Title of the invention: Thermoplastic resin composition, its manufacturing method, and metal plated molded product manufactured therefrom
Technical field
[One]
[Mutual citation with application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0113686 filed on Sep. 21, 2018 and Korean Patent Application No. 10-2019-0108923 filed on Sep. 03, 2019, All contents disclosed in the documents of the Korean patent application are included as part of this specification.
[3]
[4]
The present invention relates to a thermoplastic resin composition, a method of manufacturing the same, and a metal plated molded article manufactured therefrom, and more particularly, the non-plating does not occur under the condition that the incidence of non-plating is high by reducing the etching time. It relates to a thermoplastic resin composition having excellent mechanical properties, thermal properties and plating adhesion, and excellent appearance quality even after plating, a method of manufacturing the same, and a metal plated molded article manufactured therefrom.
Background
[5]
ABS resins represented by acrylonitrile-butadiene-styrene (hereinafter referred to as'ABS') are the stiffness and chemical resistance of acrylonitrile, processability of butadiene and styrene, mechanical strength, and beautiful appearance properties. For this reason, it is used in various ways such as automotive supplies, electrical/electronic products, and office equipment.
[6]
Such ABS resins are often subjected to plating treatment.
[7]
However, low plating adhesion and occurrence of non-plating are critical factors for product reliability and appearance quality, so as a method to prevent this, a method of changing the conditions of the plating process such as solution composition, process time and temperature, and increasing the rubber content. A method, a method of simplifying the shape of a molded article in an injection process, and the like are proposed.
[8]
However, in this case, there is a problem that the process cost is increased, the thermal cycle decreases due to the increase of the linear expansion coefficient, or the product design is limited.
[9]
Accordingly, there is a high demand for a thermoplastic resin composition that maintains the mechanical properties inherent in ABS-based resins, while increasing process costs, reducing thermal properties, and improving plating adhesion without causing unplated.
[10]
[11]
〔Prior technical literature〕
[12]
[Patent Literature]
[13]
(Patent Document 1) Korean Laid-Open Patent No. 10-2015-0067482
Detailed description of the invention
Technical challenge
[14]
In order to solve the problems of the prior art as described above, the present invention does not cause non-plating under conditions of high non-plating occurrence rate, such as reduction of etching time, but has mechanical properties equal to or higher than the prior art, but has thermal properties and plating adhesion. It is an object of the present invention to provide a thermoplastic resin composition, a method of manufacturing the same, and a metal plated molded article manufactured therefrom, which is greatly improved and has excellent appearance quality after plating.
[15]
All of the above and other objects of the present invention can be achieved by the present invention described below.
Means of solving the task
[16]
In order to achieve the above object, the present invention is a) a conjugated diene rubber particle diameter of 0.05 ㎛ to 0.2 ㎛ vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer 5 to 40% by weight, b) conjugated diene rubber A base resin comprising 5 to 40% by weight of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer having a particle diameter of more than 0.2 μm to 0.5 μm and c) 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer 100 parts by weight; And the following formula 1
[17]
[Formula 1]
[18]

[19]
(The X is hydrogen or a hydroxy group, Y is hydrogen or , and R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independently an aryl group having 6 to 12 carbon atoms or An alkyl group having 1 to 10 carbon atoms, R 5 and R 6 are independently an alkyl group having 1 and 10 carbon atoms, Z is hydrogen or a hydroxy group, n is an integer of 1 to 100, and m is an integer of 0 to 100 Including, the a) graft copolymer is included in a smaller amount than the b) graft copolymer, and the compound represented by Formula 1 is It provides a thermoplastic resin composition, characterized in that the kinematic viscosity (25 ℃) is greater than 5 cSt to less than 200 cSt.
[20]
The a) graft copolymer and b) the graft copolymer may preferably have a weight ratio of 1:1.5 to 1:4.
[21]
The compound represented by Formula 1 may have a kinematic viscosity (25° C.) of 10 to 99 cSt.
[22]
The a) vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is, for example, 30 to 70% by weight of a conjugated diene rubber having a particle diameter of 0.05 µm to 0.2 µm, 5 to 30% by weight of a vinyl cyan compound, and 15 It may be graft polymerization, including to 50% by weight.
[23]
The b) vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is, for example, 40 to 80% by weight of a conjugated diene rubber having a particle diameter of more than 0.2 μm to 0.5 μm, 3 to 20% by weight of a vinyl cyan compound, and an aromatic vinyl compound. It may be graft polymerization, including 10 to 50% by weight.
[24]
The c) aromatic vinyl compound-vinyl cyan compound copolymer may include, for example, 55 to 85% by weight of an aromatic vinyl compound and 15 to 45% by weight of a vinylcyan compound.
[25]
For example, the thermoplastic resin composition may have a plating adhesion (10mm/80mm) of 10 N/cm or more.
[26]
For example, the thermoplastic resin composition may have a melt index (220° C., 10 kg) of 10 to 40 g/10min.
[27]
The thermoplastic resin composition may be, for example, a resin composition for plating.
[28]
The thermoplastic resin composition may further include at least one selected from the group consisting of a heat stabilizer, an antioxidant, an impact modifier, a light stabilizer, a plasticizer, a lubricant, and an antistatic agent.
