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WO2020091279A1 - Résine thermoplastique à rigidité élevée possédant un aspect métallique et article moulé produit en faisant appel à celle-ci - Google Patents

Résine thermoplastique à rigidité élevée possédant un aspect métallique et article moulé produit en faisant appel à celle-ci Download PDF

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Publication number
WO2020091279A1
WO2020091279A1 PCT/KR2019/013725 KR2019013725W WO2020091279A1 WO 2020091279 A1 WO2020091279 A1 WO 2020091279A1 KR 2019013725 W KR2019013725 W KR 2019013725W WO 2020091279 A1 WO2020091279 A1 WO 2020091279A1
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weight
parts
thermoplastic resin
metal particles
resin composition
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English (en)
Korean (ko)
Inventor
변종웅
박기충
박상현
이동현
임종관
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Samyang Corp
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Samyang Corp
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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5353—Esters of phosphonic acids containing also nitrogen
    • 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
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a high-rigidity thermoplastic resin having a metallic texture appearance and a molded article manufactured using the same, and more specifically, to include a polycarbonate resin, mineral filler, metal particles, and phosphorus-based flame retardant in a specific content to improve the metal texture. It relates to a thermoplastic resin composition and a molded article manufactured using the same, which not only realizes beautiful appearance characteristics while realizing, but also can secure high high stiffness, mechanical strength, dimensional stability after molding, flame retardancy, and post-processability.
  • thermoplastic resin has a lower specific gravity than glass or metal, and has excellent mechanical properties such as moldability and impact resistance. Plastic products using these thermoplastics are rapidly replacing the existing areas of glass or metal, including electrical and electronic products and automotive parts.
  • Patent Publication No. 2011-0057415 discloses a thermoplastic resin composition comprising a mica luster pigment coated with a thermoplastic resin and a metal oxide, but still has a problem of generating flow marks and weld lines.
  • thermoplastic resin composition for interior and exterior materials that can reduce and at the same time improve the gloss and appearance characteristics of a molded article.
  • the object of the present invention is not only to realize a beautiful appearance characteristic while realizing a metal texture by including a polycarbonate resin, mineral filler, metal particles and phosphorus-based flame retardant in a specific content, high high stiffness, mechanical similar to the case of containing glass fiber It is to provide a thermoplastic resin composition and a molded product manufactured using the thermoplastic resin composition capable of securing flame retardancy and post-processability while having strength and dimensional stability after molding.
  • the present invention is based on 100 parts by weight of the total composition, 50 to 80 parts by weight of polycarbonate resin, 1 to 20 parts by weight of phosphorus-based flame retardant represented by Formula 1, 10 to 30 parts by weight of mineral filler, and Provided is a thermoplastic resin composition comprising 0.1 to 5 parts by weight of metal particles and free of glass fibers:
  • R 1 , R 2 , R 3 and R 4 are each independently of each other, C 1 -C 20 alkyl , C 3 -C 21 cycloalkyl, C 6 -C 20 aryl or C 7 -C 20 Alkyl,
  • n 0 or 1 independently of each other
  • N 0 to 10
  • X is a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms.
  • thermoplastic resin composition of the present invention a molded article manufactured using the thermoplastic resin composition of the present invention is provided.
  • the composition according to the present invention includes polycarbonate resin, mineral filler, metal particles, and phosphorus-based flame retardant in a specific content, thereby providing flame retardancy, mechanical strength, dimensional stability after molding, workability, post-processability, and surface gloss required for the thermoplastic resin composition. At the same time, it is possible to provide a clean appearance and metal texture at the same time, and it is possible to omit or reduce the painting process after injection, thereby providing an environmental and economical effect.
  • Example 1 is a sample of Comparative Example 6 containing glass fibers (upper left) and Example 1 (upper right), Example 2 (lower left) and Example 3 (lower right) specimens showing clean appearance and metallic texture including inorganic particles. It was observed by photographing the surface of.
