WO2020091279A1 - High rigidity thermoplastic resin having metallic appearance and molded article produced using same - Google Patents

Abstract

The present invention relates to a high rigidity thermoplastic resin comprising a mineral filler and metal particles and having a metallic appearance, and a molded article produced using same and, more specifically, to a thermoplastic resin composition and a molded article produced using same, the composition comprising a polycarbonate resin, a mineral filler, metal particles, and a non-halogen-based flame retardant in specific contents, thereby realizing a metal texture and, differently from a resin comprising glass fibers, realizing a clean appearance as well as ensuring excellent high rigidity, mechanical strength, dimensional stability after molding, flame retardancy, and post-processability.

Description

High-stiffness thermoplastic resin with metallic texture appearance and molded products manufactured using the same

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.

The 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.

Recently, as the demand for an eco-friendly uncoated material has increased, the demand for a metallic material capable of realizing a metallic texture appearance similar to that of a metallic coating without a painting process has increased. In particular, plastic materials for interior and exterior use of automobiles are increasing in the case of using materials having low gloss or low gloss for the purpose of producing a luxurious feeling.

In order to apply the uncoated material excluding such a painting process, the development of a metallic material in which metal particles are applied to the material itself is ongoing, but in the case of an injection molded product requiring high rigidity in the TV bezel or thin and thin areas, high rigidity For characteristics, glass fibers are used in thermoplastic resins to apply to products. However, in developing a metallic resin using metal particles in such a thermoplastic resin, there is a problem in realizing appearance due to glass fibers. In other words, after injection molding, due to metal particles in the material and the appearance problem of the molded product generated from the glass fiber (for example, the problem of the protrusion of the glass fiber or the weld line and flow mark), additional mold changes are required or the product is applied. There is a limited problem.

In order to solve this problem, studies such as adjusting the shape and aspect ratio of metal particles or improving the surface coating material of metal particles are continuously being conducted, but the appearance of the glass fiber cannot be realized due to the protrusion of the glass fiber. to be. In addition, the improvement of the metal particles itself has limitations in improving the appearance problems caused by the tilting, aggregation, and orientation of metal particles during injection molding. For example, 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.

Therefore, while maintaining the same level of high stiffness properties as in the case of reinforcing glass fibers in a thermoplastic resin, flow marks and / or weld lines that may be caused by glass fiber protrusions and metal particles caused by glass fibers during injection molding are maintained. It is necessary to develop a 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.

In order to achieve the above object, 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:

[Formula 1]

In Formula 1, 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 is 0 or 1 independently of each other,

N is 0 to 10,

X is a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms.

According to another aspect 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.

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.

Hereinafter, the present invention will be described in detail.

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.

(A) Polycarbonate resin

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. Bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4 Halogenated bisphenols such as -hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

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 polycarbonate resin of the present invention, 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. When the average molecular weight is less than 10,000, mechanical properties such as impact strength and tensile strength may be deteriorated, and when the average molecular weight exceeds 200,000, problems may occur in the processing of the resin due to an increase in melt viscosity.

 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. When the content of the polycarbonate resin is less than 50 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.

(B) Rubber-modified aromatic vinyl resin

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.

Usually, 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. However, in the case of bulk polymerization, 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.

In the case of any of the above polymerization methods, 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 μm in Z-average, preferably 0.1 to 4 μm. Examples of such 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. When 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.

Hereinafter, the graft copolymer resin (B.1) and the copolymer resin (B.2) which are components of the rubber-modified aromatic vinyl-based resin (B) according to the present invention will be described in detail.

(B.1) Graft copolymer resin

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. Among these, "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 μm in consideration of impact strength and appearance.

The aromatic vinyl-based monomers include styrene-based monomers such as styrene, α-methylstyrene, β-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. As the monomer that can 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.

In the production of the graft copolymer, in order to impart properties such as processability and heat resistance, graft polymerization may be performed by further adding 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.

(B.2) Vinyl 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, α-methylstyrene, β-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.

As the monomer that can be copolymerized with the aromatic vinyl-based monomer, 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.

In addition, 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.

(C) Takeover Flame retardant

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.

[Formula 1]

(Wherein 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 As 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.

 [Formula 2]

(In Formula 2, 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. Preferably, Y is C ₁ -C ₇ alkylidene, and more preferably isopropylidene or methylene.)

As the phosphoric acid ester compound used in the present invention, monophosphate (N = 0), oligophosphate (N = 1 to 10), or a mixture of monophosphate and oligophosphate can be used.

In one embodiment of the present invention, 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.

In one embodiment of the present invention, 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. When the content of the flame retardant is less than 1 part 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.

(D) mineral filler

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 (Talcum) 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.

In the case of a short bed form, the length is limited. Preferably 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 µm or less.

In one embodiment of the present invention, 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. When 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.

In one embodiment of the present invention, the average particle diameter of the mineral filler is not particularly limited, but may be preferably from 3.5 μm to 11 μm, more preferably from 8 to 11 μm.