[29]
In addition, the present invention is a) a vinyl cyan compound having a conjugated diene rubber particle diameter of 0.05 μm to 0.2 μm-conjugated diene rubber-aromatic vinyl compound graft copolymer 5 to 40% by weight, b) a conjugated diene rubber particle diameter of more than 0.2 μm to 0.5 100 parts by weight of a base resin comprising 5 to 40% by weight of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer having a µm or less and c) 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; And the following formula 1
[30]
[Formula 1]
[31]

[32]
(The X is hydrogen or a hydroxy group, Y is hydrogen or , and R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independently an aryl group having 6 to 12 carbon atoms or An alkyl group having 1 to 10 carbon atoms, R 5 and R 6 are independently an alkyl group having 1 and 10 carbon atoms, Z is hydrogen or a hydroxy group, n is an integer of 1 to 100, and m is an integer of 0 to 100 An integer) greater than 0.01 parts by weight to less than 2 parts by weight of a compound represented by; in a twin screw extruder, melt-kneading and extruding, wherein a) the graft copolymer is in an amount less than that of the b) graft copolymer It is included as, and the compound represented by Formula 1 provides a method for producing a thermoplastic resin composition, characterized in that the kinematic viscosity (25 ℃) is greater than 5 cSt to less than 200 cSt.
[33]
In addition, the present invention provides a metal plated article, characterized in that the thermoplastic resin composition is molded and a metal plated layer is formed on the surface.
[34]
The metal plating layer may be formed including at least one selected from the group consisting of copper, nickel, and chromium.
[35]
The metal plating molded article may be, for example, an automobile interior material or an automobile exterior material.
[36]
In addition, the present invention comprises the step of injecting the thermoplastic resin composition to obtain an injection product, etching the injection product using an etching solution, and plating the etched injection product. Provides a way.
Effects of the Invention
[37]
According to the present invention, non-plating does not occur even under conditions of high non-plating incidence rate such as decrease in etching time or temperature, while having mechanical properties such as impact strength or fluidity equal to or higher than the conventional level, thermal properties and plating adhesion are greatly improved. It has the effect of providing a thermoplastic resin composition having excellent appearance quality after plating, a method for manufacturing the same, and a metal plated molded article manufactured therefrom.
Best mode for carrying out the invention
[38]
Hereinafter, the thermoplastic resin composition of the present disclosure, a method of manufacturing the same, and a metal plated molded article manufactured therefrom will be described in detail.
[39]
The present inventors believe that when mixing two kinds of ABS resins having different rubber particle diameters, an aromatic vinyl compound-vinyl cyan compound copolymer, and a predetermined polysiloxane having a specific kinematic viscosity within a specific content range, the etching time is reduced, mechanical properties decrease, and thermal properties It was confirmed that plating adhesion and the like were greatly improved without deterioration and non-plating, and the present invention was completed based on this.
[40]
[41]
The thermoplastic resin composition of the present invention comprises a) a conjugated diene rubber particle diameter of 0.05 μm to 0.2 μm, a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer 5 to 40% by weight, b) a conjugated diene rubber particle diameter of 0.2 μm 100 parts by weight of a base resin comprising 5 to 40% by weight of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer having an amount greater than to 0.5 μm and 50 to 80% by weight of c) an aromatic vinyl compound-vinyl cyan compound copolymer; And the following formula 1
[42]
[Formula 1]
[43]

[44]
(The X is hydrogen or a hydroxy group, Y is hydrogen or , and R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independently an aryl group having 6 to 12 carbon atoms or An alkyl group having 1 to 10 carbon atoms, R 5 and R 6 are independently an alkyl group having 1 and 10 carbon atoms, Z is hydrogen or a hydroxy group, n is an integer of 1 to 100, and m is an integer of 0 to 100 Integer is an integer) of 0.01 to 2 parts by weight of the compound; No non-plating occurs, and thermal properties, plating adhesion, and appearance quality are excellent while having mechanical properties equal to or higher than the conventional one.
[45]
In addition, the thermoplastic resin composition of the present invention is preferably a) a conjugated diene rubber particle diameter of 0.05 ㎛ to 0.2 ㎛ vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer 5 to 40% by weight, b) conjugated diene rubber A base resin comprising 5 to 40% by weight of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer having a particle diameter of more than 0.2 μm to 0.5 μm and c) 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer 100 parts by weight; And the following formula 1
[46]
[Formula 1]
[47]

[48]
(The X is hydrogen or a hydroxy group, Y is hydrogen or , and R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independently an aryl group having 6 to 12 carbon atoms or An alkyl group having 1 to 10 carbon atoms, R 5 and R 6 are independently an alkyl group having 1 and 10 carbon atoms, Z is hydrogen or a hydroxy group, n is an integer of 1 to 100, and m is an integer of 0 to 100 Including, the a) graft copolymer is contained in an amount less than that of the b) graft copolymer, and the compound represented by Formula 1 is It is characterized by having a kinematic viscosity (25 ℃) of more than 5 cSt to less than 200 cSt, and within this range, plating properties such as plating adhesion, non-plating, thermal properties and plating appearance quality are excellent, and excellent processability is excellent. There are advantages to being suitable for the composition.
[49]
[50]
Base resin
[51]
Each of the a) graft copolymer and b) the graft copolymer may be, for example, a graft-polymerized copolymer including a vinyl cyan compound and an aromatic vinyl compound in a conjugated diene rubber.