  • Figure 2 is a specimen of Comparative Example 6 containing glass fibers (upper left) and Example 1 (upper right), Example 2 (lower left) and Example 3 (lower right) specimens showing a clean appearance and metallic texture including inorganic particles. The surface of was observed through a microscopic microscope.
  • the present invention can add a mineral filler, metal particles, and phosphorus-based flame retardant to a thermoplastic resin containing polycarbonate, and does not contain glass fibers, thereby providing a high rigidity and clean appearance and metal texture.
  • the polycarbonate resin used in the resin composition of the present invention is not particularly limited as an aromatic polycarbonate resin, and can be used in general, but is prepared by reacting dihydric phenol and phosgene in the presence of a molecular weight modifier and a catalyst, or di It is preferable to prepare using ester interchange reaction of a carbonate precursor such as hydric phenol and diphenyl carbonate.
  • the dihydric phenol is preferably bisphenol and more preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
  • Bisphenol A can be partially or wholly replaced by other dihydric phenols.
  • Dihydric phenol is hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2- in addition to bisphenol A.
  • the polycarbonate resin may be a homopolymer or a copolymer using two or more kinds of dihydric phenols, or a mixture of these resins. Also, the polycarbonate resin includes linear polycarbonate, branched polycarbonate, polyester carbonate copolymer, and silicone copolymerized polycarbonate.
  • the linear polycarbonate resin is preferably a bisphenol A-based polycarbonate resin.
  • the branched polycarbonate is preferably prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride and trimellitic acid with a dihydroxyphenol and a carbonate precursor.
  • the polyester carbonate copolymer is preferably prepared by reacting a bifunctional carboxylic acid with a dihydric phenol and carbonate precursor.
  • the viscosity average molecular weight (M v ) measured in a methylene chloride solution at 25 ° C. is preferably applied to 10,000 to 200,000, more preferably applied to 10,000 to 40,000, and 17,000 to 30,000 It is more preferable.
  • M v the average molecular weight measured in a methylene chloride solution at 25 ° C.
  • the content of the polycarbonate resin of the present invention is not particularly limited, but preferably, based on 100 parts by weight of the thermoplastic resin composition of the present invention, it may be 50 parts by weight or more, 55 parts by weight or more, 60 parts by weight or more, or 65 parts by weight or more And 80 parts by weight or less, 75 parts by weight or less, 72 parts by weight or less, or 70 parts by weight or less, for example, 50 to 80 parts by weight, preferably 55 to 75 parts by weight.
  • strength characteristics such as tensile strength and flexural strength may be poor, and when it is more than 80 parts by weight, impact resistance and the like may be poor.
  • the rubber-modified aromatic vinyl-based resin is a polymer in which the rubber-like polymer is dispersed in the form of particles in a matrix (continuous phase) composed of the aromatic-vinyl-based polymer.
  • the rubber-modified aromatic vinyl-based resin may be prepared by adding an aromatic vinyl monomer and a vinyl-polymerizable vinyl monomer in the presence of a rubber-like polymer to polymerize.
  • Such a rubber-modified aromatic vinyl-based resin can be produced by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization.
  • a rubber-containing high-graft copolymer resin and a rubber-free copolymer resin are separately prepared, and then the two are mixed and extruded to prepare a rubber-modified aromatic vinyl resin.
  • a rubber-modified aromatic vinyl-based resin can be produced only by a one-step reaction process without separately preparing a graft copolymer resin and a copolymer resin.
  • the rubber content in the final rubber-modified aromatic vinyl-based resin component is 0.1 to 40% by weight, preferably 3 to 20% by weight, more preferably 5 to 5% based on the total amount of the aromatic vinyl-based resin. 15% by weight.
  • the rubber particle size is 0.05 to 6.0 ⁇ m in Z-average, preferably 0.1 to 4 ⁇ m.
  • resins are acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-acrylic rubber-styrene copolymer resin (AAS), acrylonitrile-ethylenepropylene rubber-styrene copolymer resin (AES). , Rubber reinforced polystyrene (HIPS). They can also be applied in mixtures of two or more.