(E) Metal particles

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 μm, but two or more of them may be mixed and used.

Although not particularly limited, in one embodiment, plate-shaped metal particles may be used. In addition, 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. For example, it may be any metal or an alloy of any two or more metals, but may preferably be aluminum or an aluminum-based alloy. In addition, 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.

In one embodiment of the invention, 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 . When the content of the metal particles is less than 0.1 parts 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 smaller the average particle size of the metal particles is, the better the effect of imparting the metal texture and surface gloss may be, but the decomposition of the thermoplastic resin may increase the amount of gas generated and increase the generation of weld lines. In addition, as the average particle size of the metal particles increases, 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. .

In one embodiment of the present invention, the average particle size of the metal particles may be preferably 10 to 100 μm, and more preferably 15 to 60 μm. When the average particle size of the metal particles is less than 10 μm, 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 μm , The sparkling effect is increased, and the effect of imparting a metal texture may be negligible.

In one embodiment of the present invention, two or more metal particles having different average particle diameters may be mixed and used. At this time, the mixture of metal particles may be a mixture of one or more metal particles having an average particle diameter of less than 10 μm and one or more metal particles having an average particle diameter of 10 to 100 μm (preferably 15 to 60 μm). In the mixture of the metal particles, the metal particles having an average particle diameter of less than 10 μm 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 μm (preferably 15 to 60 μm) ) Is 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.

In the mixture of the metal particles, the content of metal particles having an average particle diameter of less than 10 μm is 3 parts by weight or more, or the content of metal particles having an average particle diameter of 10 to 100 μm (preferably 15 to 60 μm) is 5 parts by weight or more. In the case, the decomposition of the thermoplastic resin may occur and the amount of gas generated may increase.

(F) Other additives

In addition to the above-mentioned “components”, the “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.” For example, 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.

According to one embodiment 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. When 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.

The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited to the following examples.

Example  1 to 3 and Comparative example  1 to 6

The 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.

In the case of 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.

<Ingredient explanation>

-PC: Bisphenol A type linear polycarbonate with a viscosity average molecular weight of about 20,000

-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 μm

-Kaolin: Kaolin with an average particle diameter of 10 ㎛

<Physical property evaluation>

(1) Appearance evaluation (mineral protrusion)

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.

-Phase: Invisible minerals

-Medium: The form of the mineral is visible

-Bottom: The shape of the mineral is clearly visible

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.

(2) metal texture

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. Did

[Equation 1]

L ^* _{15 °} : Luminance of reflected light measured at an angle of 15 °

L ^* _{45 °} : Luminance of reflected light measured at an angle of 45 °

L ^* _{115 °} : Luminance of reflected light measured at an angle of 115 °

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,” and the “metal texture” can be visually felt. The “flop” index of a conspicuous surface is 6

(3) Tensile strength

Tensile strength was measured according to ASTM D638 for the “injection” specimens prepared in Examples and Comparative Examples.

(4) Flexural strength

The flexural strength of the “injection” specimens prepared in Examples and Comparative Examples was measured according to ASTM D760.

(5) Impact strength

Impact strength (1/8 "thick Izod Notched type) was measured according to ASTM D256 for the" injection "specimens prepared in Examples and Comparative Examples.

(6) Flame retardant

The flame retardant grade was measured according to the UL94 method for the injection specimens prepared in Examples and Comparative Examples.

[Table 1]

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.

However, in Comparative Examples 1 to 6, it was confirmed that the surface condition was not good, such as protruding glass fibers, the metal texture was not excellent, and the physical properties such as tensile strength were also poor.

Claims (6)

Based on 100 parts by weight of the total composition, 50 to 80 parts by weight of a polycarbonate resin, 1 to 20 parts by weight of a phosphorus-based flame retardant represented by the following Chemical Formula 1, 10 to 30 parts by weight of a mineral filler and 0.1 to 5 parts by weight of metal particles, A thermoplastic resin composition containing no glass fibers: [Formula 1]

In Formula 1, 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 is 0 or 1 independently of each other, N is 0 to 10, X is a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms. The thermoplastic resin composition of claim 1, further comprising 1 to 30 parts by weight of a rubber-modified aromatic vinyl-based resin based on 100 parts by weight of the composition. The thermoplastic resin composition according to claim 1, wherein the mineral filler is any one selected from the group consisting of talc, kaolin, urastonite, or combinations thereof. The thermoplastic resin composition according to claim 1, wherein the metal particles are one or two or more mixtures of metal particles having an average particle diameter of 10 to 100 μm. The phosphorus-based flame retardant according to claim 1, wherein the resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), N, N'-bis [di- (2,6-xylyl) phosphoryl]- A thermoplastic resin composition, which is any one selected from the group consisting of piperazine or mixtures thereof. A molded article manufactured using the thermoplastic resin composition according to any one of claims 1 to 5.

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