KR101583223B1 - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition and a molded article using the thermoplastic resin composition and a thermoplastic resin having a melt flow index (MI) of 30 to 150 g / 10 min measured at 220 DEG C / 10 kg in accordance with ASTM D1238, Composition can be provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition and a molded article using the thermoplastic resin composition.

A thermoplastic resin composition 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 are mainly made of plastic resin by adding metal or the like to the metal surface of the resin. This is disclosed in Japanese Patent Laid-Open Nos. 2001-262003 and 2007-137963. Japanese Laid-Open Patent Application No. 1995-196901 discloses that a metal micro-plate obtained by punching a plastic resin and having a luster of an average aspect ratio (thickness / average particle diameter) of 1/100 to 1/8 is added to exhibit the metal texture.

Conventional products that add metal particles to plastic resin may give a feeling of compounding metal to the resin, but it is inevitable to separate from the painting product that shows the metal texture. It was not enough to function.

One embodiment of the present invention is to provide a thermoplastic resin composition having little appearance of flow marks and weld lines and having an appearance of excellent metallic texture.

In one embodiment of the present invention, there is provided a thermoplastic resin composition comprising a thermoplastic resin and metal particles having a melt flow index (MI) of 30 to 150 g / 10 min measured at 220 ° C / 10 kg according to ASTM D1238 do.

The thermoplastic resin composition may further comprise a rubbery polymer having an average particle diameter of 0.4 to 10 mu m.

The metal particles may include first metal particles having a long diameter of 1 to 20 mu m.

The metal particles may include second metal particles having a long diameter of 50 to 120 占 퐉.

The metal particles may include first metal particles having a long diameter of 1 to 20 m and second metal particles having a long diameter of 50 to 120 m.

When the first metal particles and the second metal particles are simultaneously contained, the content ratio of the first metal particles and the second metal particles (the weight of the first metal particles / the weight of the second metal particles) 2 < / RTI >

The content of the metal particles may be 0.05 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin.

The metal particles may be aluminum, copper, gold, or a combination thereof.

The thermoplastic resin composition may further include inorganic particles such as glass particles, mica, graphite, pearl particles, or a combination thereof.

The inorganic particles may be included in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin.

The thermoplastic resin may be a polycarbonate resin, a rubber-modified vinyl copolymer resin, a polyester resin, a polyalkyl (meth) acrylate resin, a styrene polymer, a polyolefin resin or a combination thereof.

The thermoplastic resin may be a rubber-reinforced polystyrene (HIPS) resin.

The thermoplastic resin may be an acrylonitrile-butadiene-styrene copolymer (ABS) resin.

Another embodiment of the present invention provides a molded article using the above-mentioned thermoplastic resin composition.

The molded article has a flop index of 8 to 15, a sparkle intensity of 8 to 15, and a luminance measured based on a gloss level at an angle of 60 ° may be 50 to 95% have.

The thermoplastic resin composition according to one embodiment of the present invention can minimize the change in the orientation of metal particles with respect to the flow velocity during injection molding of a molded product, thereby improving the flow mark and weld line in the appearance of the molded article Hardly occurs.

Therefore, the present invention can be applied to a resin molded product having a metallic texture on the exterior without a painting process.

1 is a schematic view showing a method of measuring the sparkle strength of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

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 defined otherwise herein, "copolymerization" may mean block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and "copolymer" is a block copolymer, random copolymer, graft copolymer or Quot; alternate copolymer ".

The term " long diameter "means the longest length of a line connecting two points on a closed curve, and " long diameter " At this time, "closed curve" means a curve on a curve that moves in one direction and returns to the starting point again.

In one embodiment of the present invention, a composition providing a metal texture without painting and a molded article thereof are provided, and a flop index (FI) is used as a performance index of the molded article. The flop index is an index representing the metal texture of the surface, and can be expressed by the following equation (1). More specifically, the flop index is a value obtained by measuring a change in reflectance by rotating a reflection angle, and the luminance (L) of each reflected light at 15 °, 45 °, and 110 ° is measured. L (x °) means the luminance measured at x °. In the present invention, the flop index was measured using BYK Mac spectrophotometer BYK.