  • the "rubber-modified aromatic vinyl-based resin” can be applied by using a graft resin alone or a graft copolymer resin and a copolymer resin in combination, and it is preferable to mix in consideration of each compatibility. More specifically, it is preferable to blend 10 to 100% by weight of the graft copolymer resin (B.1) and 0 to 90% by weight of the copolymer resin (B.2) in the rubber-modified aromatic vinyl resin. In embodiments, the rubber-modified aromatic vinyl-based resin (B) may be blended with graft copolymer resin (B.1) 55 to 90 wt% and copolymer resin (B.2) 10 to 45 wt%. In another embodiment, the rubber-modified aromatic vinyl-based resin (B) may be blended with 15 to 50% by weight of the graft copolymer resin (B.1) and 50 to 85% by weight of the copolymer resin (B.2).
  • the thermoplastic resin composition of the present invention may further include the rubber-modified aromatic vinyl-based resin, the content of which is based on 100 parts by weight of the thermoplastic resin composition, 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, or 5 It may be more than parts by weight, 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less or 10 parts by weight or less, for example, 1 to 30 parts by weight, 2 to 20 parts by weight, 3 to 10 parts by weight It can be wealth.
  • the content is less than 1 part by weight, impact resistance and the like may be poor, and when the content exceeds 30 parts by weight, strength characteristics such as tensile strength and flexural strength may be deteriorated.
  • the graft copolymer resin (B.1) used in the present invention is produced by polymerizing an aromatic vinyl monomer capable of graft copolymerization with a rubber-like polymer and a monomer copolymerizable with the aromatic vinyl monomer.
  • Examples of the rubber used in the graft copolymer resin include diene-based rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), saturated rubbers obtained by hydrogenating the diene-based rubbers, isoprene rubbers, Chloroprene rubber, acrylic rubber such as butyl polyacrylate, ethylene-propylene rubber, ethylene-propylene-diene monomer terpolymer (EPDM), and the like.
  • the rubber may be used alone or in combination of two or more.
  • "diene-based” rubber is preferable, and more preferably, butadiene-based rubber is suitable.
  • the content of rubber is 5 to 95% by weight of the total weight of the graft copolymer resin.
  • the average particle size of the rubber particles is suitable in the range of 0.1 to 4 ⁇ m in consideration of impact strength and appearance.
  • the aromatic vinyl-based monomers include styrene-based monomers such as styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, monochlorostyrene, dichlorostyrene, and dibromostyrene. It can be used representatively.
  • the styrene-based monomers may be used alone or in combination of two or more. Of these, styrene is the most preferred.
  • the content of the aromatic vinyl monomer is 34 to 94 parts by weight out of 100 parts by weight of the entire graft copolymer resin.
  • One or more monomers copolymerizable to the aromatic vinyl-based monomer may be introduced.
  • unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile are preferred.
  • the unsaturated nitrile-based compounds may be used alone or in combination of two or more.
  • the content of the copolymerizable monomer may be used as 1 to 30 parts by weight out of 100 parts by weight of the total graft copolymer resin.
  • graft polymerization may be performed by further adding monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleide.
  • monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleide.
  • Monomers that add the above processability and heat resistance may be used alone or in combination of two or more. The added content is in the range of 0 to 15 parts by weight of 100 parts by weight of the total graft copolymer resin.
  • the vinyl-based copolymer resin of the present invention is polymerized in consideration of compatibility with an amount equivalent to the monomer ratio excluding rubber among the components of the graft copolymer.
  • Aromatic vinyl monomers used in the copolymer resin include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para t-butylstyrene, ethylstyrene, monochlorostyrene, dichlorostyrene, and dibromostyrene Styrene-based monomers may be used, but are not limited thereto. Of these, styrene is the most preferred. These may be used alone or in combination of two or more. 60 to 90 parts by weight of the total 100 parts by weight of the copolymer resin is preferred.
  • an unsaturated nitrile-based compound such as acrylonitrile and methacrylonitrile is preferable.
