KR20180066735A - Thermoplastic resin composition for plating - Google Patents

Abstract

A thermoplastic resin composition for plating of the present invention comprises: 40-60 wt% of a polycarbonate resin; 10-30 wt% of a first rubber-modified vinyl-based graft copolymer having an average particle diameter of the rubber polymer of 220-340 nm; 5-25 wt% of a second rubber-modified vinyl-based graft copolymer having an average particle diameter of rubber polymer of 100-160 nm; and 10-40 wt% of an aromatic vinyl-cyanide vinyl copolymer resin. The thermoplastic resin composition for plating and the plated molded article containing the same are excellent in plating adhesion, impact resistance, heat resistance, and the balance of physical properties.

Description

[0001] THERMOPLASTIC RESIN COMPOSITION FOR PLATING [0002]

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

2. Description of the Related Art Demand for plated plastic products has been increasing for the purpose of achieving a cost saving effect by reducing the weight of materials in automobiles, electric and electronic appliances and office automation equipment, There is an increasing demand for a new thermoplastic resin composition for plating (plastic material).

In the thermoplastic resin composition, the thermoplastic resin composition (PC / ABS blend, etc.) comprising a polycarbonate (PC) resin and a rubber-modified aromatic vinyl copolymer resin such as acrylonitrile-butadiene-styrene It is possible to improve workability and chemical resistance without lowering the impact resistance and heat resistance, and it is possible to reduce the cost, so that it is utilized for various purposes.

However, the PC / ABS blend and the like have a much lower plating adhesion than conventional thermoplastic resin compositions for plating, such as ABS resin, and there is a fear that a reliability problem such as dropping of the plating layer and resin layer and occurrence of buckling may occur at a rapid temperature change .

Accordingly, development of a thermoplastic resin composition for plating that can improve impact resistance, heat resistance and the like without deteriorating the plating adhesion has been demanded.

The background art of the present invention is disclosed in Korean Patent No. 10-0292878.

It is an object of the present invention to provide a thermoplastic resin composition for plating which is excellent in plating adhesion, impact resistance, heat resistance, physical properties and the like.

Another object of the present invention is to provide a plated molded article comprising the 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. Wherein the thermoplastic resin composition for plating comprises 40 to 60% by weight of a polycarbonate resin; 10 to 30% by weight of a first rubber-modified vinyl-based graft copolymer having an average particle diameter of the rubber polymer of 220 to 340 nm; 5 to 25% by weight of a second rubber-modified vinyl-based graft copolymer having an average particle diameter of rubber polymer of 100 to 160 nm; And 10 to 40% by weight of an aromatic vinyl-cyanide vinyl copolymer resin.

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

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

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

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

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

In a specific example, the weight ratio of the first rubber-modified aromatic vinyl-based copolymer and the second rubber-modified aromatic vinyl-based copolymer may be 1: 0.2 to 1: 1.

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

In the specific example, the injection molding specimen having a size of 10 cm x 10 cm x 0.3 cm was chrome plated to a thickness of 30 mu m, and then the plated layer measured at a peeling speed of 50 mm / min using a tensile tester May have an adhesion strength of 580 to 700 gf / cm.

In the specific example, the thermoplastic resin composition for plating may have a notched Izod impact strength of 48 to 65 kgf · cm / cm measured with a 1/8 "thick specimen according to ASTM D256.

In a specific example, the thermoplastic resin composition for plating may have a heat distortion temperature (HDT) of 90 to 110 DEG C measured under the conditions of a load of 1.8 MPa and a temperature raising rate of 120 DEG C / hr, according to ASTM D648.

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

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a thermoplastic resin composition for plating excellent in plating adhesion, impact resistance, heat resistance, physical properties and the like, and a plated molded article containing the same.

1 schematically shows a cross-section of a plated molded article according to one 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-based graft copolymer and (B2) a second rubber-modified aromatic vinyl-based graft copolymer B) a rubber-modified aromatic vinyl-based graft copolymer and (C) an aromatic vinyl-cyanide vinyl copolymer resin.

