WO2013062169A1 - Composition de résine thermoplastique et moulage l'utilisant - Google Patents

Composition de résine thermoplastique et moulage l'utilisant Download PDF

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Publication number
WO2013062169A1
WO2013062169A1 PCT/KR2011/009108 KR2011009108W WO2013062169A1 WO 2013062169 A1 WO2013062169 A1 WO 2013062169A1 KR 2011009108 W KR2011009108 W KR 2011009108W WO 2013062169 A1 WO2013062169 A1 WO 2013062169A1
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Prior art keywords
thermoplastic resin
metal particles
plate
particles
particle diameter
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PCT/KR2011/009108
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English (en)
Korean (ko)
Inventor
김영신
하두한
허진영
김혜영
이완희
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제일모직 주식회사
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Publication of WO2013062169A1 publication Critical patent/WO2013062169A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a thermoplastic resin composition having an excellent injection appearance and a molded article using the same.
  • plastic exterior products having various colors in electric and electronic parts and automobile parts have become popular, and plastic exterior products that can feel more luxurious textures are increasing.
  • 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.
  • 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.
  • thermoplastic resin (B1) comprises a plate-shaped metal particles having an average particle diameter of 8 to 25 ⁇ m, and (C) spherical metal particles, the flop index (FI) is 6.5
  • FI flop index
  • thermoplastic resin (A) a thermoplastic resin, (B1) comprising a plate-shaped metal particles having an average particle diameter of 8 to 25 ⁇ m, 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.
  • the average particle diameter of the plate-shaped metal particles (B1) is referred to as L 1
  • 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 ⁇ m.
  • the particle average particle diameter of the spherical metal particles (C) may be 1 to 32 ⁇ m.
  • 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.
  • 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.
  • D inorganic particle
  • 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).
  • thermoplastic resin composition has little flow marks and weld lines, and has an excellent appearance with a metallic texture.
  • (meth) acrylate means that both “acrylate” and “methacrylate” are possible.
  • (meth) acrylic acid alkyl ester means that both “acrylic acid alkyl ester” and “methacrylic acid alkyl ester” are possible, and “(meth) acrylic acid ester” means both “acrylic acid ester” and “methacrylic acid ester”. It means everything is possible.
  • 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
  • closed curve means a curve in which a point on the curve moves in one direction and returns to the starting point.
  • 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 Equation 1 below.
  • L (x ⁇ ) means luminance measured at x ⁇ .
  • Equation 1 FI is a flop index and L (15 °), L (45 °), and L (110 °) are the luminance L of each reflected light at 15 °, 45 °, and 110 °, respectively. .
  • 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, and the surface of the metallic texture can be seen with the naked eye.
  • the flop index is about 6.5 or more.
  • 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.
  • (A) comprises a thermoplastic resin, (B1) a plate-shaped metal particles having an average particle diameter of 8 to 25 ⁇ m, 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.
  • thermoplastic resin (A) thermoplastic resin, (B1) plate-shaped metal particles having an average particle diameter of 8 to 25 ⁇ m, (B2) plate-shaped metal particles having an average particle diameter of 40 ⁇ 65 ⁇ m 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.
  • thermoplastic resin composition 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.
  • each component included in the thermoplastic resin composition will be described in detail.
  • thermoplastic resin (A) thermoplastic resin
  • thermoplastic resin known as the thermoplastic resin can be used without limitation, and for example, polycarbonate resin, rubber modified vinyl 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 diphenols with phosgene, halogen formate, carbonate ester or a combination thereof.
  • diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also called 'bisphenol-A'), 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro 4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether and the like.
  • 2,2-bis (4-hydroxyphenyl) propane 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) Cyclohexane can be used, more preferably 2,2-bis (4-hydroxyphenyl) propane.
  • 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.
  • the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.
  • group polycarbonate resin etc. are mentioned as said linear polycarbonate resin.
  • 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.
  • said polyester carbonate copolymer resin what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. 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.
  • the vinyl polymer may include 50 to 95% by weight of the 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.
  • styrene As the aromatic vinyl monomer, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, or a combination thereof may be used.
  • alkyl substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, ⁇ -methyl styrene, and the like.
  • the thing of (meth) acrylic-acid alkylester, (meth) acrylic acid ester, or a combination thereof can be used.
  • the alkyl means C1 to C10 alkyl.
  • Specific examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Meta) acrylates may be used.
  • (meth) acrylate etc. are mentioned as a specific example of the said (meth) acrylic acid ester.
  • heterocyclic monomer maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof can be used.
  • an acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof can be used as the unsaturated nitrile monomer.
  • the rubber particle diameter of the rubber-modified vinyl graft copolymer may be 0.05 to 4 ⁇ m in order to improve impact resistance and surface properties of the molded product.
  • 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.
  • the rubber-modified vinyl-based graft copolymer 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.
  • rubber-modified vinyl-based graft copolymers include those obtained by graft copolymerization of methyl (meth) acrylate on butadiene rubber, acrylic rubber or styrene / butadiene rubber.
  • rubber-modified graft copolymers include acrylonitrile-butadiene-styrene graft copolymers.
  • the rubber-modified vinyl-based graft copolymer is well known to those skilled in the art, and may be any of emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization. Examples include adding the above-mentioned aromatic vinyl monomer in the presence of a rubbery polymer and performing emulsion polymerization or bulk polymerization using a polymerization initiator.
