KR102013018B1 - Thermoplastic resin composition for plating - Google Patents

Abstract

Plating thermoplastic resin composition of the present invention is 40 to 60% by weight of a polycarbonate resin; 10 to 30% by weight of the first rubber-modified vinyl graft copolymer having an average particle diameter of the rubbery polymer of 220 to 340 nm; 5 to 25% by weight of the second rubber-modified vinyl graft copolymer having an average particle diameter of the rubbery polymer of 100 to 160 nm; And 10 to 40 wt% of an aromatic vinyl-vinyl cyanide copolymer resin. The plating thermoplastic resin composition and the plated molded article including the same have excellent plating adhesion, impact resistance, heat resistance, balance of physical properties, and the like.

Description

Thermoplastic composition for plating {THERMOPLASTIC RESIN COMPOSITION FOR PLATING}

The present invention relates to a thermoplastic resin composition for plating. More specifically, the present invention relates to a thermoplastic resin composition for plating having excellent plating adhesion, impact resistance, heat resistance, balance of physical properties, and the like, and a plated molded article including the same.

In automobiles, electronics and office automation equipment, the demand for plated plastic products is increasing for the purpose of obtaining cost-saving effects through weight reduction of materials and beautiful appearance while maintaining the texture of metal. There is an increasing demand for new plating thermoplastic resin compositions (plastic materials).

Among the thermoplastic resin compositions, thermoplastic resin compositions (PC / ABS blends, etc.) containing polycarbonate (PC) resins and rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene (ABS) include polycarbonate resins. Processability, chemical resistance, and the like can be improved without reducing the impact resistance, heat resistance, and the like, and thus cost reduction is possible, and thus it is used for various purposes.

However, the PC / ABS blend, etc., the plating adhesion is significantly lower than the conventional thermoplastic resin composition for plating, such as ABS resin, when there is a sudden temperature change, the plating layer and the resin layer may fall, there is a possibility that reliability problems such as swelling occurs. .

Therefore, the development of the thermoplastic resin composition for plating which can improve impact resistance, heat resistance, etc. without the fall of plating adhesiveness is calculated | required.

Background art of the present invention is disclosed in Republic of Korea Patent No. 10-0292878.

An object of the present invention is to provide a thermoplastic resin composition for plating having excellent plating adhesion, impact resistance, heat resistance, balance of physical properties thereof, and the like.

Another object of the present invention is to provide a plated molded article comprising the above-mentioned thermoplastic resin composition for plating.

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 for plating. The plating thermoplastic resin composition is 40 to 60% by weight of a polycarbonate resin; 10 to 30% by weight of the first rubber-modified vinyl graft copolymer having an average particle diameter of the rubbery polymer of 220 to 340 nm; 5 to 25% by weight of the second rubber-modified vinyl graft copolymer having an average particle diameter of the rubbery polymer of 100 to 160 nm; And 10 to 40 wt% of an aromatic vinyl-vinyl cyanide copolymer resin.

In embodiments, the polycarbonate resin may have a weight average molecular weight of 15,000 to 35,000 g / mol.

In embodiments, the first rubber-modified aromatic vinyl graft copolymer is a monomer mixture 35 to 65 containing an aromatic vinyl monomer and a vinyl cyanide monomer in 35 to 65% by weight of the rubbery polymer having an average particle diameter of 220 to 340 nm The weight percent may be graft copolymerized.

In an embodiment, the monomer mixture may include 60 to 90 wt% of the aromatic vinyl monomer and 10 to 40 wt% of the vinyl cyanide monomer.

In embodiments, the second rubber-modified aromatic vinyl graft copolymer is a monomer mixture 40 to 65 containing an aromatic vinyl monomer and a vinyl cyanide monomer in 35 to 60% by weight of the rubbery polymer having an average particle diameter of 100 to 160 nm The weight percent may be graft copolymerized.

In an embodiment, the monomer mixture may include 60 to 90 wt% of the aromatic vinyl monomer and 10 to 40 wt% of the vinyl cyanide monomer.