[Equation 1]

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

In the present invention, the sparkle intensity was used as an index of the metal particle feel. The sparkle strength can be obtained by the following equation (2).

&Quot; (2) "

In Equation (2),? (X °) denotes the sparkle strength measured at x °, and? Denotes the graininess of the metal particles as a diffusion value of each? (X °). The sparkle strength (? _Total ) of the molded article is determined according to the formula (2) by measuring the sparkle strength at 15 °, 45 ° and 75 °. A method of measuring the sparkle strength is schematically shown in Fig. In the present invention, the sparkle strength of the molded article was measured using an X-Rite MA98 multi-angle spectrophotometer.

The sparkle intensity measured according to Equation (2) can be said to be a value calculated by combining the following four factors.

[Four factors]

반사 Reflectance of individual metal particles

② Amount of metal particles

③ Size of metal particles

④ Orientation of metal particles

In the present invention, the brightness, which is an indicator of brightness such as metallic luster, was measured at a gloss level at an angle of 60 ° using SUGA UGV-6P digital variable glossmeter.

According to one embodiment of the present invention, there is provided a thermoplastic resin composition comprising a thermoplastic resin having a MI (melt flow index) of 30 to 150 g / 10 min measured at 220 ° C / 10 kg according to ASTM D 1238, To provide a resin composition.

When the thermoplastic resin has MI in the same range as above, it is possible to uniformly control irregular diffuse reflection depending on the angle and orientation of the metal particles. From this, it is possible to effectively improve appearance defects of an injection molded article such as a weld line, which can be caused by non-uniform distribution of metal particles.

The thermoplastic resin composition may further comprise a rubbery polymer having an average particle diameter of 0.4 to 10 mu m.

When the average particle diameter of the rubbery polymer satisfies the above range, the effect of reducing appearance defects (flow mark and / or weld line) of an injection molded article, which is actually visible to the naked eye, Can be obtained.

The metal particles may be plate-shaped metal particles.

The metal particles may include first metal particles having a long diameter of 1 to 20 mu m.

When the first metal particles satisfy the above range, there is an effect of showing a continuous metal texture.

In addition, the metal particles may include second metal particles having a long diameter of 50 to 120 탆.

When the second metal particle satisfies the above range, there is an effect that the metal particle feel of the metal itself is exhibited.

Also, for example, the metal particles may include first metal particles having a diameter of 1 to 20 μm and second metal particles having a diameter of 50 to 120 μm.

When the first metal particles and the second metal particles are included at the same time as described above, there is an effect of adding the metal grain feel of the metal itself based on the continuous metal texture.

When the first metal particles and the second metal particles are simultaneously contained, the content ratio of the first metal particles and the second metal particles (the weight of the first metal particles / the weight of the second metal particles) 2 < / RTI > When the above range is satisfied, the mixing effect of the first metal particles and the second metal particles described above can be maximized.

The thermoplastic resin composition hardly generates flow marks and weld lines during injection molding, thereby making a molded article having excellent metal texture.

Therefore, it can be advantageously applied to molded articles having excellent appearance, particularly, plastic exterior articles such as electric / electronic parts and automobile parts, without a separate coating step. Hereinafter, each component included in the thermoplastic resin composition will be specifically described.

Thermoplastic resin

The thermoplastic resin known as the thermoplastic resin may be used without limitation, and examples thereof include a polycarbonate resin, a rubber modified vinyl copolymer resin, a polyester resin, a polyalkyl (meth) acrylate resin, a styrene polymer, a polyolefin resin Or a combination thereof. The thermoplastic resin can affect the basic properties such as impact resistance, heat resistance, bending property and tensile property of the thermoplastic resin composition.

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 2.0 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-based copolymer resin includes 5 to 95% by weight of a vinyl-based copolymer and 5 to 95% by weight of a 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-based copolymer 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-modified vinyl copolymer resin may be used singly or in the form of a mixture of two or more thereof.

