KR102063375B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention is 100 parts by weight of a polycarbonate resin; Rubber modified vinyl copolymer resin 1 to 15 parts by weight; 10 to 30 parts by weight of a phosphorus flame retardant; 3 to 12 parts by weight of calcium carbonate; Talc 5 to 40 parts by weight; And 0.001 to 5 parts by weight of black pigment, wherein the weight ratio of calcium carbonate and talc is 1: 1.5 to 1: 6, and the average particle size of the black pigment is 10 to 24 nm. The thermoplastic resin composition may implement high gloss and high appearance characteristics, and is excellent in fluidity, impact resistance, heat resistance, thin film flame retardancy, dimensional stability, and the like.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE PRODUCED THEREFROM}

The present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition capable of realizing high gloss and high appearance properties, having excellent fluidity, impact resistance, heat resistance, thin film flame retardancy, dimensional stability, and the like, and a molded article manufactured therefrom.

The thermoplastic resin composition has a specific gravity lower than that of glass and metal, and is excellent in physical properties such as formability and impact resistance, and thus is useful in housings, interior / exterior materials for automobiles, exterior materials for buildings, and the like. In particular, with the recent trend toward larger and lighter electrical and electronic products, plastic products using thermoplastic resins are rapidly replacing the existing glass and metal areas.

Among these thermoplastic resin compositions, a PC / ABS thermoplastic resin composition obtained by mixing a rubber-modified aromatic vinyl copolymer resin such as acrylonitrile-butadiene-styrene (ABS) copolymer resin with a polycarbonate (PC) resin is a polycarbonate resin. It is possible to improve workability, chemical resistance, etc. without reducing impact resistance, heat resistance, and the like, and to reduce costs.

In addition, the thermoplastic resin composition may include an inorganic filler such as glass fiber, talc, wollastonite, a flame retardant, or the like, for the purpose of improving rigidity, flame retardancy, and the like.

However, thermoplastic resin compositions to which inorganic fillers, such as glass fibers, are applied may have low fluidity, elongation, and the like, and glass fibers, etc. may protrude, making it difficult to implement high appearance characteristics.

Therefore, the development of a thermoplastic resin composition that can implement high gloss, high appearance characteristics, and excellent in fluidity, impact resistance, heat resistance, thin film flame retardancy, dimensional stability, and the like is required.

Background art of the present invention is disclosed in Japanese Patent Laid-Open No. 2015-028135 and the like.

An object of the present invention is to provide a thermoplastic resin composition that can implement high gloss, high appearance characteristics, and excellent in fluidity, impact resistance, heat resistance, thin film flame retardancy, dimensional stability and the like.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition is 100 parts by weight of polycarbonate resin; Rubber modified vinyl copolymer resin 1 to 15 parts by weight; 10 to 30 parts by weight of a phosphorus flame retardant; 3 to 12 parts by weight of calcium carbonate; Talc 5 to 40 parts by weight; And 0.001 to 5 parts by weight of black pigment, wherein the weight ratio of calcium carbonate and talc is 1: 1.5 to 1: 6, and the average particle size of the black pigment is 10 to 24 nm.

In one embodiment, the rubber-modified vinyl copolymer resin may include a rubber-modified aromatic vinyl graft copolymer in which an aromatic vinyl monomer and an alkyl (meth) acrylate monomer are graft copolymerized to a rubbery polymer.

In embodiments, the phosphorus-based flame retardant may include one or more of phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds and phosphazene compounds.

In an embodiment, the content of the rubber-modified vinyl copolymer resin may be less than the content of the phosphorous flame retardant.

In an embodiment, the thermoplastic resin composition may have a melt-flow index (MI) of 30 to 50 g / 10 min, measured at 220 ° C. and 5 kgf, in accordance with ASTM D1238, and in accordance with ASTM D256. Notched Izod impact strength measured with a 1/8 "thickness specimen may be at least 5 kgfcm / cm.

In an embodiment, the thermoplastic resin composition may have a glass transition temperature of 82 to 90 ° C., and a flame retardancy of the 1.0 mm thick specimen measured according to the UL94 standard may be V1 or more.