[52]
The conjugated diene rubber may be, for example, a latex in which the conjugated diene rubber is dispersed in water in a colloidal state. In this case, mechanical strength and processability are excellent.
[53]
The conjugated diene rubber refers to a polymer or copolymer polymerized including a conjugated diene compound, which is a structure in which a double bond and a single bond are arranged, and examples thereof include butadiene polymer, butadiene-styrene copolymer and butadiene. -It may be one or more selected from the group consisting of acrylonitrile copolymers, and in this case, mechanical properties are excellent.
[54]
The a) conjugated diene rubber of the graft copolymer may have, for example, a particle diameter of 0.05 µm to 0.2 µm, 0.05 µm to 0.17 µm, or 0.07 µm to 0.15 µm, and within this range, mechanical properties, thermal properties, and plating adhesion This has an excellent effect.
[55]
The b) conjugated diene rubber of the graft copolymer may have, for example, a particle diameter of more than 0.2 µm to 0.5 µm, 0.25 µm to 0.45 µm, or 0.3 µm to 0.4 µm, and mechanical properties, processability and plating within this range. It has excellent properties.
[56]
In the present description, the conjugated diene rubber particle diameter means the average particle diameter of the conjugated diene rubber particles, and as an example, it is measured using an Intensity Gaussian Distribution (Nicomp 380) by a dynamic laser light scattering method. .
[57]
[58]
The vinyl cyan compound may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof, for example, and preferably acrylonitrile, in this case, mechanical strength and There is an effect of excellent processability.
[59]
The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, ρ-methylstyrene, ο-ethylstyrene, ρ-ethylstyrene, vinyltoluene, and derivatives thereof. In this case, mechanical properties And there is an effect of excellent plating properties.
[60]
[61]
The base resin may include, for example, a) 5 to 40% by weight of a graft copolymer, b) 5 to 40% by weight of a graft copolymer, and c) 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer. In this case, thermal properties, mechanical properties, and plating adhesion are excellent.
[62]
The a) graft copolymer may be, for example, 5 to 40% by weight, 10 to 35% by weight, or 10 to 30% by weight, preferably 10 to 15% by weight, and flowability within this range, It has excellent mechanical strength, plating adhesion and thermal properties.
[63]
The b) graft copolymer may be, for example, 5 to 40% by weight, 10 to 35% by weight, or 10 to 30% by weight, preferably 20 to 30% by weight, and more preferably 20% by weight. % Or more and may be less than 25% by weight, and within this range, there is an excellent effect of fluidity, mechanical strength, plating adhesion, and thermal properties.
[64]
The c) aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, 50 to 80% by weight, 55 to 75% by weight, or 60 to 70% by weight, preferably more than 60% by weight to 70% by weight or less. And, within this range, there is an effect of excellent mechanical strength such as impact strength and excellent plating adhesion.
[65]
The a) graft copolymer is preferably contained in a smaller amount than b) the graft copolymer, and in this case, it has excellent workability expressed by fluidity and no swelling or cracking of the plated film occurs after thermal shock evaluation, resulting in excellent thermal properties. There is.
[66]
The a) graft copolymer and b) the graft copolymer preferably have a weight ratio of 1:1.5 to 1:4, more preferably 1:1.5 to 1:3, and even more preferably 1: 1.7 to 1:3, and most preferably 1:2 to 1:3, and within this range, in this case, the fluidity is excellent, and there is no swelling or cracking of the plated film after thermal shock evaluation, so that the thermal characteristics are excellent. .
[67]
[68]
The a) vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is, for example, 30 to 70 wt% of a conjugated diene rubber of 0.05 µm to 0.2 µm, 5 to 30 wt% of a vinyl cyan compound, and 15 to 30 wt% of an aromatic vinyl compound. It may be graft polymerization, including 50% by weight, and in this case, there is an effect of excellent overall physical property balance such as mechanical properties, and excellent plating adhesion and thermal properties.
[69]
In another example, a) a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is 45 to 60% by weight of a conjugated diene rubber of 0.05 µm to 0.2 µm, 10 to 20% by weight of a vinylcyan compound, and 25 It may be graft-polymerized, including to 40% by weight, and in this case, the overall physical property balance such as mechanical properties is excellent, and plating adhesion and thermal properties are excellent.
[70]
[71]
The b) vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is, for example, 40 to 80% by weight of a conjugated diene rubber having a particle diameter of more than 0.2 μm to 0.5 μm, 3 to 20% by weight of a vinyl cyan compound, and an aromatic vinyl compound. It may be graft-polymerized, including 10 to 50% by weight, and in this case, there is an effect of excellent overall physical property balance such as mechanical properties, and excellent plating adhesion and thermal properties.
[72]
In another example, the b) vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is 50 to 70 wt. It may be graft-polymerized including 20 to 40% by weight of the vinyl compound, and in this case, there is an effect of excellent mechanical strength such as impact strength, and excellent plating adhesion and thermal properties.
[73]
[74]
The method for preparing each of the a) graft copolymer and b) the graft copolymer is not limited as long as it is a manufacturing method commonly used in this technical field, and as an example, may be prepared by emulsion polymerization. In this case, graph It has excellent mechanical properties and workability due to its excellent efficiency.