In an embodiment, the weight ratio of the first rubber modified aromatic vinyl copolymer and the second rubber modified aromatic vinyl copolymer may be 1: 0.2 to 1: 1.

In embodiments, the aromatic vinyl-vinyl cyanide copolymer resin may have a weight average molecular weight of 50,000 to 300,000 g / mol.

In a specific embodiment, the plating thermoplastic resin composition is a plating layer measured at a peel rate of 50 mm / min using a tensile tester after chrome plating the injection molded specimen of 10 cm × 10 cm × 0.3 cm to 30 ㎛ thickness Adhesion strength of the may be from 580 to 700 gf / cm.

In one embodiment, the thermoplastic resin composition for plating may have a notched Izod impact strength of 48 to 65 kgf · cm / cm measured by a 1/8 ″ thickness specimen in accordance with ASTM D256.

In an embodiment, the plating thermoplastic resin composition may have a heat deflection temperature (HDT) of 90 to 110 ° C. measured under a condition of a load of 1.8 MPa and a heating rate of 120 ° C./hr based on ASTM D648.

Another aspect of the invention relates to a plated molded article. The plating molded article is a base layer; And a plating layer formed on at least one surface of the substrate layer, wherein the substrate layer is formed from the thermoplastic resin composition for plating.

The present invention has the effect of the invention to provide a plating thermoplastic resin composition excellent in plating adhesion, impact resistance, heat resistance, balance of physical properties and the like and a plated molded article comprising the same.

1 schematically illustrates a cross section of a plated molded article according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition for plating according to the present invention comprises (A) a polycarbonate resin, (B1) a first rubber-modified aromatic vinyl graft copolymer, and (B2) a second rubber-modified aromatic vinyl graft copolymer ( B) rubber-modified aromatic vinyl graft copolymers and (C) aromatic vinyl-vinyl cyanide copolymer resins.

(A) polycarbonate resin

As the polycarbonate resin according to an embodiment of the present invention, an aromatic polycarbonate resin or the like used in a conventional thermoplastic resin composition may be used without limitation. For example, an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with carbonate 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, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, and the like, but are not limited thereto. . For example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl- 4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane can be used, specifically, 2,2-bis (4-hydroxyphenyl) propane called bisphenol-A can be used. Can be used.

In an embodiment, the polycarbonate resin may be branched chain, for example, 0.05 to 2 moles of trivalent or more polyfunctional compound, specifically, based on 100 moles of total diphenols used for polymerization. It may also be prepared by adding a compound having a trivalent or higher phenol group.

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 embodiments, the polycarbonate resin may have a weight average molecular weight (Mw) of 15,000 to 35,000 g / mol, for example, 20,000 to 32,000 g / mol, measured by gel permeation chromatography (GPC). . In the above range, the flowability, impact resistance, heat resistance, and the like of the thermoplastic resin composition for plating may be excellent.

In embodiments, the polycarbonate resin may be included in 40 to 60% by weight, for example 45 to 55% by weight of the total 100% by weight of the thermoplastic resin composition for plating. When the content of the polycarbonate resin is less than 40% by weight, the impact resistance, heat resistance and the like of the thermoplastic resin composition for plating may be lowered. When the content of the polycarbonate resin exceeds 60% by weight, plating etching of a molded article formed from the thermoplastic resin composition for plating is performed. There is a risk of deterioration.

(B) Rubber Modified Aromatic Vinyl Graft Copolymer

The rubber-modified aromatic vinyl graft copolymer according to the present invention is an average of the first rubber-modified aromatic vinyl graft copolymer and (B2) rubber polymer having an average particle diameter (D50) of (B1) rubbery polymer of 220 to 340 nm. A second rubber-modified aromatic vinyl graft copolymer having a particle diameter (D50) of 100 to 160 nm is provided and has a bimodal particle size distribution.