(A) Polycarbonate resin

As the polycarbonate resin according to one 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 prepared by reacting a diphenol (aromatic diol compound) with a carbonate precursor such as phosgene, halogen formate, or carbonic acid diester can be used.

Specific examples of the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane. . For example, 2,2-bis (3,5-dimethylphenyl) propane, 2,2-bis (3,5-dichloro- Bis (4-hydroxyphenyl) propane, or 1,1-bis (4-hydroxyphenyl) cyclohexane can be used. Specific examples thereof include 2,2- Can be used.

In an embodiment, the polycarbonate resin may have a branched chain. For example, 0.05 to 2 parts by mole of trifunctional or more polyfunctional compounds per 100 parts by mole of the total of the diphenols used for polymerization, specifically, Or by adding a compound having a trivalent or higher phenolic group.

In embodiments, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. The polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction 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), as measured by gel permeation chromatography (GPC), of from 15,000 to 35,000 g / mol, such as from 20,000 to 32,000 g / mol . Within the above range, the flowability, impact resistance, heat resistance and the like of the thermoplastic resin composition for plating can be excellent.

In an embodiment, the polycarbonate resin may be contained in an amount of 40 to 60 wt%, for example, 45 to 55 wt% of 100 wt% of the total thermoplastic resin composition for plating. If the content of the polycarbonate resin is less than 40% by weight, the impact resistance and heat resistance of the thermoplastic resin composition for plating may deteriorate. If the content exceeds 60% by weight, plating of the molded product formed from the thermoplastic resin composition for plating There is a possibility that the property is deteriorated.

(B) a rubber-modified aromatic vinyl-based graft copolymer

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

(B1) a first rubber-modified aromatic vinyl-based graft copolymer

The first rubber-modified aromatic vinyl-based graft copolymer according to one embodiment of the present invention is obtained by copolymerizing a rubber polymer having an average particle size (D50) of 220 to 340 nm, for example, 230 to 290 nm, with an aromatic vinyl monomer and a vinyl cyanide The monomer mixture comprising the monomers may be graft copolymerized. For example, it can be obtained by adding the monomer mixture to the rubbery polymer and graft copolymerizing the monomer mixture. The polymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization and the like. When the average particle diameter of the rubbery polymer is less than 220 nm, the rubber-modified aromatic vinyl-based graft copolymer does not have a bimodal particle size distribution and may have low impact resistance. When the average particle diameter is more than 340 nm, the thermoplastic resin composition There is a possibility that the plating adhesion of the molded product formed from the above-mentioned material is deteriorated.

Examples of the rubbery polymer include a diene rubber such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene) having an average particle diameter (D50) Acrylic rubber such as saturated rubber, isoprene rubber and polybutyl acrylate, and ethylene-propylene-diene monomer terpolymer (EPDM). These may be used alone or in combination of two or more. For example, a diene rubber can be used, and specifically, a polybutadiene rubber can be used. The content of the rubbery polymer may be from 35 to 65% by weight, for example, from 40 to 60% by weight, and the content of the monomer mixture is from 35 to 65% by weight in 100% by weight of the entire rubber modified aromatic vinyl-based graft copolymer. For example from 40 to 60% by weight. Within the above range, the moldability, physical properties and the like of the thermoplastic resin composition for plating can be stable.

In an embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and examples thereof include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt- , Vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, combinations thereof, and the like, but the present invention is not limited thereto. For example, styrene and 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 entire monomer mixture. Within the above range, compatibility among the components in the thermoplastic resin composition for plating may be excellent.

In an embodiment, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl-based monomer, and is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, Combinations thereof, and the like may be used, but the present invention is not limited thereto. For example, acrylonitrile and 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 entire monomer mixture. Within the above range, compatibility between the components of the thermoplastic resin composition for plating and the plating etching property of the molded product formed from the thermoplastic resin composition for plating can be excellent.

In an embodiment, the monomer mixture may further comprise a monomer for imparting processability and heat resistance in addition to the aromatic vinyl monomer and the vinyl cyanide monomer. Examples thereof include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide. These may be used alone or in combination of two or more. The monomer for imparting processability and heat resistance may be contained 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. The processability, heat resistance and the like of the thermoplastic resin composition for plating can be further improved without deteriorating the physical properties in the above range.