  • polyester resin as the aromatic polyester resin, a resin polycondensed by melt polymerization from a terephthalic acid or a terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms can be used.
  • the alkyl means C1 to C10 alkyl.
  • aromatic polyester resin examples include polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, or some of these resins.
  • a polyester resin modified to be amorphous by mixing other monomers may be used, and among these, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin and amorphous polyethylene terephthalate resin may be used. And more preferably polybutylene terephthalate resin and polyethylene terephthalate resin.
  • 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.
  • 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.
  • PTMG polytetramethylene glycol
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • the polybutylene terephthalate resin may have an intrinsic viscosity [ ⁇ ] 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.
  • 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 raw material monomer containing an alkyl (meth) acrylate by a known polymerization method such as suspension polymerization, bulk polymerization, emulsion polymerization or the like.
  • 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.
  • 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.
  • weight average molecular weight of polyalkyl (meth) acrylate is the said range, it is excellent in hydrolysis resistance, scratch resistance, workability, etc.
  • polystyrene resin for example, rubber-modified polystyrene resin (HIPS) reinforced with impact strength may be used.
  • HIPS rubber-modified polystyrene resin
  • 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).
  • ABS acrylonitrile-butadiene-styrene graft resin
  • SAN styrene-acrylonitrile copolymer resin
  • 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 ⁇ m, and may further include plate-shaped metal particles (B2) having an average particle diameter of 40 ⁇ m to 65 ⁇ m. 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.
  • plate-shaped metal particles ((B1) and (B2)) and spherical metal particles (C) will be described in detail.
  • the plate-shaped metal particles may be a kind of sparkling particles having a flat surface that reflects light.
  • 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.
  • 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. .
  • the edge portion of the plate-shaped metal particles (B1) 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.
  • 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.
  • 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.
  • 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 ⁇ m.
  • the cross-sectional area of the plate-shaped metal particles (B1) may be 5 to 10,000 ⁇ m 2 .
  • the thickness of the plate-shaped metal particles (B1) may be 0.25 to 2.5 ⁇ m, more specifically 0.5 to 2.2 ⁇ m.
  • the particle average particle diameter (L 2 ) of the spherical metal particles (C) may be 1 to 32 ⁇ m.
  • 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.
  • 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 a molded article.
  • the plate-shaped metal particles (B1) in each of three directions perpendicular to each other can be obtained.
  • 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.
  • 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
  • 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 ⁇ m and at the same time 40 to 65 ⁇ m having a larger average particle diameter than (B1)
  • B1 plate-shaped metal particles
  • C spherical metal particles
  • 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 2: 1 Pa to 1: 2 Pa, for example, may be 2: 1 Pa to 1: 1.5 Pa.
  • the plate-shaped metal particles (B1) and the plate-shaped metal particles (B2) are contained 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.
  • 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.
  • the description of the flat surface is as described above.
  • glass particles 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 ⁇ m, a thickness of 0.5 to 10 ⁇ m, and a cross-sectional area of 80 to 32,000 ⁇ m 2 .
  • 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.
  • 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.
  • 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.
  • the thermoplastic resin composition may include an antibacterial agent, a heat stabilizer, an antioxidant, a mold 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 weather 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 type, phosphite type, thioether type or amine type antioxidant, and 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.
  • 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.
  • talc or clay may be used as the nucleating agent.
  • 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.
  • thermoplastic resin composition can be manufactured by a well-known method of manufacturing resin composition.
  • the components and other additives according to one embodiment may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.
  • 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.
  • thermoplastic resin composition of the following Example is as follows.
  • thermoplastic resin (A) thermoplastic resin
  • Monomer mixture consisting of 33% by weight of acrylonitrile and 67% by weight of styrene acrylate rubber with 50 parts by weight of a 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 having a rubber particle diameter of 0.16 ⁇ m in which 50 parts by weight of graft is emulsion-polymerized
  • 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
  • (B1) a plate-shaped metal particle having an average particle diameter of 8 to 25 ⁇ m.
  • Amorphous plate-shaped aluminum particles having an average particle diameter of 17 ⁇ m and a thickness of 0.5 ⁇ m manufactured by Silverline, product name: L 11669)
  • Amorphous plate-shaped aluminum particles having an average particle diameter of 55 ⁇ m and a thickness of 2.2 ⁇ m manufactured by Yamato, product name: 3500X-90PA
  • Spherical aluminum particles with an average particle diameter of 10 ⁇ m (micro metals, product name: Al powder)
  • 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.
  • 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.
  • the prepared physical specimens were measured for physical properties by the following method and the results are shown in Table 2 below.
  • the flop index was measured using a measuring instrument (manufacturer: BYK, model name: BYK Mac).
  • the flip-flop effect which is the texture of the aluminum particles, was evaluated by combining three angles of 15 °, 45 °, and 110 °, and the values are shown in Table 1 below.
  • 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.
  • 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 ⁇ m 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.