Specific examples of the rubber-modified vinyl-based copolymer resin include resins containing a copolymer of styrene, acrylonitrile and optionally methyl (meth) acrylate graft copolymerized with butadiene rubber, acrylic rubber or styrene / butadiene rubber .

Another specific example of the rubber-modified vinyl-based copolymer resin includes a resin containing a copolymer in which methyl (meth) acrylate is graft-copolymerized with butadiene rubber, acrylic rubber or styrene / butadiene rubber.

More specific examples of the rubber-modified copolymer resin include an acrylonitrile-butadiene-styrene copolymer (ABS) resin.

The method for producing the rubber-modified vinyl-based copolymer resin is well known to those skilled in the art, and any of emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization can be used.

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 polyethylene terephthalate resin is a polymer obtained by condensation polymerization of an ethylene glycol monomer and a terephthalic acid or dimethyl terephthalate monomer directly by an esterification reaction or an ester exchange reaction.

Further, in order to increase the impact strength of the polyethylene terephthalate resin, the polyethylene terephthalate resin is copolymerized with polytetramethylene glycol (PTMG), polypropylene glycol (PPG), low molecular weight aliphatic polyester or aliphatic polyamide, It may be used in the form of a modified polyethylene terephthalate resin.

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 is a compound having an alkyl group of C1 to C10 and is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (Meth) acrylate, and the like.

The polyalkyl (meth) acrylate may have a weight average molecular weight ranging from 10,000 to 200,000 g / mol, and specifically from 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.

 Wherein the styrene-based polymer comprises 20 to 100% by weight of a styrene-based monomer; And 0 to 80% by weight of a vinyl monomer of an acrylic monomer, a heterocyclic monomer, an unsaturated nitrile monomer, or a combination thereof. As the styrene-based polymer, for example, a rubber-modified styrene-based polymer such as a rubber-reinforced polystyrene (HIPS) resin may be used.

As the styrenic 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.

Specific examples of the styrene-based polymer include a copolymer of a styrene-based monomer and an unsaturated nitrile monomer, a copolymer of a styrene-based monomer and an acrylic monomer, a copolymer of a styrene-based monomer, an unsaturated nitrile monomer and an acrylic monomer, Based homopolymer, and a combination thereof.

The styrene polymer may have a weight average molecular weight of 40,000 to 500,000 g / mol.

The styrenic polymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization or the like.

The polyolefin resin may be a polyethylene resin (PE), a polypropylene resin (PP), or a copolymer resin thereof.

The thermoplastic resin may be used in the form of a mixture of two or more kinds.

More specifically, the thermoplastic resin may be a polycarbonate resin, a rubber-modified vinyl copolymer resin, a polyester resin, a polyalkyl (meth) acrylate resin, a styrene polymer, a polyolefin resin or a combination thereof.

More specifically, the thermoplastic resin may be a rubber-reinforced polystyrene (HIPS) resin.

More specifically, the thermoplastic resin may be an acrylonitrile-butadiene-styrene copolymer (ABS) resin. However, the present invention is not limited thereto.

Metal particles

The thermoplastic resin composition may include a metal particle to impart a metal texture to the molded article. More specifically, the metal particles may be plate-shaped metal particles.

The metal particles may include first metal particles having a long diameter of 1 to 20 mu m.

In addition, the metal particles may include second metal particles having a long diameter of 50 to 120 탆.

The metal particles may include first metal particles having a long diameter of 1 to 20 m and second metal particles having a long diameter of 50 to 120 m.

In the case of containing the above-mentioned long-diameter metal particles, the appearance of smooth and luxurious metal texture and the orientation of the metal particles due to the flow velocity are suppressed, and the appearance defects of the injection-molded article caused by typical metal particles, such as flow marks and weld lines, .

When the first metal particles and the second metal particles are simultaneously contained, the content ratio of the first metal particles and the second metal particles (the weight of the first metal particles / the weight of the second metal particles) 2 < / RTI > When the above range is satisfied, there is no flow mark or weld line, and a material having excellent metal texture can be provided.

The content of the metal particles may be 0.05 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin.