[75]
[76]
The c) aromatic vinyl compound-vinyl cyan compound copolymer is a non-grafted copolymer polymerized including an aromatic vinyl compound and a vinyl cyan compound, and for example, the aromatic vinyl compound c) 55 to 85% by weight based on the total weight of the copolymer , 55 to 75% by weight, or 60 to 70% by weight, and the vinylcyan compound may be c) 15 to 45% by weight, 20 to 40% by weight, or 20 to 35% by weight based on the total weight of the copolymer, , Within this range, fluidity, mechanical properties, and plating adhesion are excellent.
[77]
In the c) aromatic vinyl compound-vinyl cyan compound copolymer, the aromatic vinyl compound is one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene. The vinyl cyan compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. In this case, the effect of excellent processability and mechanical strength while excellent plating adhesion have.
[78]
The c) aromatic vinyl compound-vinyl cyan compound copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol, 60,000 to 180,000 g/mol, or 70,000 to 150,000 g/mol, for example, and impact strength within this range. While excellent mechanical strength such as, there is an effect of excellent plating adhesion.
[79]
In the present description, the weight average molecular weight is, for example, prepared by dissolving a resin in tetrahydrofuran (THF) at a concentration of 1 mg/ml, then filtering it with a 0.45 µm syringe filter, and using gel chromatography (GPC). Can be measured.
[80]
The method for preparing the c) aromatic vinyl compound-vinyl cyan compound copolymer is not particularly limited, and may be a manufacturing method commonly used in this technical field, and as an example, may be manufactured by continuous bulk polymerization. Not only cost is reduced, but mechanical properties are excellent.
[81]
[82]
Compound represented by formula 1
[83]
The thermoplastic resin composition according to the present disclosure includes, for example, 0.01 to 2 parts by weight, preferably more than 0.01 parts by weight to less than 2 parts by weight, more preferably 0.03 to 1.5 parts by weight based on 100 parts by weight of the base resin. Parts by weight, more preferably 0.05 to 1 parts by weight, most preferably 0.05 parts by weight or more to less than 1 part by weight, may be included, and in this case, there is an effect of excellent plating adhesion and appearance quality without deteriorating mechanical properties.
[84]
[Formula 1]
[85]

[86]
X may be hydrogen or a hydroxy group as an example, and Y may be hydrogen or as an example , and R 1 and R 2 may be independently an alkyl group having 1 to 10 carbon atoms as an example, and the R 3 and R 4 As an example, may independently be an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 10 carbon atoms, and R 5 and R 6 may be independently an alkyl group having 1 and 10 carbon atoms as an example, and Z is hydrogen as an example Alternatively, it may be a hydroxy group, and n may be an integer of 1 to 100, for example, and m may be an integer of 0 to 100, for example. While having mechanical properties equal to or higher than the same level, thermal properties, plating adhesion, and appearance quality are excellent.
[87]
The R 1 and R 2 may be, for example, independently an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and in this case, plating adhesion is greatly improved and the appearance quality after plating is excellent. It works.
[88]
The R 3 and R 4 may be, for example, independently an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 10 carbon atoms, and as another example, independently may be an aryl group having 6 to 8 carbon atoms or an alkyl group having 1 to 5 carbon atoms And, as another example, it may be a phenyl group, and in this case, there is no occurrence of non-plating and there is an excellent effect of plating adhesion.
[89]
The R 5 and R 6 may be, for example, independently an alkyl group having 1 and 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and in this case, the plating adhesion is greatly improved and the appearance quality after plating is excellent. It works.
[90]
The n may be, for example, an integer of 1 to 100, an integer of 10 to 90, or an integer of 20 to 80, and in this case, there is an effect of excellent appearance quality and plating adhesion without deteriorating thermal properties.
[91]
The m may be, for example, an integer of 0 to 100, an integer of 1 to 80, or an integer of 10 to 60, and in this case, there is an effect of excellent appearance quality and plating adhesion without deteriorating thermal properties.
[92]
The compound represented by Formula 1 may have, for example, a kinematic viscosity (25° C.) of 10 to 20,000 cSt, 10 to 15,000 cSt, or 10 to 10,000 cSt, preferably more than 5 cSt to less than 200 cSt, more preferably 10 to 100 cSt, more preferably 10 cSt or more to less than 100 cSt, even more preferably 10 to 50 cSt, most preferably 15 to 50 cSt, in this case, plating adhesion, non-plating, thermal properties and It has excellent plating properties such as plating appearance quality, and has excellent processability.
[93]
[94]
In the present description, the kinematic viscosity may be a value obtained by dividing the absolute viscosity by the density, and the absolute viscosity may be measured at 25° C. according to ASTM D445-46T.
[95]
The compound represented by Formula 1 may be, for example, at least one selected from the group consisting of terminally modified or unmodified polydimethylsiloxane and terminally modified or unmodified polymethylphenylsiloxane, and preferably, terminally modified or unmodified It may be polymethylphenylsiloxane, and in this case, gas generation is lowered during injection, heat resistance is increased, and thermal characteristics are excellent, and plating adhesion is greatly improved, so that the appearance quality is also excellent.
[96]
The terminal denaturation is not limited in the case of terminal denaturation conventional in the art.