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  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne une composition de résine thermoplastique et un moulage obtenu à partir de celle-ci, la composition de résine thermoplastique étant caractérisée en ce qu'elle est constituée de (A) une résine thermoplastique, (B1) des particules métalliques en forme de plaque ayant un diamètre moyen de 8-25 µm et (C) des particules métalliques sphériques, et l'indice d'orientation du moulage étant de 6,5 ou plus.
PCT/KR2011/009108 2011-10-27 2011-11-28 Composition de résine thermoplastique et moulage l'utilisant WO2013062169A1 (fr)

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WO2016007896A1 (fr) * 2014-07-11 2016-01-14 Tyco Electronics Corporation Formulation composite et composant électronique
CN111019318A (zh) * 2020-01-14 2020-04-17 宁波公牛电器有限公司 一种具有细腻金属质感的pc改性材料及其制备方法

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KR101874666B1 (ko) * 2014-07-08 2018-07-05 (주)엘지하우시스 자동차 내장재용 복합시트 및 그의 제조방법
KR102020608B1 (ko) * 2017-12-15 2019-09-10 주식회사 삼양사 판상 첨가물을 포함하는 열가소성 수지 조성물 및 이를 포함하는 성형품
KR102262931B1 (ko) * 2017-12-15 2021-06-10 주식회사 삼양사 구상 금속 입자를 포함하는 열가소성 수지 조성물 및 이를 포함하는 성형품
KR102290956B1 (ko) 2017-12-21 2021-08-19 주식회사 엘지화학 열가소성 수지 조성물 및 이를 포함하는 열가소성 수지 성형품
KR102360000B1 (ko) 2018-06-29 2022-02-09 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 이용한 성형품
KR102209795B1 (ko) * 2018-10-31 2021-02-01 주식회사 삼양사 금속 입자를 포함하는 열가소성 수지 조성물 및 이를 이용하여 제조된 성형품
KR102201718B1 (ko) * 2018-10-31 2021-01-13 주식회사 삼양사 금속질감의 외관을 갖는 고강성 열가소성 수지 및 이를 이용하여 제조된 성형품
KR102490389B1 (ko) 2018-12-19 2023-01-19 주식회사 엘지화학 열가소성 수지 조성물 및 이를 이용하여 제조된 성형품
KR20210037227A (ko) 2019-09-27 2021-04-06 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조되는 성형품
KR102305165B1 (ko) * 2019-10-28 2021-09-28 주식회사 삼양사 내화학성이 우수하며, 금속질감을 갖는 열가소성 수지 조성물 및 이를 포함하는 성형품
KR20220052814A (ko) 2020-10-21 2022-04-28 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조된 성형품
KR102478645B1 (ko) * 2021-02-09 2022-12-19 주식회사 삼양사 항균성 및 금속질감을 갖는 열가소성 수지 조성물 및 이를 포함하는 성형품

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WO2016007896A1 (fr) * 2014-07-11 2016-01-14 Tyco Electronics Corporation Formulation composite et composant électronique
CN111019318A (zh) * 2020-01-14 2020-04-17 宁波公牛电器有限公司 一种具有细腻金属质感的pc改性材料及其制备方法
CN111019318B (zh) * 2020-01-14 2022-04-12 宁波公牛电器有限公司 一种具有细腻金属质感的pc改性材料及其制备方法

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