(B1) first rubber-modified aromatic vinyl graft copolymer

The first rubber-modified aromatic vinyl graft copolymer according to an embodiment of the present invention is an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer having an average particle diameter (D50) of 220 to 340 nm, for example, 230 to 290 nm. The monomer mixture comprising monomers may be graft copolymerized. For example, the monomer mixture may be added to the rubbery polymer and obtained by graft copolymerization. The polymerization may be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, and bulk polymerization. When the average particle diameter of the rubbery polymer is less than 220 nm, the rubber-modified aromatic vinyl graft copolymer may not have a bimodal particle size distribution and may have a low impact resistance. When the rubber-modified aromatic vinyl graft copolymer exceeds 340 nm, the thermoplastic resin composition for plating There exists a possibility that plating adhesiveness etc. of the molded article formed from this may fall.

In an embodiment, the rubbery polymer is hydrogenated to diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene) having the average particle diameter (D50) range, and hydrogenated to the diene rubber. And acrylic rubbers such as saturated rubber, isoprene rubber and polybutyl acrylate, and ethylene-propylene-diene monomer terpolymer (EPDM). These can be applied individually or in mixture of 2 or more types. For example, diene rubber may be used, and specifically, polybutadiene rubber may be used. The content of the rubbery polymer may be 35 to 65% by weight, for example 40 to 60% by weight of the total 100% by weight of the rubber-modified aromatic vinyl graft copolymer, the content of the monomer mixture is 35 to 65% by weight, For example, it may be 40 to 60% by weight. Formability, physical properties, and the like of the thermoplastic resin composition for plating in the above range may be stable.

In an embodiment, the aromatic vinyl monomer may be graft copolymerized to the rubbery polymer, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene , Vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, combinations thereof, and the like may be used, but is not limited thereto. For example, styrene or the like can be used. The content of the aromatic vinyl monomer may be 60 to 90% by weight, for example 60 to 80% by weight, based on 100% by weight of the total monomer mixture. Within the above range, compatibility between components in the thermoplastic resin composition for plating may be excellent.

In embodiments, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, Combinations of the above may be used, but the present invention is not limited thereto. For example, acrylonitrile or the like can be used. The content of the vinyl cyanide monomer may be 10 to 40% by weight, for example 20 to 40% by weight, based on 100% by weight of the total monomer mixture. Within the above range, the compatibility between the components of the thermoplastic resin composition for plating and the plating etching property of the molded article formed from the thermoplastic resin composition for plating may be excellent.

In embodiments, the monomer mixture may further include a monomer for imparting processability and heat resistance in addition to the aromatic vinyl monomer and the vinyl cyanide monomer. For example, acrylic acid, methacrylic 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 monomer for imparting processability and heat resistance may be included in an amount of 30 parts by weight or less, for example, 1 to 25 parts by weight, based on 100 parts by weight of the aromatic vinyl monomer and the vinyl cyanide monomer. In the above range, the workability, heat resistance, and the like of the thermoplastic resin composition for plating may be further improved without deteriorating other physical properties.

In one embodiment, the first rubber-modified aromatic vinyl graft copolymer may be included in 10 to 30% by weight, for example 15 to 25% by weight of the total 100% by weight of the thermoplastic resin composition for plating. When the content of the first rubber-modified aromatic vinyl graft copolymer is less than 10% by weight, impact resistance of the thermoplastic resin composition for plating, plating adhesion of a molded article formed from the thermoplastic resin composition for plating, etc. may be deteriorated. When it exceeds weight%, there exists a possibility that heat resistance, fluidity | liquidity, etc. of the thermoplastic resin composition for plating may fall.

(B2) second rubber-modified aromatic vinyl graft copolymer

The second rubber-modified aromatic vinyl graft copolymer according to one embodiment of the present invention has an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer having an average particle diameter (D50) of 100 to 160 nm, for example, 110 to 150 nm. The monomer mixture comprising monomers may be graft copolymerized. For example, the monomer mixture may be added to the rubbery polymer and obtained by graft copolymerization. The polymerization may be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, and bulk polymerization. When the average particle diameter of the rubbery polymer is less than 100 nm, impact resistance of the thermoplastic resin composition for plating, plating etching property of a molded article formed from the thermoplastic resin composition for plating, and the like may be lowered. There is a fear that vinyl-based graft copolymers do not have bimodal particle size distribution.