In embodiments, the thermoplastic resin composition may have a linear expansion coefficient of 20 to 45 cm / cm ℃ measured on a 6.4 mm bend specimen at 90 ℃ according to ASTM D696, 400 mm × 100 mm × 10 mm thick Using a luminescent mold of size, injection specimens are prepared by packing pressure (30 bar, 50 bar and 70 bar) at a molding temperature of 260 ° C., and the injection molded specimens have no burr. After measuring for 24 hours at 23 ℃ the horizontal length of the injection specimen may be 390 to 400 mm.

In embodiments, the thermoplastic resin composition may have a glossiness (Gloss (60 °)) of 95 to 100% of the injection specimen measured at an angle of 60 ° according to ASTM D523, 3.2 mm measured according to ASTM D2244 The lightness (L *) value of the thickness specimen may be 90 to 100, the a * value is -0.1 to 0.3, and the b * value may be -0.1 to 0.3.

Another aspect of the invention relates to a molded article. The molded article is formed from the thermoplastic resin composition.

In an embodiment, the molded article may be a plastic member of an electronics housing including a metal frame and a plastic member in contact with at least one surface of the metal frame.

The present invention can realize high gloss, high appearance properties, and has the effect of providing the thermoplastic resin composition and molded articles formed therefrom having excellent fluidity, impact resistance, heat resistance, thin film flame retardancy, dimensional stability, and the like.

1 is a schematic cross-sectional view of an electronics housing according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention includes (A) a polycarbonate resin; (B) rubber-modified vinyl copolymer resin; (C) phosphorus-based flame retardants; (D) calcium carbonate; (E) talc; And (F) a black pigment.

(A) polycarbonate resin

As the polycarbonate resin according to one embodiment of the present invention, a polycarbonate resin used in a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with precursors such as phosgene, halogen formate, and carbonic acid diester can be used.

In an embodiment, the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane and the like can be exemplified, but is not limited thereto. For example, 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, and specifically, 2, 2-bis (4-hydroxyphenyl) propane called bisphenol-A can be used.

In embodiments, the polycarbonate resin may be a branched chain, for example, 0.05 to 2 mol% of a trivalent or more polyfunctional compound, specifically, 3 to the total diphenols used for polymerization It is also possible to use a branched polycarbonate resin prepared by adding a compound having a phenol group or more.

In an embodiment, the polycarbonate resin may be used in the form of a homo polycarbonate resin, a copolycarbonate resin or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, such as a bifunctional carboxylic acid.

In an embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 50,000 g / mol, for example, 15,000 to 40,000 g / mol. In the above range, the flowability (processability) of the thermoplastic resin composition may be excellent.

In an embodiment, the polycarbonate resin may have a Melt Flow Index (MI) of 5 to 80 g / 10 min, measured under a load condition of 300 ° C. and 1.2 kg based on ISO 1133. In addition, the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indices.

(B) Rubber-modified vinyl copolymer resin

The rubber-modified vinyl copolymer resin of the present invention uses a rubber-modified aromatic vinyl graft copolymer in which (B1) the rubbery polymer is graft copolymerized with an aromatic vinyl monomer and an alkyl (meth) acrylate monomer, or The rubber-modified aromatic vinyl graft copolymer (B1) and (B2) aromatic vinyl copolymer resin may be mixed and used.

Unless otherwise stated herein, "(meth) acryl" means that both "acryl" and "methacryl" are possible. For example, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

(B1) rubber modified aromatic vinyl graft copolymer

The rubber-modified aromatic vinyl graft copolymer according to one embodiment of the present invention is a monomer which adds an aromatic vinyl monomer, an alkyl (meth) acrylate monomer, and the like to the rubbery polymer, and, if necessary, gives a processability and heat resistance. After further comprising, it can be obtained by polymerization (graft copolymerization), the polymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization, block polymerization.