When the above range is satisfied, the thermoplastic resin composition and the molded article using the thermoplastic resin composition can satisfy the required metal texture. However, when the content of the metal particles is less than the above range, sufficient metal texture can not be exhibited. If the content is more than the above range, the properties of the resin composition may be deteriorated.

In addition, the average particle diameter or the long diameter of the metal particles can be selected according to the properties of the required molded article, and is not limited to the above range.

The plate-like metal particles may be one of sparkling particles having a flat surface reflecting light. In this case, the flat surface means a flat surface to the extent that the naked eye confirms that the particles are shiny. For example, the flat surface means a surface of a plate glass or a metal surface finished by polishing.

The plate-shaped metal particles may be made of aluminum, copper, gold, or a combination thereof, and preferably aluminum.

Inorganic particle

The thermoplastic resin composition may further include inorganic particles.

The inorganic particles may be other kinds of glitter particles having a flat surface reflecting light. Here, the description of the flat surface is as described above.

The inorganic particles may be glass particles, mica, graphite, pearl particles or a combination thereof. Among them, glass particles can be preferably used.

The glass particles have a plate-like structure, and thus are different from glass fibers having a mainly cylindrical shape. The glass fiber of the cylindrical shape can not reflect light and it is difficult to show the metal texture. The cross section of the glass particles may have a shape such as a circle, an ellipse, or an amorphous shape.

The inorganic particles may have an average particle diameter of 10 to 200 mu m, a thickness of 0.1 to 10 mu m, and a cross-sectional area of 80 to 32,000 mu m < ² >. When the inorganic particles have an average particle diameter, a thickness, and a cross-sectional area within the above-mentioned range, a molded article having excellent metal texture and luminance can be obtained with almost no generation of flow marks and weld lines.

The inorganic particles may be included in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin, more specifically 0.1 to 4 parts by weight. When the inorganic particles satisfy the above-mentioned range, the resin composition containing the inorganic particles satisfies the above-described range, is excellent in impact strength, is free from generation of flow marks and weld lines, and is advantageous for producing a molded article having excellent metal texture and brightness.

Other additives

The thermoplastic resin composition may be used in combination with an antistatic agent such as an antimicrobial agent, a thermal stabilizer, an antioxidant, a releasing agent, a light stabilizer, a surfactant, a coupling agent, a plasticizer, an admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, A nucleating agent, an adhesion promoter, an adhesive, or a combination thereof.

As the antioxidant, phenol type, phosphite type, thioether type or amine type antioxidant may be used. Examples of the releasing agent include fluorine-containing polymer, silicone oil, metal salt of stearic acid, montanic acid, , A montanic ester wax or a polyethylene wax can be used. As the weather stabilizer, benzophenone type, benzotriazole type or amine type weather resistance stabilizer can be used. As the coloring agent, a dye or pigment can be used. As the ultraviolet light blocking agent, titanium dioxide (TiO ₂ ) or carbon black Can be used. As the nucleating agent, talc or clay may be used.

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

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

According to another embodiment, there is provided a molded article produced by molding the above-mentioned thermoplastic resin composition. That is, the thermoplastic resin composition can be used to produce a molded article by various processes such as injection molding, blow molding, extrusion molding, and compression molding. Particularly, it can be effectively applied to molded articles having almost no appearance of flow marks and weld lines and having an appearance of metallic texture, especially plastic exterior products such as electric / electronic parts and automobile parts.

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

Example

A thermoplastic resin composition was prepared as shown in Table 1 below.

Constituent unit Example Comparative Example One 2 3 4 5 6 7 One 2 3 (A) weight% 100 100 100 - - - - - - - (B) weight% - - - 100 100 - - - - - (C) weight% - - - - - 30 30 - - - (D) weight% - - - - - 10 10 18 18 18 (E) weight% - - - - - 5 5 10 10 10 (F) weight% - - - - - 55 55 52 52 52 (G) weight% - - - - - - - 20 20 20 Thermoplastic resin
MI
(220 DEG C / 10 kg) g / 10 min 110 110 110 60 60 33 33 22 22 22 Rubber polymer
Average particle diameter of the particles ㎛ 2.0 2.0 2.0 0.5 0.5 2.4 2.4 0.2 0.2 0.2 (H) Weight portion 0.5 3.0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - (I) Weight portion 2.0 - 2.0 2.0 2.0 - 2.0 - 2.0 0.5 (J) Weight portion - - 3.0 - 3.0 - 3.0 3.0 3.0 -

The components used in Table 1 are as follows.