In an embodiment, the first rubber-modified aromatic vinyl-based graft copolymer may be contained in an amount of 10 to 30% by weight, for example, 15 to 25% by weight, of 100% by weight of the total thermoplastic resin composition for plating. If the content of the first rubber-modified aromatic vinyl-based graft copolymer is less than 10% by weight, the impact resistance of the thermoplastic resin composition for plating and the plating adhesion of the molded article formed from the thermoplastic resin composition for plating may decrease. If the content exceeds the above range, the heat resistance and fluidity of the thermoplastic resin composition for plating may be lowered.

(B2) a second rubber-modified aromatic vinyl-based graft copolymer

The second rubber-modified aromatic vinyl-based graft copolymer according to one embodiment of the present invention is obtained by copolymerizing a rubber polymer having an average particle size (D50) of 100 to 160 nm, for example, 110 to 150 nm, with an aromatic vinyl monomer and a vinyl cyanide The monomer mixture comprising the monomers may be graft copolymerized. For example, it can be obtained by adding the monomer mixture to the rubbery polymer and graft copolymerizing the monomer mixture. The polymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization and the like. When the average particle diameter of the rubbery polymer is less than 100 nm, the impact resistance of the thermoplastic resin composition for plating, the plating etching property of the molded product formed from the thermoplastic resin composition for plating may be lowered, and if it exceeds 160 nm, There is a possibility that the vinyl-based graft copolymer does not have a bimodal particle size distribution.

Examples of the rubbery polymer include a diene rubber such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene) having an average particle diameter (D50) Acrylic rubber such as saturated rubber, isoprene rubber and polybutyl acrylate, and ethylene-propylene-diene monomer terpolymer (EPDM). These may be used alone or in combination of two or more. For example, a diene rubber can be used, and specifically, a polybutadiene rubber can be used. The content of the rubbery polymer may be from 35 to 60% by weight, for example, from 40 to 60% by weight, and the content of the monomer mixture is from 40 to 65% by weight in 100% by weight of the entire rubber modified aromatic vinyl-based graft copolymer. For example from 40 to 60% by weight. In the above range, the plating adhesion of the molded product formed from the thermoplastic resin composition for plating can be excellent.

In an embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and examples thereof include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt- , Vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, combinations thereof, and the like, but the present invention is not limited thereto. For example, styrene and 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 entire monomer mixture. Within this range, compatibility between the components of the thermoplastic resin composition for plating can be excellent.

In an embodiment, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl-based monomer, and is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, Combinations thereof, and the like may be used, but the present invention is not limited thereto. For example, acrylonitrile and 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 entire monomer mixture. Within the above range, compatibility between the components of the thermoplastic resin composition for plating and the plating etching property of the molded product formed from the thermoplastic resin composition for plating can be excellent.

In an embodiment, the monomer mixture may further comprise 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 and the like can be exemplified, but are not limited thereto. These may be used alone or in combination of two or more. The monomer for imparting processability and heat resistance may be contained 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 monomer mixture. The processability, heat resistance and the like of the thermoplastic resin composition for plating can be further improved without deteriorating the physical properties in the above range.

In a specific example, the second rubber-modified aromatic vinyl-based graft copolymer may be contained in an amount of 5 to 25% by weight, for example, 5 to 20% by weight, based on 100% by weight of the total thermoplastic resin composition for plating. If the content of the second rubber-modified aromatic vinyl-based graft copolymer is less than 5% by weight, the effect of increasing the plating adhesion of the thermoplastic resin composition for plating may be insignificant. If it exceeds 25% by weight, The impact resistance and the like may be lowered.

In a specific example, 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: For example, from 1: 0.3 to 1: 0.9. Within the above range, the mechanical properties of the thermoplastic resin composition for plating, the plating adhesion of the molded product formed from the thermoplastic resin composition for plating, and the like can be further improved.