In an embodiment, the rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers hydrogenated to the diene rubber, isoprene rubber, and polybutylacrylic acid. Acrylic rubber, ethylene-propylene-diene monomer terpolymer (EPDM), etc. can be illustrated. These can be applied individually or in mixture of 2 or more types. For example, a diene rubber can be used and specifically, a butadiene rubber can be used. The content of the rubbery polymer may be 20 to 70% by weight, for example 30 to 65% by weight, based on the total weight (100% by weight) of the rubber-modified aromatic vinyl graft copolymer. Impact resistance, mechanical properties and the like of the thermoplastic resin composition may be excellent in the above range. In addition, the average particle size (Z-average) of the rubbery polymer (rubber particles) may be 0.05 to 6 μm, for example 0.15 to 4 μm, specifically 0.25 to 3.5 μm. In the above range, the thermoplastic resin composition may have excellent impact resistance, appearance, flame retardant properties, and the like. Here, the average particle size (Z-average) was measured using a Mastersizer 2000E series (Malvern) instrument by dry method, according to a known method.

In an embodiment, the aromatic vinyl monomer may be graft copolymerized to the rubbery copolymer, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl Styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, etc. may be used, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. The content of the aromatic vinyl monomer may be 5 to 40% by weight, for example, 10 to 30% by weight of the total weight (100% by weight) of the rubber-modified aromatic vinyl graft copolymer. In the above range, the fatigue resistance of the thermoplastic resin composition may be excellent in impact resistance, mechanical properties, and the like.

In an embodiment, the alkyl (meth) acrylate monomers may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like, and may be used alone or in combination of two or more. have. For example, methyl (meth) acrylate, specifically methyl methacrylate, can be used. The content of the alkyl (meth) acrylate-based monomer may be 1 to 35% by weight, for example 5 to 30% by weight of the total weight of the rubber-modified aromatic vinyl graft copolymer. Impact resistance, mechanical properties and the like of the thermoplastic resin composition may be excellent in the above range.

In specific embodiments, the monomer for imparting the processability and heat resistance, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. Vinyl cyanide compounds, acrylic acid, maleic anhydride, N-substituted maleimide and the like can be exemplified, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. The content of the monomer for imparting processability and heat resistance may be 15 wt% or less, for example, 0.1 to 10 wt% of the total weight of the rubber-modified aromatic vinyl graft copolymer. In the above range, processability, heat resistance, mechanical properties, and the like of the thermoplastic resin composition may be further improved without deteriorating other physical properties.

In embodiments, the rubber-modified aromatic vinyl graft copolymer may be included in more than 60% by weight, for example 80 to 100% by weight of 100% by weight of the total rubber-modified vinyl-based copolymer resin. In the above range, the impact resistance, mechanical properties, fluidity and the like of the thermoplastic resin composition may be excellent.

(B2) aromatic vinyl copolymer resin

The aromatic vinyl copolymer resin according to one embodiment of the present invention may be an aromatic vinyl copolymer resin used in a conventional rubber-modified vinyl copolymer resin. For example, the aromatic vinyl copolymer resin may be a polymer of a monomer mixture including a monomer copolymerizable with an aromatic vinyl monomer such as an aromatic vinyl monomer and a vinyl cyanide monomer.

In an embodiment, the aromatic vinyl copolymer resin may be obtained by mixing an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer, and then polymerizing them, and the polymerization may be emulsion polymerization, suspension polymerization, bulk polymerization, or the like. It can be carried out by a known polymerization method of.

In embodiments, the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene Vinyl naphthalene may be used, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. The content of the aromatic vinyl monomer may be 20 to 90% by weight, for example 30 to 80% by weight, of 100% by weight of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.

In a specific embodiment, as the monomer copolymerizable with the aromatic vinyl monomer, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. Vinyl cyanide monomers and the like can be used, and can be used alone or in combination of two or more. The content of the monomer copolymerizable with the aromatic vinyl monomer may be 10 to 80% by weight, for example 20 to 70% by weight, based on 100% by weight of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.

In embodiments, the aromatic vinyl copolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 300,000 g / mol, for example, 15,000 to 150,000 g / mol. In the above range, the mechanical strength, moldability, and the like of the thermoplastic resin composition may be excellent.

In an embodiment, the aromatic vinyl copolymer resin may be included in 20% by weight or less, for example, 10% by weight or less of 100% by weight of the total rubber-modified vinyl-based copolymer resin. In the above range, it may be excellent in the fluidity, thermal stability and the like of the thermoplastic resin composition.