[97]
[98]
Thermoplastic resin composition
[99]
The thermoplastic resin composition of the present disclosure may be, for example, a resin composition for plating, and 1 selected from the group consisting of heat stabilizers, antioxidants, impact modifiers, light stabilizers, plasticizers, lubricants, and antistatic agents within a range that does not affect physical properties. It may further include more than one type of additive, and in this case, there is an effect of implementing the function of the additive without deteriorating the underlying physical properties of the thermoplastic resin composition of the present invention.
[100]
The additive may be, for example, 0.1 to 10 parts by weight, or 1 to 5 parts by weight based on 100 parts by weight of the base resin, and within this range, the function of the additive without deteriorating the inherent properties of the thermoplastic resin composition of the present substrate Has the effect of implementing it.
[101]
The thermoplastic resin composition of the present disclosure, for example, has a melt index (220° C., 10 kg) of 10 to 40 g/10min, or 10 to 30 g/10min, preferably 15 to 30 g/10min, more preferably 18 to 30 g It may be /10min, and within this range, there is an effect of excellent physical property balance and workability.
[102]
The thermoplastic resin composition of the present disclosure, for example, has an impact strength of 20 kgf·cm/cm 2 or more, or 20 to 40 kgf·cm/cm 2 , preferably 20 to 36 kgf·cm/cm 2 , more preferably 23 to 36 It may be kgf·cm/cm 2 , and there is an effect of having an excellent balance of properties within this range.
[103]
The thermoplastic resin composition of the present disclosure may, for example, have a plating adhesion (10mm/80mm) of 10 N/cm or more, or 10 to 25 N/cm, preferably 10 to 16 N/cm, and the appearance after plating within this range There is an excellent effect in the balance of quality and physical properties.
[104]
[105]
Hereinafter, a method of manufacturing the thermoplastic resin composition of the present invention and a metal plated molded article including the composition will be described. In describing the method of manufacturing the thermoplastic resin composition of the present invention and a metal plated molded article including the composition, all the contents of the above-described thermoplastic resin composition are included.
[106]
[107]
Metal plating molded products
[108]
The metal-plated molded article of the present substrate may be molded with the thermoplastic resin composition of the present substrate and formed with a metal plating layer on the surface thereof. In this case, there is an effect of excellent plating adhesion and appearance quality between the surface and the plated film.
[109]
The metal plating layer may be anchored to the surface of the substrate made of the thermoplastic resin composition, and in this case, the plating adhesion between the surface and the plating film and the appearance quality are excellent.
[110]
The method of manufacturing the metal-plated molded article includes, for example, injecting the thermoplastic resin composition of the present invention to obtain an injection article; Etching the injection product using an etching solution; And plating the etched injection product. In this case, there is an effect of excellent plating adhesion without deteriorating mechanical properties and thermal properties.
[111]
The thermoplastic resin composition may be, for example, extruded pellets, and in this case, reproducibility, process stability, and process ease are excellent.
[112]
[113]
The etching process is a process of dissolving the rubber part in the ABS resin to give unevenness to the surface, and through this process, the hole formed by melting the rubber acts as an anchoring part that has a physical bonding force with the plating film, and thus plating adhesion In addition to giving the surface a polarity, it suppresses the occurrence of non-plating during the subsequent plating process.
[114]
In the etching step, the etching time may be, for example, 2 to 10 minutes, or 3 to 7 minutes, and the etching temperature may be, for example, 60 to 75 °C, or 65 to 70 °C, while reducing the process cost within this range. It is possible to obtain a molded article excellent in plating adhesion and thermal properties.
[115]
The etching solution may be one or more aqueous solutions selected from the group consisting of chromic anhydride, sulfuric acid, phosphoric acid, potassium permanganate, and hydrogen peroxide, for example, and in this case, there is an effect of excellent plating adhesion without deteriorating mechanical properties and thermal properties.
[116]
The manufacturing method of the metal-plated molded article may include, for example, a degreasing step of removing oil or the like from the injection article prior to the etching step.
[117]
In the degreasing step, oil may be removed by preferably treating the injection product with a surfactant, and the surfactant is not particularly limited if it is a surfactant commonly used in the degreasing step in the technical field to which the present invention belongs.
[118]
The degreasing step may be preferably carried out at 40 to 60°C for 1 to 30 minutes, more preferably at 50 to 60°C for 5 to 10 minutes, and there is an advantage of excellent degreasing efficiency within this range. .
[119]
The plating may include, for example, a plating pretreatment step including at least one of a neutralization step, a catalyzing step, and an activation step, and a plating treatment step including at least one of chemical plating and electroplating.
[120]
The neutralization step may be preferably treated with an aqueous hydrochloric acid solution, and in this case, there is an advantage in that residual chromic acid and the like are efficiently removed.
[121]
The neutralization step may be preferably treated with an aqueous hydrochloric acid solution at 20 to 30°C for 15 seconds to 1 minute, and more preferably treated with an aqueous hydrochloric acid solution at 25 to 30°C for 20 to 30 seconds, within this range There is an advantage in that residual chromic acid and the like are effectively removed from.
[122]
The catalytic step may preferably be a step of adsorbing metal to the anchor hole using a metal catalyst, and the metal catalyst is not particularly limited if it is a metal catalyst commonly used in pretreatment for plating in the technical field to which the present invention belongs. However, it may preferably be a palladium-tin catalyst, in which case palladium is adsorbed to the anchor hole.