(A) Rubber reinforced polystyrene (HIPS) resin (Cheil Industries)

A low light HIPS resin having an average particle diameter of the rubbery polymer particles of 2.0 占 퐉 and an MI (220 占 폚 / 10 kg) measured according to ASTM D1238 of 110

(B) Rubber-reinforced polystyrene (HIPS) resin (Cheil Industries)

High-gloss HIPS resin having an average particle diameter of the rubbery polymer particles of 0.5 占 퐉 and an MI (220 占 폚 / 10kg) measured according to ASTM D1238 of 60

(C) Acrylonitrile-butadiene-styrene copolymer (ABS) resin (Cheil Industries)

A low-density ABS resin having an average particle diameter of the rubbery polymer particles of 9 mu m and an MI (220 DEG C / 10 kg) measured according to ASTM D1238 of 30

(D) Graft acrylonitrile-butadiene-styrene copolymer (g-ABS) resin (Cheil Industries)

G-ABS resin having an average particle diameter of the rubbery polymer particles of 0.25 占 퐉, an acrylonitrile content of 10.5% by weight, a styrene content of 31.5% by weight and a rubbery polymer content of 58%

(E) graft acrylonitrile-butadiene-styrene copolymer (g-ABS) resin (Cheil Industries)

G-ABS resin having an average particle diameter of the rubbery polymer particles of 0.13 占 퐉, an acrylonitrile content of 15% by weight, a styrene content of 37% by weight and a rubbery polymer content of 48%

(F) Styrene-acrylonitrile copolymer (SAN) resin (Cheil Industries)

SAN resin having an acrylonitrile content of 24% by weight, a styrene content of 76% by weight and a weight average molecular weight of about 150,000 g / mol

(G) Styrene-acrylonitrile copolymer (SAN) resin (Cheil Industries)

SAN resin having an acrylonitrile content of 32% by weight, a styrene content of 64% by weight and a weight average molecular weight of about 120,000 g / mol

(H) Metal particle-1 (Silberline)

An amorphous plate-like aluminum particle having a long diameter of 8 mu m and a thickness of 0.1 mu m

(I) Metal Particles-2 (Nihonboitz)

A rectangular plate-like aluminum particle having a long diameter of 100 mu m and a thickness of 10 mu m

(J) Synthetic mica (Eckart)

And a long diameter of not 20㎛, a thickness of 0.3㎛, titanium dioxide (TiO ₂₎ is contained 40% by weight of the synthetic mica

Example  1 to 7 and comparison Example  1 to 3

Using the above-mentioned components, the thermoplastic resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 3 were mixed with the composition shown in Table 1, and then the mixture was extruded at a temperature of 180 to 240 ° C After extrusion in the range, the extrudates were made in the form of pellets. The contents of (A), (B), (C), (D), (D), (E) (A), (B), (C), (D), (E), (F) and (G) (A) + (B) + (C) + (D) + (E) + (F) + (G) = 100 (Parts by weight) relative to parts by weight.

The pellets prepared according to Examples 1 to 7 and Comparative Examples 1 to 3 were dried at 80 DEG C for 4 hours and then molded into a mold having a cylinder temperature of 220 to 250 DEG C and a mold temperature Molded by using a mold having two gates so that a weld line is formed on the surface of a molded product by setting test pieces (length x width x length x thickness = 100 mm x 15 mm x 3 mm) Respectively.

The prepared test pieces were measured by the following methods, and the results are shown in Table 2 below.