The rubber-modified vinyl copolymer resin (B) according to one embodiment of the present invention may be included in an amount of 1 to 15 parts by weight, for example, 3 to 10 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). When the content of the rubber-modified vinyl copolymer resin (B) is less than 1 part by weight based on 100 parts by weight of the polycarbonate resin (A), the impact resistance, mechanical properties, etc. of the thermoplastic resin composition may decrease. When it exceeds 15 weight part, there exists a possibility that the fluidity | liquidity, flame retardance, etc. of a thermoplastic resin composition may fall.

(C) phosphorus flame retardant

The phosphorus flame retardant according to one embodiment of the present invention may be a phosphorus flame retardant used in a conventional flame retardant thermoplastic resin composition. For example, phosphorus-based flame retardants such as phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphazene compounds, and metal salts thereof Can be used. These may be used alone or in combination of two or more thereof.

In embodiments, the phosphorus flame retardant may include an aromatic phosphate ester compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ , R ₂ , R _4, and R ₅ each independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or a C 6 -C 20 aryl substituted with an alkyl group having 1 to 10 carbon atoms. R ₃ is a C 6 -C 20 arylene group substituted with a C 6 -C 20 arylene group or a C 1 -C 10 alkyl group, for example, dialcohol such as resorcinol, hydroquinone, bisphenol-A, bisphenol-S, etc. Derived from n is an integer from 0 to 10, for example from 0 to 4.

As the aromatic phosphate ester compound represented by the formula (1), when n is 0, diaryl phosphates such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trigylenyl phosphate, and tri (2,6-dimethyl) Phenyl) phosphate, tri (2,4,6-trimethylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dimethylphenyl) phosphate, etc., and n is 1 Bisphenol-A bis (diphenylphosphate), resorcinol bis (diphenylphosphate), resorcinol bis [bis (2,6-dimethylphenyl) phosphate], resorcinol bis [bis (2,4) -Dibutylbutylphenyl) phosphate], hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], hydroquinone bis [bis (2,4-diarybutylphenyl) phosphate] and the like, but may be exemplified. It is not limited. These may be applied alone or in the form of mixtures of two or more.

In embodiments, the phosphorous flame retardant (C) may be included in 10 to 30 parts by weight, for example 15 to 25 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the content of the phosphorus-based flame retardant (C) is less than 10 parts by weight based on 100 parts by weight of the polycarbonate resin (A), the (thin film) flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds 30 parts by weight. There exists a possibility that the impact resistance, thermal stability, etc. of a thermoplastic resin composition may fall.

In an embodiment, the content of the rubber-modified vinyl copolymer resin (B) may be less than the content of the phosphorous flame retardant (C).

(D) calcium carbonate

The calcium carbonate of the present invention, together with talc and wollastonite, can improve the fluidity, rigidity, (thin film) flame retardancy, dimensional stability, balance of physical properties, and the like of the thermoplastic resin composition.

In embodiments, the calcium carbonate may be amorphous or crystalline. The amorphous calcium carbonate has an advantage that the specific surface area is larger than the crystalline calcium carbonate and the particles are fine.

In embodiments, the calcium carbonate may be natural calcium carbonate or synthetic calcium carbonate. The said synthetic calcium carbonate can be manufactured by well-known methods, such as a carbonation reaction method and an aqueous solution method. Specifically, according to the aqueous solution method, amorphous calcium carbonate can be prepared by mixing and precipitating an aqueous solution in which calcium salt is dissolved and an aqueous solution in which salt having a carbonate group is dissolved.

In an embodiment, the calcium carbonate has an aragonite, batrite or calsite structure, and may have a fusiform or cubic particle form. The average particle size of the calcium carbonate particles is not particularly limited, but may be 0.03 to 30 μm. Here, average particle size was measured using a particle size distributor.

In embodiments, the calcium carbonate (D) may be included in 3 to 12 parts by weight, for example 5 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the content of the calcium carbonate (D) is less than 3 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A), the glossiness, stiffness, dimensional stability, etc. of the thermoplastic resin composition may decrease, and 12 parts by weight When it exceeds, there exists a possibility that the impact resistance, flame retardance, mechanical properties, etc. of a thermoplastic resin composition may fall.