[123]
The catalysis step may be preferably carried out at 20 to 40 °C for 1 to 10 minutes, more preferably at 25 to 35 °C for 1 to 5 minutes, and the anchor hole adsorption efficiency of metal within this range It has an excellent advantage.
[124]
The activation step may preferably be a step of activating by treatment with an aqueous sulfuric acid solution. In this case, the effect of activating the metal adsorbed to the anchor hole by removing other metals other than the metal to be adsorbed to the anchor hole is great.
[125]
The activation step may be preferably carried out at 45 to 65 °C for 1 to 10 minutes, more preferably at 50 to 60 °C for 1 to 5 minutes, and within this range, the activation effect is large.
[126]
The chemical plating may preferably be electroless plating using a metal salt, and the metal salt may preferably be nickel sulfate.
[127]
The chemical plating may be preferably carried out at 20 to 40 °C for 1 to 30 minutes, more preferably at 25 to 35 °C for 1 to 10 minutes, and within this range, the electroless plating properties are excellent. have.
[128]
The electroplating is preferably at least one electroplating selected from the group consisting of copper electroplating, nickel electroplating and chromium electroplating.
[129]
The copper electroplating may use without limitation a copper salt commonly used for copper electroplating in the technical field to which the present invention belongs, but preferably copper sulfate may be used.
[130]
The copper electroplating may be preferably carried out at 2 to 4 A/dm 2 for 20 to 60 minutes at 20 to 30 °C, and more preferably 2.5 to 3.5 A/dm 2 at 23 to 27 °C for 30 to 40 minutes . can do.
[131]
For the nickel electroplating, a nickel salt commonly used for nickel electroplating in the technical field of the present invention may be used without limitation, but nickel sulfate may be preferably used.
[132]
The nickel electroplating is preferably from 50 to 60 ℃ 10 to 30 minutes from 2 to 4 A / dm 2 may be carried out, and more preferably from 55 to from 60 ℃ 10 - 20 min 2.5 to 3.5 A / dm 2, carried out in can do.
[133]
In the chromium electroplating, a chromium-based compound commonly used in chromium electroplating in the technical field of the present invention may be used without limitation, but chromic anhydride may be preferably used.
[134]
The chromium electroplating is preferably from 45 to 65 ℃ 1 to 15 minutes 10 to 20 A / dm 2 may be carried out, and more preferably from 50 to 60 ℃ 1 to 5 minutes 13 to 18 A / dm 2 carried out in can do.
[135]
[136]
The plating method in the plating step is not particularly limited, and may be appropriately selected and carried out within a range commonly practiced in the art.
[137]
The use of the molded article is not particularly limited, but may preferably be an interior material or exterior material for an automobile, and in this case, there is an advantage of greatly satisfying the difficult plating reliability of the automotive field.
[138]
[139]
Method for producing a thermoplastic resin composition
[140]
The method for preparing the thermoplastic resin composition of the present disclosure is, for example, a) a conjugated diene rubber particle diameter of 0.05 µm to 0.2 µm. Base consisting of 5 to 40% by weight of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer having a rubber particle diameter of more than 0.2 μm to 0.5 μm and c) 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer 100 parts by weight of resin; And the following formula 1
[141]
[Formula 1]
[142]

[143]
(The X is hydrogen or a hydroxy group, Y is hydrogen or , and R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independently an aryl group having 6 to 12 carbon atoms or An alkyl group having 1 to 10 carbon atoms, R 5 and R 6 are independently an alkyl group having 1 and 10 carbon atoms, Z is hydrogen or a hydroxy group, n is an integer of 1 to 100, and m is an integer of 0 to 100 0.01 to 2 parts by weight of a compound represented by (is an integer); injecting into a twin screw extruder to melt kneading and extruding, and the compound represented by Formula 1 has a kinematic viscosity (25° C.) of 10 to 20,000 cSt In this case, the non-plating does not occur under a high unplated incidence rate, but the thermal properties, plating adhesion and appearance quality are excellent while having mechanical properties equal to or higher than the conventional one.
[144]
The method for preparing the thermoplastic resin composition of the present disclosure is preferably a) a vinyl cyan compound having a conjugated diene rubber particle diameter of 0.05 μm to 0.2 μm-conjugated diene rubber-aromatic vinyl compound graft copolymer 5 to 40% by weight, b) conjugated Diene rubber particle diameter of more than 0.2 μm to 0.5 μm or less vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer 5 to 40% by weight and c) aromatic vinyl compound-vinyl cyan compound copolymer 50 to 80% by weight consisting of 100 parts by weight of the base resin; And the following formula 1
[145]
[Formula 1]
[146]

[147]
(The X is hydrogen or a hydroxy group, Y is hydrogen or , and R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independently an aryl group having 6 to 12 carbon atoms or An alkyl group having 1 to 10 carbon atoms, R 5 and R 6 are independently an alkyl group having 1 and 10 carbon atoms, Z is hydrogen or a hydroxy group, n is an integer of 1 to 100, and m is an integer of 0 to 100 An integer) greater than 0.01 parts by weight to less than 2 parts by weight of the compound represented by; in a twin screw extruder, melt-kneading and extruding, wherein a) the graft copolymer is in an amount less than that of the b) graft copolymer The compound represented by Formula 1 is characterized in that the kinematic viscosity (25° C.) is greater than 5 cSt to less than 200 cSt, and the resin composition prepared within this range includes plating adhesion, non-plating, thermal properties, and It has an advantage that is suitable for a resin composition for plating because it has excellent plating properties such as plating appearance quality, and excellent processability.