  • the unsaturated nitrile-based compounds may be used alone or in combination of two or more.
  • the content of the copolymerizable monomer may be used as 10 to 40 parts by weight out of 100 parts by weight of the total graft copolymer resin.
  • copolymer resin 0 to 30 parts by weight of monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleide are added to 100 parts by weight of the copolymer resin in order to impart properties such as processability and heat resistance to the “copolymer” resin. Can be copolymerized.
  • monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleide
  • the phosphorus flame retardant (C) used in the present invention may be a phosphoric acid ester compound, and the phosphoric acid ester compound is preferably a compound represented by [Formula 1] below.
  • R 1 , R 2 , R 3 and R 4 are each independently of each other, C 1 -C 20 alkyl, C 3 -C 21 cycloalkyl, C 6 -C 20 aryl or C 7 -C 20 aralkyl N may be 0 or 1 independently of each other, preferably 1.
  • N is 0 to 10, preferably 0.3 to 8, and more preferably 0.5 to 5.
  • X is 6 to 30 carbon atoms
  • a mononuclear aromatic or polynuclear aromatic group it is preferably derived from diphenylphenol, bisphenol A, lesocinol or hydroquinone.
  • the phosphoric acid ester compound is also preferably a phosphoric acid ester compound of [Formula 2] below.
  • R 1 , R 2 , R 3 , R 4 , n, N are as defined in Formula 1, R 5 and R 6 are independently of each other C 1 -C 6 alkyl, preferably Y is C 1 -C 7 alkylidene, C 1 -C 7 alkylene, C 5 -C 12 cycloalkylene, C 5 -C 12 cycloalkylidene, -O-, -S-, -SO- , -SO 2 -or -CO-, and a represents an integer from 0 to 2.
  • Y is C 1 -C 7 alkylidene, and more preferably isopropylidene or methylene.
  • the type of the non-halogen-based flame retardant is not particularly limited, but preferably, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), N, N'-bis [ Di- (2,6-xylylphosphoryl) -piperazine or a phosphorus-based flame retardant selected from mixtures thereof can be used.
  • the content of the phosphorus-based flame retardant is not particularly limited, based on 100 parts by weight of the thermoplastic resin composition of the present invention, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more Or it may be 13 parts by weight or more, 20 parts by weight or less, 18 parts by weight or less, 16 parts by weight or less, 12 parts by weight or less, or 10 parts by weight or less, for example, 1 to 20 parts by weight, 5 to 17 parts by weight, 8 to It may be 15 parts by weight or 13 to 17 parts by weight.
  • the effect of imparting flame retardancy may be negligible, and when the content of the flame retardant is more than 20 parts by weight, decomposition of the thermoplastic resin may result in a large amount of gas, mechanical properties and moldability This can be poor.
  • the mineral filler used in the present invention is an inorganic material having a plate-like shape or a short needle-like shape, and may perform a role of realizing a clean appearance without protrusion on the exterior when injection molding using a thermoplastic resin composition, and is not limited.
  • the mineral filler may be used alone or in combination of two or more.
  • the type of the mineral filler is not particularly limited as long as it has a plate shape, but may be preferably plate talc and kaolin.
  • Plate Talc A natural mineral in the form of a plate, and contains silicate minerals including magnesium.
  • the chemical formula of talc may be H 2 Mg 3 (SiO 3 ) 4 or Mg 3 Si 4 O 10 (OH) 2 , but is not limited thereto.
  • the plate-like talc has the lowest Mohs hardness of about 1.0 to 1.5, a specific gravity of 2.6 to 2.7, has a high whiteness, has excellent electrical insulation, heat resistance and chemical stability, and has a weak layered structure or interlayer bonding strength, and can be easily peeled off.
  • Kaolin is a silicate mineral that is a natural mineral that has gone through a plate shape.
  • the chemical formula of kaolin may be Al 2 Si 2 O 5 (OH) 4 , but is not limited thereto.