In an embodiment, the rubbery polymer is hydrogenated to diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene) having the average particle diameter (D50) range, and hydrogenated to the diene rubber. And acrylic rubbers such as saturated rubber, isoprene rubber and polybutyl acrylate, and ethylene-propylene-diene monomer terpolymer (EPDM). These can be applied individually or in mixture of 2 or more types. For example, diene rubber may be used, and specifically, polybutadiene rubber may be used. The content of the rubbery polymer may be 35 to 60% by weight, for example 40 to 60% by weight of the total 100% by weight of the rubber-modified aromatic vinyl graft copolymer, the content of the monomer mixture is 40 to 65% by weight, For example, it may be 40 to 60% by weight. Plating adhesion of the molded article formed from the thermoplastic resin composition for plating in the above range may be excellent.

In an embodiment, the aromatic vinyl monomer may be graft copolymerized to the rubbery polymer, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene , Vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, combinations thereof, and the like may be used, but is not limited thereto. For example, styrene or the like can be used. The content of the aromatic vinyl monomer may be 60 to 90% by weight, for example 60 to 80% by weight, based on 100% by weight of the total monomer mixture. In the above range may be excellent compatibility between the components of the thermoplastic resin composition for plating.

In embodiments, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, Combinations of the above may be used, but the present invention is not limited thereto. For example, acrylonitrile or the like can be used. The content of the vinyl cyanide monomer may be 10 to 40% by weight, for example 20 to 40% by weight, based on 100% by weight of the total monomer mixture. Within the above range, the compatibility between the components of the thermoplastic resin composition for plating and the plating etching property of the molded article formed from the thermoplastic resin composition for plating may be excellent.

In embodiments, the monomer mixture may further include a monomer for imparting processability and heat resistance in addition to the aromatic vinyl monomer and the vinyl cyanide monomer. For example, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, etc. may be illustrated, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. The monomer for imparting processability and heat resistance may be included in 30 parts by weight or less, for example, 1 to 25 parts by weight of 100 parts by weight of the monomer mixture. In the above range, the workability, heat resistance, and the like of the thermoplastic resin composition for plating may be further improved without deteriorating other physical properties.

In embodiments, the second rubber-modified aromatic vinyl graft copolymer may be included in 5 to 25% by weight, for example 5 to 20% by weight of the total 100% by weight of the thermoplastic resin composition for plating. When the content of the second rubber-modified aromatic vinyl graft copolymer is less than 5% by weight, the effect of increasing the plating adhesion of the plating thermoplastic resin composition may be insignificant, and when the content of the second rubber modified aromatic vinyl graft copolymer is greater than 25% by weight, There exists a possibility that impact resistance etc. may fall.

In embodiments, the weight ratio ((B1) :( B2)) of the first rubber-modified aromatic vinyl copolymer (B1) and the second rubber-modified aromatic vinyl copolymer (B2) is 1: 0.2 to 1: 1, For example, it may be 1: 0.3 to 1: 0.9. In the above range, the mechanical properties of the thermoplastic resin composition for plating and the plating adhesion of the molded article formed from the thermoplastic resin composition for plating may be further excellent.

(C) Aromatic vinyl-vinyl cyanide copolymer resin

Aromatic vinyl-vinyl cyanide copolymer resin according to an embodiment of the present invention is to improve the workability of the thermoplastic resin composition for plating, the plating etching of a molded article formed from the thermoplastic resin composition for plating, and the like, and an aromatic vinyl monomer. And a monomer mixture comprising a vinyl cyanide monomer. For example, the aromatic vinyl cyanide copolymer is a copolymer including a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a vinyl cyanide monomer, and the monomer mixture is prepared according to a known polymerization method. It can be obtained by reacting. In addition, if necessary, an aromatic vinyl-vinyl cyanide copolymer may further be included in the monomer mixture to further include a monomer providing processability and heat resistance, further comprising a repeating unit derived from a monomer providing processability and heat resistance. .