(C) an aromatic vinyl-cyanide vinyl copolymer resin

The aromatic vinyl-cyanide vinyl copolymer resin according to one embodiment of the present invention is capable of improving the processability of the thermoplastic resin composition for plating and the plating etching property of a molded product formed from the thermoplastic resin composition for plating, And a polymer of a monomer mixture comprising a vinyl cyanide monomer. For example, the aromatic vinyl-cyanide vinyl copolymer is a copolymer comprising a repeating unit derived from an aromatic vinyl monomer and a repeating unit derived from a vinyl cyan monomer, wherein the monomer mixture is prepared by a known polymerization method . If necessary, an aromatic vinyl-cyanide vinyl copolymer further containing a monomer for imparting processability and heat resistance to the above monomer mixture and further containing a repeating unit derived from a monomer giving workability and heat resistance can be obtained .

In an embodiment, the aromatic vinyl-based monomer is a monomer capable of forming a repeating unit derived from an aromatic vinyl-based monomer by being polymerized with a vinyl cyanide monomer or the like, and examples thereof include styrene,? -Methylstyrene,? -Methylstyrene, but are not limited to, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinylnaphthalene. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer (repeating unit derived from an aromatic vinyl monomer) is 60 to 90% by weight, for example, 65 to 80% by weight, based on 100% by weight of the monomer mixture (aromatic vinyl-cyanide vinyl copolymer) Lt; / RTI > Within the above range, the processability and fluidity of the thermoplastic resin composition for plating can be excellent.

In an embodiment, the vinyl cyanide monomer may be a polymer which is capable of forming a repeating unit derived from a vinyl cyanide monomer by being polymerized with an aromatic vinyl-based monomer or the like. The vinyl monomer may be acrylonitrile, methacrylonitrile, ethacrylonitrile, Nitrile,? -Chloroacrylonitrile, fumaronitrile, and the like, but are not limited thereto. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like can be used. The content of the vinyl cyanide monomer (repeating unit derived from a vinyl cyanide monomer) is 10 to 40% by weight, for example, 15 to 35% by weight, based on 100% by weight of the monomer mixture (aromatic vinyl-cyanide vinyl copolymer) Lt; / RTI > Within the above range, the compatibility of the thermoplastic resin composition for plating and the plating adhesion of the molded product formed from the thermoplastic resin composition for plating can be excellent.

In the specific examples, examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide and the like. When the monomer for imparting processability and heat resistance is used, the content thereof may be 30 parts by weight or less, for example, 1 to 25 parts by weight, based on 100 parts by weight of the monomer mixture. The processability and heat resistance can be imparted to the plastics thermoplastic resin composition without deteriorating the other properties in the above range.

In an embodiment, the aromatic vinyl-cyanide vinyl copolymer resin is a copolymer of styrene and acrylonitrile, a copolymer of styrene,? -Methylstyrene and acrylonitrile, and a copolymer of? -Methylstyrene and acrylonitrile And may include one or more species.

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

In an embodiment, the aromatic vinyl-cyanide vinyl copolymer may be contained in an amount of 10 to 40% by weight, for example, 15 to 35% by weight, based on 100% by weight of the total thermoplastic resin composition for plating. If the content of the aromatic vinyl-cyanide vinyl copolymer is less than 10% by weight, the plating etching property of the molded product formed from the thermoplastic resin composition for plating may be deteriorated. If the content exceeds 40% by weight, There is a possibility that the adhesion of the formed product formed from the composition to the plating is deteriorated.

The thermoplastic resin composition according to one embodiment of the present invention may contain an inorganic filler, a flame retardant, a flame retardant, a compatibilizing agent, a releasing agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer, an antioxidant, And the like. 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, the rubber-modified aromatic vinyl copolymer and the aromatic vinyl-cyanide vinyl copolymer resin, but is not limited thereto.

The thermoplastic resin composition for plating according to one embodiment of the present invention may be in the form of a pellet obtained by melt-extruding the above components and mixing them at a temperature of 200 to 280 DEG C, for example, 250 to 260 DEG C using a conventional twin-screw extruder .