[148]
[149]
The melt-kneading step may further include the above-described additives as an example.
[150]
The melt-kneading and extruding step may be performed using one or more selected from the group consisting of a single screw extruder, a twin screw extruder, and a Benbury mixer, for example, preferably a twin screw extruder, and uniformly mixing the composition using this After extruding, for example, a thermoplastic resin composition in the form of a pellet can be obtained. In this case, there is an effect of excellent plating adhesion and appearance quality without deterioration in mechanical properties, thermal properties, and non-plating occurrence.
[151]
The thermoplastic resin composition used in the method for producing the thermoplastic resin composition of the present invention includes all the contents of the thermoplastic resin composition of the present description.
[152]
[153]
Hereinafter, preferred embodiments are presented to aid in the understanding of the present invention, but the following examples are only illustrative of the present invention, and that various changes and modifications are possible within the scope of the present invention and the scope of the technical idea will be apparent to those skilled in the art, It is natural that such modifications and modifications fall within the appended claims.
[154]
[155]
[Example]
[156]
Materials used in Examples 1 to 8 and Comparative Examples 1 to 12 are as follows.
[157]
a) Vinylcyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer: ABS resin with a rubber particle diameter of 0.1 μm (DP229M from LG Chem)
[158]
b) Vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer: ABS resin with a rubber particle diameter of 0.3 μm (DP270M from LG Chemical)
[159]
c) Aromatic vinyl compound-vinyl cyan compound copolymer: Styrene-acrylonitrile copolymer (95 RF from LG Chemical)
[160]
d-1) Compound represented by Formula 1: Polydimethylsiloxane (PDMS) with a kinematic viscosity of 10 cSt (Shin-Etsu KF96-10cs)
[161]
d-2) Compound represented by Formula 1: Polymethylphenylsiloxane (PMPS) with a kinematic viscosity of 15 cSt (Shin-Etsu KF56)
[162]
d-3) Compound represented by Formula 1: Polydimethylsiloxane (PDMS) with a kinematic viscosity of 50 cSt (Shin-Etsu KF96-50cs)
[163]
d-4) Compound represented by Formula 1: Polydimethylsiloxane (PDMS) with a kinematic viscosity of 200 cSt (Shin-Etsu KF96-200cs)
[164]
d-5) Compound represented by Formula 1: Polydimethylsiloxane (PDMS) with a kinematic viscosity of 10,000 cSt (Shin-Etsu KF96H-10,000cs)
[165]
d-6) Compound represented by Formula 1: Polydimethylsiloxane (PDMS) with a kinematic viscosity of 5 cSt (Shin-Etsu KF96L-5cs)
[166]
d-7) Compound represented by Formula 1: Polymethylphenylsiloxane (PMPS) with a kinematic viscosity of 3,000 cSt (Shin-Etsu KF50)
[167]
[168]
Examples 1 to 8 and Comparative Examples 1 to 12
[169]
Each component was put into a twin-screw extruder so as to have the composition and content shown in Tables 1 and 2, respectively, and melted and kneaded at 220 to 250°C to prepare a pellet-type resin composition, and the prepared pellet-type resin composition was injected to physical properties. A specimen for measuring was prepared. A square specimen of 100mm X 100mm X 3mm standard and a cap-shaped specimen of 150mm X 80mm X 3mm standard were prepared through injection.
[170]
The prepared specimen was formed with a plating film having a uniform thickness of 30 μm or more in the following manner.
[171]
First, the oil was removed by treatment with a surfactant at 55° C. for 5 minutes, and butadiene was oxidized at 65° C. for 5 minutes using an aqueous chromic acid anhydride-sulfuric acid solution. Then, an aqueous hydrochloric acid solution was treated at 25° C. for 25 seconds to remove residual chromic acid, and an anchor hole adsorption of palladium was attempted using a palladium-tin catalyst at 30° C. for 2 minutes. The activation step was performed at 55° C. for 2 minutes to remove tin using an aqueous sulfuric acid solution, and electroless plating was performed at 30° C. for 5 minutes using nickel sulfate. In the electroplating performed after the electroless plating, copper, nickel, and chromium were used, and copper electroplating using copper sulfate was performed at 25° C. for 35 minutes at 3 A/dm 2 . And nickel electroplating using nickel sulfate was performed at 55° C. for 15 minutes at 3 A/dm 2 , and chromium electroplating using anhydrous chromic acid solution was performed at 55° C. at 15 A/dm 2 for 3 minutes .
[172]
[173]
[Test Example]
[174]
The properties of the specimens prepared in Examples 1 to 10 and Comparative Examples 1 to 12 were measured by the following method, and the results are shown in Tables 1 and 2 below.
[175]
* Melt Index (g/10min): Measured at 220° C. and 10 kg according to standard measurement ASTM D1238 using the prepared specimen.