  • the kaolin has a specific gravity of 1.8 to 2.6, has a gray color, and has excellent electrical insulation, heat resistance, and chemical stability.
  • the length is limited.
  • it may be urastonite.
  • the chemical formula of urastonite may be CaSiO 3 , but is not limited thereto.
  • Ulastonite is a calcium silicate mineral that has a needle shape.
  • the urastonite has a specific gravity of 2.7 to 2.9, and has a high whiteness.
  • the Molass hardness of the urastonite is about 4.5 and the length should be 10 ⁇ m or less.
  • the content of the mineral filler may be 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, or 15 parts by weight or more based on 100 parts by weight of the thermoplastic resin composition of the present invention, and 30 parts by weight or more Hereinafter, it may be 25 parts by weight or less, 22 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less, for example, 10 to 30 parts by weight, 15 to 25 parts by weight, 20 to 25 parts by weight, or 10 to 15 parts by weight have.
  • the content of the mineral filler is less than 10 parts by weight, stiffness may be deteriorated, and when the content of the plate-like inorganic material is more than 30 parts by weight, decomposition of the thermoplastic resin may cause deterioration in productivity and cause a decrease in impact strength. Can be.
  • the average particle diameter of the mineral filler is not particularly limited, but may be preferably from 3.5 ⁇ m to 11 ⁇ m, more preferably from 8 to 11 ⁇ m.
  • the metal particles used in the present invention may serve to impart a metallic texture to the thermoplastic resin composition.
  • the metal particles may be used alone as one of the metal particles having a particle diameter of 10 to 100 ⁇ m, but two or more of them may be mixed and used.
  • plate-shaped metal particles may be used.
  • it can be used by mixing the metal particles of the spherical type as well as the metal particles of the plate type.
  • the material of the metal particles used in the present invention is not particularly limited, and the material of the metal particles used according to the metallic appearance required in the molded article to which the thermoplastic resin composition of the present invention is applied may be selected.
  • it may be any metal or an alloy of any two or more metals, but may preferably be aluminum or an aluminum-based alloy.
  • the surface of the metal particles may be coated or surface treated, and a silica or silane coupling agent may be used as a coating or surface treatment agent, but is not limited thereto.
  • the content of the metal particles is based on 100 parts by weight of the thermoplastic resin composition of the present invention, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.8 parts by weight or more or 1 part by weight or more May be 5 parts by weight or less, 3 parts by weight or less, 2.5 parts by weight or less, 2 parts by weight or less or 1.5 parts by weight or less, for example, 0.1 to 5 parts by weight, 0.5 to 3 parts by weight, 0.5 to 1 part by weight .
  • the effect of imparting the metal texture may be insignificant, and when the content of the metal particles is more than 5 parts by weight, decomposition of the thermoplastic resin may occur, resulting in a large amount of gas, and mechanical The physical properties and moldability are poor, and the appearance characteristics may be poor due to weld lines.
  • the amount of gas generated may not decrease due to no decomposition of the thermoplastic resin, and the generation of weld lines may be reduced, but the effect of imparting the metallic texture and surface gloss may be insignificant due to the increased sparkling effect. .
  • the average particle size of the metal particles may be preferably 10 to 100 ⁇ m, and more preferably 15 to 60 ⁇ m.
  • the average particle size of the metal particles is less than 10 ⁇ m, the surface area in contact with the thermoplastic resin is large to cause decomposition of the thermoplastic resin well, and thus gas generation amount may increase, and when the average particle size of the metal particles is greater than 100 ⁇ m , The sparkling effect is increased, and the effect of imparting a metal texture may be negligible.
  • the mixture of metal particles may be a mixture of one or more metal particles having an average particle diameter of less than 10 ⁇ m and one or more metal particles having an average particle diameter of 10 to 100 ⁇ m (preferably 15 to 60 ⁇ m).