(E) Talc

The talc of the present invention, together with calcium carbonate and wollastonite, can improve the fluidity, rigidity, (thin film) flame retardancy, dimensional stability, glossiness, appearance properties, balance of physical properties, and the like of the thermoplastic resin composition.

In an embodiment, the talc can be a conventional plate-shaped talc. The average particle size of the talc may be 2 to 10 μm, for example 3 to 7 μm. In the above range, the thermoplastic resin composition may have excellent rigidity, dimensional stability, glossiness (appearance), and the like.

In embodiments, the talc may have a bulk density of 0.3 to 1.0 g / cm ³ , for example 0.4 to 0.8 g / cm ³ . In the above range, the thermoplastic resin composition may have excellent rigidity, dimensional stability, glossiness (appearance), and the like.

In an embodiment, the talc (E) may be included in an amount of 5 to 40 parts by weight, for example, 10 to 30 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). When the content of the talc (E) is less than 5 parts by weight based on 100 parts by weight of the polycarbonate resin (A), there is a fear that the fluidity, dimensional stability, rigidity, etc. of the thermoplastic resin composition may be lowered and exceed 40 parts by weight. In this case, the impact resistance, mechanical properties, flame retardancy, etc. of the thermoplastic resin composition may be lowered.

In embodiments, the weight ratio ((D) :( E)) of the calcium carbonate (D) and talc (E) may be 1: 1.5 to 1: 6, for example, 1: 2 to 1: 5. When the weight ratio ((D) :( E)) of the calcium carbonate (D) and talc (E) is less than 1: 1.5, there is a concern that the dimensional stability, flame retardancy, glossiness (appearance), etc. of the thermoplastic resin composition may decrease. When 1: 6 is exceeded, glossiness (appearance), impact resistance, fluidity, flame retardancy, dimensional stability, etc. of the thermoplastic resin composition may be lowered.

(F) black pigment

The thermoplastic resin composition of the present invention may include a black pigment having an average particle size of 10 to 24 nm, for example, 15 to 22 nm, so that the combination of the calcium carbonate and talc black pigment may have a high quality gloss and appearance. . For example, carbon black or the like can be used as the black pigment. If the average particle size of the black pigment is less than 10 nm, there is a fear that the dispersibility, mechanical properties and the like of the thermoplastic resin composition is lowered, if it exceeds 24 nm, the gloss, color, etc. of the thermoplastic resin composition may be lowered There is. Here, the average particle size (Z-average) was measured according to a known method, and the average particle size (Z-average) was measured using a Mastersizer 2000E series (Malvern) equipment by dry method.

In an embodiment, the black pigment (F) may be included in an amount of 0.001 to 5 parts by weight, for example 0.1 to 2 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). When the content of the black pigment is less than 0.001 parts by weight based on 100 parts by weight of the polycarbonate resin, the gloss, color, etc. of the thermoplastic resin composition may be lowered. When the content of the black pigment exceeds 5 parts by weight, the inside of the thermoplastic resin composition may be There is a risk that impact properties, mechanical properties, and the like may decrease.

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive such as a release agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer, a flame retardant aid, an antidropping agent, an antioxidant, a mixture thereof, and the like.

In an embodiment, as the additive, an additive used in a conventional thermoplastic resin composition may be used without limitation. For example, the additives include mold release agents such as polyethylene wax, fluorine-containing polymer, silicone oil, metal salt of stearyl acid, metal salt of montanic acid and montanic acid ester wax; Nucleating agents such as clay; Antioxidants such as hindered phenol compounds; Mixtures thereof and the like may be used, but are not limited thereto. The additive may be included in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the polycarbonate resin, but is not limited thereto.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of pellets which are mixed with the above components and melt-extruded at 200 to 280 ° C, for example, 250 to 260 ° C, using a conventional twin screw extruder.

In an embodiment, the thermoplastic resin composition has a melt-flow index (MI) of 30-50 g / 10 min, for example 35-45, measured at 220 ° C. and 5 kgf in accordance with ASTM D1238. g / 10 minutes.