In the specific example, the thermoplastic resin composition for plating was prepared by chrome plating an injection-molded specimen having a size of 10 cm x 10 cm x 0.3 cm to a thickness of about 30 mu m and measuring the peeling speed at a rate of 50 mm / min using a tensile tester The adhesion strength of the plated layer may be 580 to 700 gf / cm, for example 600 to 680 gf / cm.

In the specific example, 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 with a 1/8 "thick sample according to ASTM D256 Lt; / RTI >

In the specific example, the thermoplastic resin composition for plating has a heat distortion temperature (HDT) of 90 to 110 DEG C, for example, 95 to 105 DEG C, measured under the conditions of a load of 1.8 MPa and a heating rate of 120 DEG C / hr according to ASTM D648 Lt; / RTI >

1 schematically shows a cross-section of a plated molded article according to one embodiment of the present invention. In the drawings, the size of elements constituting the invention is exaggerated for clarity of description, and is not limited thereto. In addition, the shape of each component is not limited to the drawing, and may have various shapes. 1, a plated molded article according to one embodiment of the present invention includes a substrate layer 10; And a plating layer (20) formed on at least one side of the base layer (10), wherein the base layer (10) is formed from the thermoplastic resin composition for plating.

In the specific example, the base layer 10 may be formed in various forms from the thermoplastic resin composition for plating by various molding methods such as injection molding, extrusion molding, vacuum molding, casting molding and the like. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains.

In an embodiment, the plating layer 20 may be formed by a conventional method of manufacturing a plated plastic product such as ABS resin plating. For example, the base layer 10 may be etched, For example, electroless plating and electroplating, after formation of an anchor, but the present invention is not limited thereto.

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

In an embodiment, the plating layer 20 may include at least one of chromium, nickel, and copper. The thickness of the plating layer 20 may be 0.1 to 100 탆, but is not limited thereto.

The plated molded article of the present invention is excellent in the plating adhesion of the base layer and the plating layer and is excellent in impact resistance and heat resistance and can be used as an internal and external material for metallic exterior such as automobile, It is useful for automobile exterior materials.

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

Example

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) Polycarbonate resin

A bisphenol-A polycarbonate resin (weight average molecular weight (Mw): 25,000 g / mol) was used.

(B) a rubber-modified aromatic vinyl-based graft copolymer

(B1) First rubber-modified aromatic vinyl-based graft copolymer was prepared by mixing 60 wt% of polybutadiene rubber (PBR) having an average particle diameter (D50) of 280 nm and 40 wt% of styrene and acrylonitrile (weight ratio: 70/30 ) Graft copolymerized g-ABS was used.

(B2) 50 wt% of a polybutadiene rubber (PBR) having an average particle diameter (D50) of 150 nm as a second rubber-modified aromatic vinyl-based graft copolymer, 50 wt% of styrene and acrylonitrile ) Graft copolymerized g-ABS was used.

(C) an aromatic vinyl-cyanide vinyl copolymer resin

SAN resin (weight average molecular weight (Mw): 130,000 g / mol) which is a copolymer of styrene and acrylonitrile (weight ratio: 70/30) was used.

Examples 1 to 3 and Comparative Examples 1 to 4

The above components were added in the amounts as shown in Table 1, and then extruded at 250 캜 to prepare pellets. The extrudate was a biaxial extruder having an L / D of 36 and a diameter of 45 mm. The pellets were dried at 80 to 100 ° C. for 4 hours or more, and then dried in a 6 oz injection molding machine (molding temperature 250 ° C., mold temperature 60 ° C.) The specimens were prepared by injection molding. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Adhesion Strength of Plating Layer (Unit: gf / cm): An injection molded specimen of 10 cm x 10 cm x 0.3 cm was chrome plated to a thickness of about 30 μm, and then the central portion of the chromium plated layer was cut using a tensile tester After being bitten by a jig of a tensile tester, the adhesive strength of the base layer and the plating layer was measured by pulling at a peeling speed of 50 mm / min in the 90 占 direction of the surface of the plating layer.

(2) Notch Izod impact strength (unit: kgf cm / cm): A notch was formed on a 1/8 "thick Izod (IZOD) specimen according to the evaluation method described in ASTM D256.