Item Example Comparative Example One 2 3 4 5 6 7 One 2 3 Metal texture
(Flop index) 11 15 15 10 14 12 14 13 15 5 Metallic texture
(Sparkle intensity) 13 10 15 13 14 10 15 12 13 15 Luminance
(Gloss level, 60 DEG) 63% 81% 83% 66% 87% 55% 80% 87% 92% 65% Appearance of molded article Flow mark ○ ○ ○ ○ ○ ○ ○ × × ◎ Weld line ○ ○ ○ ○ ○ △ △ × × ◎

The physical property measurement standard of Table 2 is as follows.

Metal texture

As described above, the flop index was measured using a spectrophotometer (manufacturer: BYK, model name: BYK-Mac). The flip-flop effect, which is a texture unique to metal particles, was evaluated by integrating three angles of 15 °, 45 ° and 110 °, and the values are shown in Table 2 above.

Metallic texture

The sparkle intensity was measured using a spectrophotometer (manufacturer: X-Rite, model name: MA98) as described above, and the results are shown in Table 2 above.

Luminance

As described above, the brightness was measured at a gloss level of 60 ° using SUGA UGV-6P digital variable glossmeter, and the results are shown in Table 2 above.

Appearance of molded article

A weld line may be generated because a mold having two gates is used for injection molding of the molded product of the test piece. The appearance of the molded product of the test piece was visually observed, and the results of the evaluation according to the following evaluation criteria are shown in Table 2 above. The criteria for the appearance of the molded article were determined as shown in Table 3 below.

&Amp; cir &: A state in which there is no unusual color in a flow mark or a weld line

∘: no flow mark but slightly different color on the weld line

[Delta]: A state in which a different color appears in the flow mark and the weld line

X: A state in which the unusual color appears in the flow mark and the weld line

Indicators Appearance of molded article ×

△

○

◎

Through the above Table 2, the thermoplastic resin compositions of Examples 1 to 7 were excellent in metal texture, and excellent results were obtained in terms of flow marks and weld line reduction. On the other hand, in the thermoplastic resin compositions of Comparative Examples 1 to 3, the MI of the thermoplastic resin constituting each resin composition was as low as less than 30 g / min, the average particle diameter of the rubbery polymer contained in each resin composition was as low as less than 0.4 탆 It can be confirmed that the appearance of the metal texture or the molded article is poor when compared with the corresponding embodiments in which the types and the contents of the metal particles are the same.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (15)

And a thermoplastic resin and metal particles having a melt flow index (MI) of 30 to 150 g / 10 min as measured according to ASTM D 1238 at 220 ° C / 10 kg,
Wherein the metal particles include first metal particles having a major axis of 1 to 20 占 퐉 and second metal particles having a major axis of 50 to 120 占 퐉,
The content ratio of the first metal particles to the second metal particles (weight of the first metal particles / weight of the second metal particles) is 1/10 to 2,
Wherein the metal particles are aluminum, copper, gold or a combination thereof.
The method according to claim 1,
Wherein the thermoplastic resin composition further comprises a rubbery polymer having an average particle diameter of 0.4 to 10 占 퐉.
delete delete delete delete The method according to claim 1,
Wherein the content of the metal particles is 0.05 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin.
delete The method according to claim 1,
Wherein the thermoplastic resin composition further comprises inorganic particles which are glass particles, mica, graphite, pearl particles or a combination thereof.
10. The method of claim 9,
Wherein the inorganic particles are contained in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin.
The method according to claim 1,
Wherein the thermoplastic resin is a polycarbonate resin, a rubber-modified vinyl copolymer resin, a polyester resin, a polyalkyl (meth) acrylate resin, a styrene polymer, a polyolefin resin or a combination thereof.
The method according to claim 1,
Wherein the thermoplastic resin is a rubber-reinforced polystyrene (HIPS) resin.
The method according to claim 1,
Wherein the thermoplastic resin is an acrylonitrile-butadiene-styrene copolymer (ABS) resin.
A molded article using the thermoplastic resin composition according to claim 1.
15. The method of claim 14,
Wherein the molded article has a flop index of 8 to 15, a sparkle intensity of 8 to 15, and a luminance of 50 to 95% as measured on a gloss level at an angle of 60 [deg.] Shaped article.

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