In an embodiment, the aromatic vinyl monomer may be polymerized with a vinyl cyanide monomer to form a repeating unit derived from an aromatic vinyl monomer. Styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butyl styrene, ethyl styrene, vinyl xylene, monochloro styrene, dichloro styrene, dibromostyrene, vinyl naphthalene, etc. may be illustrated, but is not limited thereto. These may be used alone or in combination of two or more thereof. The content of the aromatic vinyl monomer (repeat unit derived from an aromatic vinyl monomer) is 60 to 90% by weight, for example 65 to 80% by weight, in 100% by weight of the monomer mixture (aromatic vinyl-vinyl cyanide copolymer). Can be. In the above range, the processability, fluidity, and the like of the thermoplastic resin composition for plating may be excellent.

In an embodiment, the vinyl cyanide monomer may be polymerized with an aromatic vinyl monomer to form a repeating unit derived from a vinyl cyanide monomer, and may include acrylonitrile, methacrylonitrile, ethacrylonitrile, and phenylacrylonitrile. Nitrile, α-chloroacrylonitrile, fumaronitrile and the like can be exemplified, but is not limited thereto. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer (repeating unit derived from the vinyl cyanide monomer) is 10 to 40% by weight, for example 15 to 35% by weight, of 100% by weight of the monomer mixture (aromatic vinyl-vinyl cyanide copolymer). Can be. In the above range, the compatibility of the thermoplastic resin composition for plating and the plating adhesion of the molded article formed from the thermoplastic resin composition for plating may be excellent.

In an embodiment, examples of the monomer for imparting processability and heat resistance may include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, and the like. When using the monomer to impart the processability and heat resistance, the content may be 30 parts by weight or less, for example 1 to 25 parts by weight of 100 parts by weight of the monomer mixture. In the above range, processability and heat resistance can be imparted to the thermoplastic resin composition for plating without deterioration of other physical properties.

In an embodiment, the aromatic vinyl-vinyl cyanide copolymer resin is selected from among copolymers of styrene and acrylonitrile, copolymers of styrene, α-methylstyrene and acrylonitrile and copolymers of α-methylstyrene and acrylonitrile. It may include one or more.

In embodiments, the aromatic vinyl-vinyl cyanide copolymer may have a weight average molecular weight of 50,000 to 300,000 g / mol, for example, 90,000 to 200,000 g / mol, measured by gel permeation chromatography (GPC). have. In the above range may be excellent in workability of the thermoplastic resin composition for plating.

In embodiments, the aromatic vinyl cyanide-based copolymer may be included in 10 to 40% by weight, for example 15 to 35% by weight of the total 100% by weight of the thermoplastic resin composition for plating. When the content of the aromatic vinyl-vinyl cyanide copolymer is less than 10% by weight, there is a fear that the plating etching property of the molded article formed from the thermoplastic resin composition for plating may decrease, and when the content of the aromatic vinyl-vinyl cyanide copolymer exceeds 40% by weight, the thermoplastic resin for plating There exists a possibility that plating adhesiveness etc. of the molded article formed from the composition may fall.

Thermoplastic resin composition according to an embodiment of the present invention, if necessary, inorganic fillers, flame retardants, flame retardant aids, compatibilizers, mold release agents, lubricants, plasticizers, heat stabilizers, light stabilizers, anti-dropping agents, antioxidants, pigments, dyes, these It may further include an additive such as a mixture of. 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, rubber-modified aromatic vinyl 꼐 copolymer and aromatic vinyl-vinyl cyanide copolymer resin, but is not limited thereto.

The thermoplastic resin composition for plating according to an embodiment of the present invention may be in the form of pellets obtained by mixing the components and melt extrusion at 200 to 280 ° C, for example, 250 to 260 ° C, using a conventional twin screw extruder. .

In an embodiment, the plating thermoplastic resin composition is chromium plated 10 cm × 10 cm × 0.3 cm injection molded specimens having a thickness of about 30 μm, and then measured at a peel rate of 50 mm / min using a tensile tester. The adhesion strength of the plating layer may be 580 to 700 gf / cm, for example, 600 to 680 gf / cm.

In one embodiment, the thermoplastic resin composition for plating has a notched Izod impact strength of 48 to 65 kgf · cm / cm, for example 48 to 60 kgf · cm / cm, measured on a 1/8 ”test piece according to ASTM D256. Can be.