  • the metal particles having an average particle diameter of less than 10 ⁇ m may be less than 3 parts by weight, based on 100 parts by weight of the thermoplastic resin composition of the present invention, and have an average particle diameter of 10 to 100 ⁇ m (preferably 15 to 60 ⁇ m) )
  • a metal particle, based on 100 parts by weight of the thermoplastic resin composition of the present invention may be less than 5 parts by weight
  • the content of the mixture of the metal particles may be 0.1 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin composition of the present invention It may be, preferably 0.5 to 3 parts by weight, more preferably 1 to 2.5 parts by weight.
  • the content of metal particles having an average particle diameter of less than 10 ⁇ m is 3 parts by weight or more, or the content of metal particles having an average particle diameter of 10 to 100 ⁇ m (preferably 15 to 60 ⁇ m) is 5 parts by weight or more.
  • the decomposition of the thermoplastic resin may occur and the amount of gas generated may increase.
  • thermoplastic resin “composition” of the present invention may additionally contain one or more other additives that are commonly added to “thermoplastic” resin “composition” for injection molding or extrusion “forming.”
  • plasticizer, coupling agent, heat stabilizer It may additionally contain one or more other additives selected from the group consisting of tablets, mold release agents, lubricants, dispersants, anti-dropping agents, matting agents, weathering stabilizers or a mixture of two or more of these.
  • the content of the other additives is not particularly limited, and is an amount that can be used to add additional functions in a range that does not impair the desired physical properties of the thermoplastic resin composition of the present invention.
  • the content of other additives may be 0.1 to 20 parts by weight, and preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total thermoplastic resin composition of the present invention.
  • the content of the other additives is less than 0.1 parts by weight, the effect of improving various functions according to the use of the other additives may be insignificant, and when the content of the other additives exceeds 20 parts by weight, mechanical properties may be poor.
  • thermoplastic resin composition of Examples 1 to 3 and the thermoplastic resin composition of Comparative Examples 1 to 6 were prepared by mixing in the contents shown in Tables 1 and 2 below. Thereafter, extrusion was performed by melt-kneading the prepared thermoplastic resin composition using a 32-pi twin-screw extruder at 210 ° C to 260 ° C and 200 rpm to 250 rpm, and the clamping force of 100 ton to 200 ton at the same temperature condition Injection specimens were prepared using an injection machine having a.
  • injection test specimens for appearance evaluation measurement a rectangular specimen having a size of 250 mm x 150 mm was prepared, and in the case of injection specimens for measuring mechanical properties, injection specimens conforming to the respective ASTM standards were suitable for measuring tensile strength, flexural strength, and impact strength. In the case of injection specimens for flame retardancy measurement, injection specimens conforming to UL94 standards were prepared.
  • ABS Acrylonitrile / butadiene / styrene (ABS) resin (Lotte Chemical CH-T)
  • -Phosphorus-based flame retardant bisphenol A bis (diphenyl phosphate); BDP (CR-741)
  • -Talc plate-shaped talc having an average particle diameter of 10 ⁇ m
  • the injection specimens prepared in Examples and Comparative Examples were subjected to surface observation through a micro lens to measure the degree of inorganic protruding.
  • Example 1 is a sample of Comparative Example 6 containing glass fibers (upper left) and Example 1 (upper right), Example 2 (lower left) and Example 3 (lower right) specimens showing clean appearance and metallic texture including inorganic particles. It was observed by photographing the surface of.
  • Figure 2 is a specimen of Comparative Example 6 containing glass fibers (upper left) and Example 1 (upper right), Example 2 (lower left) and Example 3 (lower right) specimens showing a clean appearance and metallic texture including inorganic particles. The surface of was observed through a microscopic microscope.
  • the flop index was measured using BYK's BYK-Mac i Spectrophotometer. Specifically, after measuring the “luminance” of the reflected light at an angle of “15 °, 45 ° and“ 110 ° ”against the“ surface ”of the“ injection ”specimen prepared in the above Examples and Comparative Examples, and then substituting“ Equation 1 ”to calculate the flop index.