In an embodiment, the thermoplastic resin composition may have a notched Izod impact strength of 5 kgf · cm / cm or more, for example, 5 to 8 kgf · cm / cm, measured in a 1/8 ”thickness specimen in accordance with ASTM D256. .

In embodiments, the thermoplastic resin composition may have a glass transition temperature of 82 to 90 ℃, for example 84 to 87 ℃.

In an embodiment, the thermoplastic resin composition may have a flame retardancy of 1.0 mm thick specimen measured in accordance with UL94 standards or more.

In one embodiment, the thermoplastic resin composition may have a linear expansion coefficient of 20 to 45 cm / cm ° C., for example, 25 to 42 cm / cm ° C., measured for a bent specimen at 90 ° C. according to ASTM D696.

In an embodiment, the thermoplastic resin composition is a luminescent mold having a size of 400 mm × 100 mm × 10 mm thick, and the injection specimens are pressure-reduced (30 bar, 50 bar and 70 bar) at a molding temperature of 260 ° C. ), And the horizontal length of the injection test specimen measured after leaving for 24 hours at 23 ° C. using a test specimen injected without burrs in the condition is 390 to 400 mm, for example, 396 to 399 mm. Can be.

In embodiments, the thermoplastic resin composition has a glossiness (Gloss (60 °)) of 95-100%, for example 96-99%, of the injection specimen (black pigment addition) measured at an angle of 60 ° according to ASTM D523. Can be.

In embodiments, the thermoplastic resin composition may have a brightness (L *) value of 90 to 100, for example 95 to 99, of a 3.2 mm thick specimen (added with black pigment) measured according to ASTM D2244, and a * ( Saturation) and b * (saturation) values may each independently be -0.1 to 0.3, for example 0 to 0.2.

The molded article according to the present invention is formed from the thermoplastic resin composition.

In an embodiment, the molded article may be a plastic member of an electronics housing including a metal frame and a plastic member in contact with at least one surface of the metal frame.

1 is a schematic cross-sectional view of an electronics housing according to an embodiment of the present invention. In the drawings, the sizes of components constituting the invention are exaggerated for clarity and are not limited thereto. As shown in FIG. 1, an electronics housing according to an embodiment of the present invention includes a metal frame 10; And at least one plastic member 20 in contact with at least one surface of the metal frame 10, wherein the plastic member is formed from the thermoplastic resin composition.

In an embodiment, the shape of the metal frame 10 and the plastic member 20 is not limited to the drawings and may have various shapes. However, the metal frame 10 and the plastic member 20 have a structure in which at least one surface is in contact with each other. The contact structure may be implemented by adhesion or insertion, and the method of contacting is not limited.

In an embodiment, the metal frame 10 may be a product applied to a conventional electronic housing, such as a stainless steel frame, the plastic member, and is easy to purchase commercially.

In an embodiment, the plastic member 20 may be formed from the polycarbonate resin composition through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Specifically, the plastic member 20 may be molded in a hot water mold method or a steam mold method (rapid heat cycle molding (RHCM) method, etc.), and may be a front cover of a 22 to 75 inch thin film television, a thin film monitor, or the like. cover, rear cover, and the like. Since the plastic member 20 is excellent in glossiness, the plastic member 20 is suitable for high glossiness specification (level of glossiness of 98%), and can be applied to appearance specifications such as hair line patterns and corrosion patterns.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, the specification of each component used in the Example and the comparative example is as follows.

(A) polycarbonate resin

Bisphenol-A type polycarbonate resin (flow index (MI, measured at 300 degreeC and 1.2 kg conditions based on ISO 1133): 60 +/- 10g / 10min) was used.

(B) Rubber-modified vinyl copolymer resin

A rubber-modified aromatic vinyl graft copolymer (g-MBS) in which 25% by weight of styrene and 15% by weight of methyl methacrylate were graft-coated in a polybutadiene rubber (PBR) having a Z-average of 310 nm by weight of 60 mW. Used.

(C) phosphorus flame retardant

Oligomeric bisphenol-A diphosphate (bisphenol-A diphosphate, manufactured by Yoke Chemical, product name: YOKE BDP) was used.