In one embodiment, the thermoplastic resin composition for plating has a heat deflection temperature (HDT) of 90 to 110 ° C, for example 95 to 105 ° C, measured under conditions of a load of 1.8 MPa and a heating rate of 120 ° C / hr based on ASTM D648. Can be.

1 schematically illustrates a cross section of a plated molded article 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. In addition, the shape of each component is not limited to the drawings and may have various shapes. As shown in Figure 1, the plated molded article according to an embodiment of the present invention is a base layer (10); And a plating layer 20 formed on at least one surface of the substrate layer 10, wherein the substrate layer 10 is formed from the thermoplastic resin composition for plating.

In an embodiment, the base layer 10 may be formed in various forms through various molding methods such as injection molding, extrusion molding, vacuum molding, casting molding, etc., from the thermoplastic resin composition for plating. Such molding methods are well known by those skilled in the art.

In an embodiment, the plating layer 20 may be formed according to a conventional plating plastic product manufacturing method such as ABS resin plating. For example, the substrate layer 10 may be etched and then etched on the etched portion. After forming the anchor (anchor), it may be formed by plating, for example, electroless plating and electroplating, but is not limited thereto.

In embodiments, the plating may be a conventional wet plating or dry plating method such as chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma CVD, thermal spray coating, etc., in addition to electroless plating and electroplating.

In an embodiment, the plating layer 20 may include one or more of chromium, nickel, and copper, and the thickness of the plating layer 20 may be 0.1 to 100 μm, but is not limited thereto.

The plated molded article of the present invention has excellent plating adhesion between the base layer and the plated layer, excellent impact resistance, heat resistance, and the like, and can be used as an interior and exterior material of a metallic appearance such as automobiles, electric electronics, and office automation equipment, and in particular, a radiator grille It is useful as car exterior materials.

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 (weight average molecular weight (Mw): 25,000 g / mol) was used.

(B) Rubber Modified Aromatic Vinyl Graft Copolymer

(B1) A first rubber-modified aromatic vinyl graft copolymer comprising 40% by weight of styrene and acrylonitrile in 60% by weight of polybutadiene rubber (PBR) having an average particle diameter (D50) of 280 nm. G-ABS graft copolymerized) was used.

(B2) A second rubber-modified aromatic vinyl graft copolymer comprising 50% by weight of styrene and acrylonitrile in 50% by weight of polybutadiene rubber (PBR) having an average particle diameter (D50) of 150 nm. G-ABS graft copolymerized) was used.

(C) Aromatic vinyl-vinyl cyanide copolymer resin

A SAN resin (weight average molecular weight (Mw): 130,000 g / mol) which was a copolymer of styrene and acrylonitrile (weight ratio: 70/30) 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 prepared pellets were dried at 80 to 100 ° C. for at least 4 hours, and then in a 6 oz injection molding machine (molding temperature 250 ° C., mold temperature: 60 ° C.). The specimen was prepared by injection molding. 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) Plating layer adhesion strength (unit: gf / cm): Chrome plated 10 cm × 10 cm × 0.3 cm injection molded specimens with a thickness of about 30 μm, and then using a tensile tester to cut the center portion of the chromium plating layer. After being bitten by the jig of the tensile tester, the sheet was stretched at a peel rate of 50 mm / min in the 90 ° direction of the surface of the plated layer, and the adhesion strength between the base layer and the plated layer was measured.

(2) Notched Izod Impact Strength (Unit: kgf · cm / cm): Notches were made by evaluating notches on 1/8 ”IZOD specimens according to the evaluation method specified in ASTM D256.

(3) Heat deflection temperature (HDT, unit: ℃): measured under the conditions of load 1.8MPa, heating rate 120 ℃ / hr according to ASTM D648.