(3) Heat distortion temperature (HDT, unit: 占 폚): Measured under the conditions of a load of 1.8 MPa and a heating rate of 120 占 폚 / hr in accordance with ASTM D648.

Example Comparative Example One 2 3 One 2 3 4 (A) (% by weight) 50 50 50 50 50 50 50 (B1) (% by weight) 16 19 14 26 - 6 24 (B2) (% by weight) 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 Notch Izod impact strength (kgf · cm / cm) 50 51 50 53 45 47 52 Heat deformation temperature (캜) 100 100 100 100 100 100 100

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

On the other hand, when the second rubber-modified aromatic vinyl-based graft copolymer is not contained or the content thereof is small (Comparative Examples 1 and 4), it is found that the coating adhesion is lowered, and the first rubber- modified aromatic vinyl-based graft copolymer (Comparative Examples 2 and 3), the plating adhesion and the impact resistance are lowered.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (12)

40 to 60% by weight of a polycarbonate resin;
10 to 30% by weight of a first rubber-modified vinyl-based graft copolymer having an average particle diameter of the rubber polymer of 220 to 340 nm;
5 to 25% by weight of a second rubber-modified vinyl-based graft copolymer having an average particle diameter of rubber polymer of 100 to 160 nm; And
And 10 to 40% by weight of an aromatic vinyl-cyanide vinyl copolymer resin.
The thermoplastic resin composition for plating according to claim 1, wherein the polycarbonate resin has a weight average molecular weight of 15,000 to 35,000 g / mol.
The rubber composition according to claim 1, wherein the first rubber-modified aromatic vinyl-based graft copolymer comprises 35 to 65% by weight of a rubbery polymer having an average particle diameter of 220 to 340 nm, a monomer mixture 35 comprising an aromatic vinyl monomer and a vinyl cyanide monomer To 65% by weight of the thermoplastic resin is a graft copolymerized polymer.
The thermoplastic resin composition for plating according to claim 3, wherein the monomer mixture comprises 60 to 90% by weight of the aromatic vinyl monomer and 10 to 40% by weight of the vinyl cyanide monomer.
The rubber-modified aromatic vinyl-based graft copolymer according to claim 1, wherein the second rubber-modified aromatic vinyl-based graft copolymer is a mixture of aromatic vinyl monomer and vinyl cyanide monomer-based monomer mixture 40 to 60% by weight of a rubbery polymer having an average particle size of 100 to 160 nm To 65% by weight of the thermoplastic resin is a graft copolymerized polymer.
6. The thermoplastic resin composition for plating according to claim 5, wherein the monomer mixture comprises 60 to 90% by weight of the aromatic vinyl monomer and 10 to 40% by weight 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-based copolymer and the second rubber-modified aromatic vinyl-based copolymer is 1: 0.2 to 1: 1.
The thermoplastic resin composition for plating according to claim 1, wherein the aromatic vinyl-cyanide vinyl copolymer resin has a weight average molecular weight of 50,000 to 300,000 g / mol.
The thermoplastic resin composition for plating according to claim 1, wherein the injection molded specimen having a size of 10 cm x 10 cm x 0.3 cm is chrome plated to a thickness of 30 mu m and then measured at a peeling speed of 50 mm / min using a tensile tester Wherein the adhesion strength of one of the plated layers is 580 to 700 gf / cm.
2. The thermoplastic resin composition for plating according to claim 1, wherein the thermoplastic resin composition for plating has a notched Izod impact strength of 48 to 65 kgf / cm / cm measured with a 1/8 "thick sample according to ASTM D256 .
The plating method according to claim 1, wherein the thermoplastic resin composition for plating has a heat distortion temperature (HDT) of 90 to 110 DEG C measured under the conditions of a load of 1.8 MPa and a heating rate of 120 DEG C / hr according to ASTM D648 And a thermoplastic resin composition.
A base layer; And
And a plating layer formed on at least one surface of the substrate layer,
Wherein the base layer is formed from the thermoplastic resin composition for plating according to any one of claims 1 to 11.

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