(D) calcium carbonate

Calcium carbonate (manufacturer: OMYA company, product name: 2B) was used.

(E) Talc

Talc (manufactured by KOCH, product name: KCM 6300, bulk density: 0.4 to 0.6 g / cm ³ ) was used.

(F) black pigment

(F1) Carbon black (manufacturer: Orion, product name: High Black 50L, average particle size: 19 nm) was used.

(F2) Carbon black (manufacturer: Orion, product name: High Black 80L, average particle size: 27 nm) was used.

Examples 1 to 3 and Comparative Examples 1 to 4

Each of the components was added in an amount as described in Table 1 below, followed by extrusion at 250 ° C. to prepare pellets. Extrusion was performed using a twin screw extruder having a diameter of L / D = 36 and 45 mm, and the pellets were dried at 80 ° C. for at least 4 hours, and then injected in a 6 Oz injection machine (molding temperature 250 to 260 ° C., mold temperature: 60 ° C.). To prepare a specimen. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Table 1 below.

Property measurement method

(1) Melt-flow index (MI, unit: g / 10 min): measured under the conditions of 220 ° C. and 5 kgf according to ASTM D1238.

(2) Notched Izod impact strength (unit: kgf · cm / cm): Notched Izod impact strength of the 1/8 ”thickness specimen was measured according to ASTM D256.

(3) Glass transition temperature (unit: ℃): After vacuum drying 5-10 mg of a sample at 80 degreeC for 4 hours using TA Q20 measuring instrument (Differential Scanning Calorimeter (DSC)) (moisture 3,000 ppm or less), In a nitrogen atmosphere, the temperature was raised from 30 ° C. to 400 ° C. at a rate of 20 ° C./min, followed by 1 minute of stay at 400 ° C., followed by cooling to 30 ° C. at a rate of 20 ° C./min. The glass transition temperature was measured from the transition temperature which was raised to 400 ° C./min (2nd scan).

(4) Flame retardancy: 1.0 mm thickness was measured using the specimen according to the UL 94 flammability testing standard.

(5) Linear expansion coefficient (unit: cm / cm ℃): The coefficient of linear expansion of the 6.4 mm bending specimen was measured at 90 ℃ in accordance with ASTM D696.

(6) Luminous flat mold dimension evaluation (unit: mm): Using a luminous mold having a size of 400 mm × 100 mm × 10 mm in thickness, the injection specimens were subjected to pressure retention (30 bar) at a molding temperature of 260 ° C. , 50 bar and 70 bar), and after using the specimen injected under the condition of no burr (dual), and left for 24 hours at 23 ℃, the horizontal length of the injection specimen was measured.

(7) Glossiness (Gloss (60 °), unit:%): The injection molding specimens of 90 mm × 50 mm × 2 mm size were measured by Konica Minolta MG-268 gloss meter according to ASTM D523.

(8) Color (brightness (L *), saturation (a * and b *)): According to ASTM D2244, Konica Minolta for 3.2 mm thick injection molded specimens with specular component excluded (SCE) Brightness (L *) and saturation (a * and b *) values were measured with a CM-3600d colorimeter.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) (parts by weight) 100 100 100 100 100 100 100 (B) (parts by weight) 6 6 6 6 6 6 6 (C) (parts by weight) 21 21 21 21 21 21 21 (D) (parts by weight) 5 10 5 3 12 3 10 (E) (parts by weight) 10 20 25 3.9 5 30 20 (F1) (parts by weight) One One One One One One - (F2) (parts by weight) - - - - - - One (D): (E) (weight ratio) 1: 2 1: 2 1: 5 1: 1.3 1: 0.42 1:10 1: 2 Melt flow index 45 40 35 47 30 30 40 Notch Izod Impact Strength 8 6 5 6 6 4 6 Glass transition temperature 85 85 85 85 83 85 85 Flame Retardant (1.0T) V1 V1 V1 V1 V2 V2 V1 Coefficient of linear expansion 41 35 30 50 55 50 35 Luminous Mold Dimensional Evaluation 396 398 399 388 385 395 398 Glossiness 98 98 98 98 95 85 90 L * 98 98 98 98 98 95 95 a * 0.1 0.1 0.1 0.1 0.1 0.1 0.2 b * 0.1 0.1 0.1 0.1 0.5 0.6 1.0

From the results in Table 1, it can be seen that the thermoplastic resin composition of the present invention is excellent in fluidity (molding processability), impact resistance, heat resistance, thin film flame retardancy, gloss, appearance characteristics such as color, dimensional stability, balance of physical properties, and the like. have.