Example Comparative example One 2 3 One 2 3 4 (A) (% by weight) 50 50 50 50 50 50 50 (B1) (wt%) 16 19 14 26 - 6 24 (B2) (wt%) 10 7 12 - 26 20 2 (C) (% by weight) 24 24 24 24 24 24 24 Plating layer adhesion strength (gf / cm) 640 670 620 550 450 480 560 Notched Izod Impact Strength (kgfcm / cm) 50 51 50 53 45 47 52 Heat deflection temperature (℃) 100 100 100 100 100 100 100

From the above results, it can be seen that the thermoplastic resin composition for plating of the present invention is excellent in all of the plating adhesion, impact resistance and heat resistance.

On the other hand, when the second rubber-modified aromatic vinyl graft copolymer is not included or the content is low (Comparative Examples 1 and 4), it can be seen that the plating adhesion is reduced, the first rubber-modified aromatic vinyl graft copolymer If it does not contain, or if the content is small (Comparative Examples 2 and 3), it can be seen that the plating adhesion and impact resistance is reduced.

Simple modifications and variations of the present invention can be easily made 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 (12)

40 to 60 weight percent of a polycarbonate resin;
10 to 30% by weight of the first rubber-modified vinyl graft copolymer having an average particle diameter of the rubbery polymer of 220 to 340 nm;
5 to 25% by weight of the second rubber-modified vinyl graft copolymer having an average particle diameter of the rubbery polymer of 100 to 160 nm; And
A thermoplastic resin composition for plating, comprising 10 to 40% by weight of an aromatic vinyl-vinyl cyanide copolymer resin.
The method of claim 1, wherein the polycarbonate resin has a weight average molecular weight of 15,000 to 35,000 g / mol, the plating thermoplastic resin composition.
The monomer mixture of claim 1, wherein the first rubber-modified aromatic vinyl graft copolymer comprises an aromatic vinyl monomer and a vinyl cyanide monomer in an amount of 35 to 65 wt% of the rubbery polymer having an average particle diameter of 220 to 340 nm. To 65% by weight is a graft copolymerized polymer, characterized in that the thermoplastic resin composition for plating.
According to claim 3, The monomer mixture is a thermoplastic resin composition for plating comprising 60 to 90% by weight of the aromatic vinyl monomer and 10 to 40% by weight of the vinyl cyanide monomer.
The monomer mixture of claim 1, wherein the second rubber-modified aromatic vinyl graft copolymer comprises an aromatic vinyl monomer and a vinyl cyanide monomer in 35 to 60 wt% of the rubbery polymer having an average particle diameter of 100 to 160 nm. To 65% by weight is a graft copolymerized polymer, characterized in that the thermoplastic resin composition for plating.
The thermoplastic resin composition for plating according to claim 5, wherein the monomer mixture comprises 60 to 90 wt% of the aromatic vinyl monomer and 10 to 40 wt% of the vinyl cyanide monomer.
The thermoplastic resin composition for plating according to claim 1, wherein the weight ratio of the first rubber modified aromatic vinyl copolymer and the second rubber modified aromatic vinyl copolymer is 1: 0.2 to 1: 1.
The thermoplastic resin composition for plating according to claim 1, wherein the aromatic vinyl-vinyl cyanide copolymer resin has a weight average molecular weight of 50,000 to 300,000 g / mol.
The method of claim 1, wherein the thermoplastic resin composition for plating the chromium plated 10 cm × 10 cm × 0.3 cm injection molded specimens to a thickness of 30 ㎛, measured at a peel rate of 50 mm / min using a tensile tester Adhesive strength of one plating layer is 580 to 700 gf / cm thermoplastic resin composition for plating.
The plating thermoplastic resin composition of claim 1, wherein the plating thermoplastic resin composition has a notched Izod impact strength of 48 to 65 kgf · cm / cm measured by a 1/8 ″ test specimen according to ASTM D256. .
The plating method of claim 1, wherein the plating thermoplastic resin composition has a heat deflection temperature (HDT) of 90 to 110 ° C measured under a condition of a load of 1.8 MPa and a heating rate of 120 ° C / hr based on ASTM D648. Thermoplastic resin composition for.
Base layer; And
It includes a plating layer formed on at least one surface of the base layer,
The base material layer is formed from a plated thermoplastic resin composition according to any one of claims 1 to 11.

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