) and the plate-shaped metal particles (B2) may be in the range of 2: 1 1: to 1: 2, for example, may be: 12: 1 to 1: 1.5. When the plate-shaped metal particles (B1) and the plate-shaped metal particles (B2) are included in the thermoplastic resin composition in the above-described weight ratio, there is almost no flow mark and weld lines, and a molded article having excellent metal texture can be obtained.

(D) inorganic particles

The thermoplastic resin composition may further include the inorganic particles.

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

The inorganic particles may be included as 0.1 to 3.0 parts by weight based on 100 parts by weight of the thermoplastic resin, more specifically 0.1 to 1.2 parts by weight may be included. When the inorganic particles are used at 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin, the impact strength is excellent, there is little flow marks and weld lines, and it is advantageous to prepare molded articles having excellent metal texture.

The mixture of the plate-shaped metal particles ((B1) + (B2)) and the spherical metal particles (C) and the inorganic particles (D) are in a weight ratio of 1: 5 to 5: 1, specifically, 1: 2 to 2: 1. It may be mixed in the thermoplastic resin composition in a weight ratio of. When the mixture of the thin plate-shaped metal particles ((B1) + (B2)) and the spherical metal particles (C) and the inorganic particles (D) is mixed in the range of the weight ratio, the impact strength is excellent as well as the flow mark and the weld line. It rarely occurs and is advantageous for producing molded articles having excellent metal texture.

(E) 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. In addition, a benzophenone type or an amine type weathering agent may be used as the weathering agent, a dye or a pigment may be used as the coloring agent, and titanium dioxide (TiO ₂ ) or carbon black may be used as the sunscreen. As the nucleating agent, talc or clay may be used.

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

The above-mentioned thermoplastic resin composition can be manufactured by a well-known method of manufacturing resin composition. For example, the components and other additives according to one embodiment may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.

According to another embodiment, 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.

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

(a1) polycarbonate

SC-1080 of Cheil Industries with a weight average molecular weight of 29,000

(a2) polycarbonate

SC-1190 of Cheil Industries with a weight average molecular weight of 23,000

(a3) acrylate copolymer

Monomer mixture consisting of 33% by weight of acrylonitrile and 67% by weight of styrene acrylate rubber in 50 parts by weight of a double-core butyl acrylate rubber composed of an inner core copolymerized with butyl acrylate and styrene and an outer core made of butyl acrylate rubber Graft ASA resin in the form of a double core-shell with a rubber particle diameter of 0.16 μm in which 50 parts by weight of graft is emulsion-polymerized

(a4) styrene-acrylonitrile copolymer

SAN resin with an acrylonitrile content of 24% by weight, styrene content of 76% by weight and a weight average molecular weight of 150,000

(B) Plate type  Metal particles

(B1) a plate-shaped metal particle having an average particle diameter of 8 to 25 µm.

Amorphous plate-shaped aluminum particles having an average particle diameter of 17 μm and a thickness of 0.5 μm (manufactured by Silverline, product name: L 11669)

(B2) plate-shaped metal particles having an average particle diameter of 40 to 65㎛

Amorphous plate-shaped aluminum particles with an average particle diameter of 55 µm and a thickness of 2.2 µm (manufactured by Yamato, Product Name: 3500X-90PA)

(C) spherical metal particles

Spherical aluminum particles with an average particle diameter of 10 µm (micro metals, product name: Al powder)

Example  1 to 5 and Comparative example  1 to 4

The thermoplastic resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 4 were prepared using the above-mentioned components and the compositions shown in Table 1 below, followed by extrusion at a temperature range of 240 ° C. in a conventional twin screw extruder. The extrudate was then prepared in pellet form. In Table 1, the contents of (a1), (a2), (a3) and (a4) were calculated from the values of (a1), (a2) + ), (a3) and (a4) are expressed in terms of% by weight, and the metal particles have a relative content (parts by weight) relative to 100 parts by weight of (a1) + (a2) + (a3) + Respectively.

The pellets prepared according to Examples 1 to 5 ° and Comparative Examples 1 to 4 were dried at 80 ° C. for 4 hours, and then, using an injection molding machine having an injection capacity of 6 Oz, a cylinder temperature of 250 ° C., a mold temperature of 80 ° C., The molding cycle was set to 30 seconds, and the ASTM dumbbell test piece was injection molded to prepare a physical specimen.