On the other hand, in Comparative Example 1 in which the weight ratio of calcium carbonate and talc is 1: 1.3 (less than 1: 1.5) and a small amount of talc (3.9 parts by weight), the dimensional stability (coefficient of linear expansion and luminescence mold dimensions) It can be seen that, in Comparative Example 2 in which the weight ratio of calcium carbonate and talc is 1: 0.42 (less than 1: 1.5), the dimensional stability is greatly reduced, and the fluidity, impact resistance, flame retardancy, appearance characteristics, and the like are deteriorated. In the case of Comparative Example 3 in which the weight ratio of calcium carbonate and talc is 1:10 (greater than 1: 6), it can be seen that physical properties such as glossiness, flowability, impact resistance, dimensional stability, and flame retardancy were generally reduced. In addition, in the case of Comparative Example 4 using a black pigment ((F2) carbon black) having an average particle size of 27 nm (greater than 24 nm), it can be seen that appearance characteristics such as glossiness, color, and the like were deteriorated.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (10)

100 parts by weight of polycarbonate resin;
Rubber modified vinyl copolymer resin 1 to 15 parts by weight;
10 to 30 parts by weight of a phosphorus flame retardant;
3 to 12 parts by weight of calcium carbonate;
Talc 5 to 40 parts by weight; And
0.001 to 5 parts by weight of black pigment,
The weight ratio of the calcium carbonate and talc is 1: 1.5 to 1: 6, the average particle size of the black pigment is 10 to 24 nm,
The glossiness (Gloss (60 °)) of the injection test specimen measured at an angle of 60 ° according to ASTM D523 is 95 to 100%,
A thermoplastic resin composition, characterized in that the linear expansion coefficient of 20 to 45 cm / cm ℃ measured for 6.4 mm bend specimen at 90 ℃ based on ASTM D696.
The rubber-modified vinyl copolymer resin of claim 1, wherein the rubber-modified vinyl copolymer resin comprises a rubber-modified aromatic vinyl graft copolymer in which an aromatic vinyl monomer and an alkyl (meth) acrylate monomer are graft copolymerized in a rubbery polymer. Thermoplastic resin composition.
The thermoplastic resin composition of claim 1, wherein the phosphorus-based flame retardant comprises at least one of a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, and a phosphazene compound.
The thermoplastic resin composition of claim 1, wherein a content of the rubber-modified vinyl copolymer resin is less than that of the phosphorus-based flame retardant.
According to claim 1, wherein the thermoplastic resin composition has a melt flow index (MI) of 30 to 50 g / 10 minutes measured at 220 ℃ and 5 kgf conditions in accordance with ASTM D1238, ASTM D256 And a notched Izod impact strength measured by a 1/8 "thickness specimen of at least 5 kgfcm / cm.
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a glass transition temperature of 82 to 90 ° C., and has a flame retardancy of 1.0 mm thick specimen measured according to the UL94 standard.
The method of claim 1, wherein the thermoplastic resin composition using a luminescent mold having a size of 400 mm × 100 mm × 10 mm thick, at a molding temperature of 260 ℃ conditions, the injection specimens by pressure (30 bar, 50 bar and 70 bar), the thermoplastic resin characterized in that the horizontal length of the injection specimen measured after leaving for 24 hours at 23 ℃ using a specimen injected in a condition that there is no burr (dual) is 390 to 400 mm Composition.
The method of claim 1, wherein the thermoplastic resin composition has a brightness (L *) value of 90 to 100, a * value of -0.1 to 0.3, b * value of-3.2 mm thick specimen measured according to ASTM D2244. The thermoplastic resin composition, characterized in that 0.1 to 0.3.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 8.
The molded article of claim 9, wherein the molded article is a plastic member of an electronics housing including a metal frame and a plastic member contacting at least one surface of the metal frame.

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