  • the “flop” index on the object surface without metal texture is “0”
  • the “flop” index on the actual metal surface is “15 to 17”
  • the “flop” index on the surface of the injection molded product coated with the coating composition is “11 to 14”
  • the “metal texture” can be visually felt.
  • the “flop” index of a conspicuous surface is 6
  • the flame retardant grade was measured according to the UL94 method for the injection specimens prepared in Examples and Comparative Examples.
  • thermoplastic resins As can be seen from Table 1, in Examples 1 to 3, containing thermoplastic resins, metal particles, inorganic particles other than glass fibers, and flame retardants, flame retardancy, mechanical strength, dimensional stability after molding, and work required for thermoplastic resin compositions It was confirmed that it was possible to implement a clean appearance and a metal texture at the same time while providing a castle, post-processability, and surface gloss.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une résine thermoplastique à rigidité élevée comprenant une charge minérale et des particules métalliques et présentant un aspect métallique, et un article moulé produit en faisant appel à celle-ci et, plus précisément, concerne une composition de résine thermoplastique et un article moulé produit en faisant appel à celle-ci, la composition comprenant une résine de polycarbonate, une charge minérale, des particules métalliques, et un agent ignifuge non halogéné en des teneurs spécifiques, ce qui permet d'obtenir une texture métallique et, différemment d'une résine comprenant des fibres de verre, d'obtenir un aspect propre tout en garantissant d'excellentes propriétés de rigidité élevée, de résistance mécanique, de stabilité dimensionnelle après moulage, d'ininflammabilité et d'aptitude à un traitement ultérieur.
PCT/KR2019/013725 2018-10-31 2019-10-18 Résine thermoplastique à rigidité élevée possédant un aspect métallique et article moulé produit en faisant appel à celle-ci Ceased WO2020091279A1 (fr)

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KR1020180131989A KR102201718B1 (ko) 2018-10-31 2018-10-31 금속질감의 외관을 갖는 고강성 열가소성 수지 및 이를 이용하여 제조된 성형품

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KR102597538B1 (ko) * 2021-10-26 2023-11-03 단국대학교 산학협력단 금속감을 가지는 고분자 매트릭스 복합재료의 제조방법 및 이에 의해 제조된 고분자 매트릭스 복합재료

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KR20010074740A (ko) * 1998-07-27 2001-08-09 제이 엘. 차스킨, 버나드 스나이더, 아더엠. 킹 금속성 외관을 갖는 난연성 폴리카보네이트/고무-변성된그래프트 공중합체 수지 블렌드
JP2009203270A (ja) * 2008-02-26 2009-09-10 Teijin Chem Ltd 外観に優れたポリカーボネート樹脂組成物
KR20130046154A (ko) * 2011-10-27 2013-05-07 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
KR20160059529A (ko) * 2014-11-18 2016-05-27 삼성에스디아이 주식회사 외관 특성이 우수한 열가소성 수지 조성물 및 이를 이용한 성형품
KR20180048273A (ko) * 2016-11-02 2018-05-10 롯데첨단소재(주) 열가소성 수지 조성물 및 이로부터 제조된 성형품

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Publication number Priority date Publication date Assignee Title
KR20010074740A (ko) * 1998-07-27 2001-08-09 제이 엘. 차스킨, 버나드 스나이더, 아더엠. 킹 금속성 외관을 갖는 난연성 폴리카보네이트/고무-변성된그래프트 공중합체 수지 블렌드
JP2009203270A (ja) * 2008-02-26 2009-09-10 Teijin Chem Ltd 外観に優れたポリカーボネート樹脂組成物
KR20130046154A (ko) * 2011-10-27 2013-05-07 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
KR20160059529A (ko) * 2014-11-18 2016-05-27 삼성에스디아이 주식회사 외관 특성이 우수한 열가소성 수지 조성물 및 이를 이용한 성형품
KR20180048273A (ko) * 2016-11-02 2018-05-10 롯데첨단소재(주) 열가소성 수지 조성물 및 이로부터 제조된 성형품

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KR20200050050A (ko) 2020-05-11

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