Constituent unit Example Comparative example One 2 3 4 One 2 3 4 The thermoplastic resin (A) Polycarbonate (a1) weight% 10 10 10 10 10 10 10 10 Polycarbonate (a2) weight% 40 40 40 40 40 40 40 40 Acrylate
Copolymer (a3) weight% 20 20 20 20 20 20 20 20 Styrene-acrylonitrile
Copolymer (a4) weight% 30 30 30 30 30 30 30 30 Plate-shaped metal particles (B1) having an average particle diameter of 8 to 25 µm Weight portion 0.3 0.3 0.5 0.3 0.5 - - 0.3 Plate-shaped metal particles (B2) having an average particle diameter of 40 to 65 µm Weight portion - - - 0.2 - - 0.3 0.2 Spherical Metal Particles (C) Weight portion 0.2 0.5 0.5 0.5 - 0.5 0.2 -

(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:

The flop index was measured using a measuring instrument (manufacturer: BYK, model name: BYK Mac). The flip-flop effect, which is the texture of aluminum particles, was evaluated by combining three angles of 15 °, 45 °, and 110 °, and the values are shown in Table 1 below.

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): No abnormal color in a flow mark and a weld line.

(Circle): There is no flow mark but there is a little difference in weld line.

(Triangle | delta): A state where a different color appears in a flow mark and a weld line.

X: The state which aberrant color appears badly in a flow mark and a weld line.

Item Example Comparative example One 2 3 4 One 2 3 4 Injection appearance Metal texture
(flop index) 6.9 7.6 8.9 12.8 10.4 4.5 5.9 11.0 Flow mark ○ ◎ ○ ◎ × ◎ ○ △ Weld line ○ ◎ ○ ◎ × ◎ ○ ×

Through the above Table 2, the thermoplastic resin composition of Examples 1 to 4 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, Comparative Example 2 using only spherical metal particles and Comparative Example 3 without using a plate-shaped metal particle having an average particle diameter of 8 to 25 μm did not satisfy the required physical properties in terms of metal texture, and used plate-shaped metal particles alone. Comparative Examples 1 and 4 were unsatisfactory in terms of flow marks and weld lines.

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 (13)

(A) a thermoplastic resin, (B1) a plate-shaped metal particle whose average particle diameter is 8-25 micrometers, and (C) spherical metal particle,
A thermoplastic resin molded article characterized by a flop index of 6.5 or more. (A) a thermoplastic resin, (B1) a plate-shaped metal particle whose average particle diameter is 8-25 micrometers, and (C) spherical metal particle,
The flop index of a molded article is 6.5 or more, The thermoplastic resin composition characterized by the above-mentioned. The method of claim 2,
When the average particle diameter of the plate-shaped metal particles (B1) is referred to as L ₁ , and the average particle diameter of the particles of the spherical metal particles (C) is referred to as L ₂ , the average particle diameter of the particles of the spherical metal particles is 0 <L ₂ ≤ L ₁ , characterized in that the thermoplastic resin composition. The method of claim 2,
The thickness ratio with respect to the average particle diameter of the said plate-shaped metal particle (B1) is 1 / 400-1 / 2, The thermoplastic resin composition characterized by the above-mentioned. The method of claim 2,
The thermoplastic resin composition, characterized in that the composition further comprises a plate-shaped metal particles (B2) having an average particle diameter of 40 to 65㎛. The method of claim 2,
The particle average particle diameter of the said spherical metal particle (C) is 1-32 micrometers, The thermoplastic resin composition characterized by the above-mentioned. The method of claim 2,
The plate-shaped metal particles (B1) and the spherical metal particles (C) is a thermoplastic resin composition, characterized in that included in a weight ratio of 1: 3 to 3: 1. The method of claim 2,
The thermoplastic resin (A) is a thermoplastic resin comprising a polycarbonate resin, rubber modified vinyl copolymer resin, polyester resin, polyalkyl (meth) acrylate resin, polystyrene resin, polyolefin resin or a combination thereof Composition. The method of claim 1,
The thermoplastic resin (A) is a mixture of polycarbonate, acrylonitrile-butadiene-styrene graft resin (ABS) and styrene-acrylonitrile copolymer resin (SAN); Or a mixture of polycarbonate, acrylate-styrene-acrylonitrile graft resin (ASA) and styrene-acrylonitrile copolymer resin (SAN). The method of claim 2,
The plate-shaped metal particles (B1) and the spherical metal particles (C) are made of a material selected from aluminum, copper, gold and combinations thereof. 6. The method according to claim 2 or 5,
The total amount of the plate-shaped metal particles ((B1) + (B2)) and the spherical metal particles (C) is 0.1 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin (A). The method of claim 2,
The thermoplastic resin composition further comprises an inorganic particle (D) comprising one selected from glass particles, mica, graphite, pearl particles, and combinations thereof. The method of claim 12,
The inorganic particles (D) is a thermoplastic resin composition, characterized in that contained in 0.1 to 3 parts by weight based on 100 parts by weight of the thermoplastic resin (A).