[176]
* Impact strength (Notched Izod Impact Strength, kgf·cm/cm 2 ): It was measured according to standard measurement ASTM D256 using a specimen having a thickness of 6.4 mm.
[177]
* Plating adhesion (N/cm): A scratch of 10 mm width is made on the front surface of a plated square specimen (standard 100mm X 100mm X 3mm) and 80 mm vertically using a push-pull gage. The average value of the measured value was shown while peeling.
[178]
* Evaluation of unplated occurrence: The appearance of a cap-shaped specimen of 150mm X 80mm X 3mm standard was visually observed, indicating that there was no unplated part, and if there was any part of it, it was classified by X.
[179]
* Thermal shock test: In the case that no cracks or swelling of plating occur at all by visually observing the appearance of the plating film after performing the procedures as below ① to ⑤ in the chamber using a cap-shaped specimen ○, cracks and plating If the swelling occurred at least in part, it is indicated by classifying it with an X.
[180]
① Maintain the temperature in the chamber at -40 ℃ for 60 minutes
[181]
② Increase the temperature in the chamber to 80 ℃ within 1 minute
[182]
③ Maintain the temperature in the chamber at 80 ℃ for 60 minutes
[183]
④ Cool down the temperature in the chamber to -40 ℃ within 1 minute
[184]
⑤ Repeat the process of ① to ④ 4 times
[185]
* Plating appearance quality: After plating the cap-shaped specimen, visually observe the appearance quality (excluding unplated areas), and if there is no fogging area on the outermost plated surface, it is referred to as'no problem' and fogging. If there is a part, it was evaluated as'defective'.
[186]
[187]
[Table 1]
division Example
One 2 3 4 5 6 7 8 9 10
a 10 10 10 10 10 10 10 15 6 5
b 20 20 20 20 20 20 30 25 24 25
c 70 70 70 70 70 70 60 60 70 70
d-1 0.2 - - - - - - - - -
d-2 - 0.2 - - - - - - - -
d-3 - - 0.05 0.2 0.5 One 0.2 0.2 0.2 0.2
d-4 - - - - - - - - - -
d-5 - - - - - - - - - -
d-6
d-7
Melt index 28 28 28 30 28 27 22 18 35 35
Impact strength 24 23 24 25 25 27 36 34 28 29
Plating adhesion 11 11 10 12 11 11 14 16 10 8
Whether non-plating occurs ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Thermal shock test ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Plating appearance quality nothing strange
[188]
[Table 2]
division Comparative example
One 2 3 4 5 6 7 8 9 10 11 12
a 10 10 10 10 10 10 10 - 30 20 5 20
b 20 20 20 20 20 20 20 30 - 20 10 40
c 70 70 70 70 70 70 70 70 70 60 85 40
d-1 - - - - - - - - - - - -
d-2 - - - - - - - - - - - -
d-3 - 0.01 2 - - - - 0.2 0.2 0.2 0.2 0.2
d-4 - - - 0.2 - - - - - - - -
d-5 - - - - 0.2 - - - - - - -
d-6 0.2
d-7 0.2
Melt index 30 29 27 28 28 30 28 33 16 12 42 8
Impact strength 24 24 27 24 25 23 24 28 13 32 10 40
Plating adhesion 8 9 4 6 5 10 6 5 10 14 3 17
Whether non-plating occurs X X ○ ○ ○ ○ ○ ○ ○ ○ X ○
Thermal shock test ○ ○ X X X ○ X X X X X X
Plating appearance quality nothing strange Bad nothing strange
[189]
(The contents of a, b, and c in Tables 1 and 2 are weight percent based on 100 weight percent of the total base resin, and the content of d is weight parts based on the total 100 weight percent of the base resin.) Table 1 above. As shown in, in the case of Examples 1 to 9 of the present invention, excellent Due to the melt index, it was confirmed that the processability was excellent, and the impact strength, plating adhesion, and thermal properties were greatly improved.
[190]
Furthermore, it was confirmed that the present invention did not generate unplated at all even under the condition that the unplated generation rate should be increased by reducing the etching time in the usual plating process, but the mechanical properties and thermal properties were excellent, and in particular, the plating adhesion was greatly improved. .
[191]
For reference, in Example 10, in which the weight ratio of a) graft copolymer and b) graft copolymer is 1:5, the plating adhesion was slightly lowered, but the melt index and impact strength were excellent, and the occurrence of non-plating, thermal shock test And it was confirmed that it was excellent without any abnormality in the plating appearance quality.
[192]
On the other hand, as shown in Table 2, d) non-plating occurs in the case of Comparative Examples 1 and 2 that do not contain a siloxane resin or fall within the content range according to the present invention, and d) the content of the silicone resin according to the present invention. In the case of Comparative Example 3 exceeding the range, it was confirmed that the plating adhesion was significantly lowered, and swelling or cracking of the plating film occurred after thermal shock evaluation, resulting in poor thermal properties.
[193]
In addition, d) Comparative Examples 4, 5, and 7 in which the kinematic viscosity of the siloxane resin was 200 cSt or higher had poor plating adhesion, and swelling or cracking of the plated film was generated after thermal shock evaluation, resulting in poor thermal properties, and d) the kinematic viscosity of the silicone resin was 5 In Comparative Example 6 below cSt, it was confirmed that the plating appearance quality was very poor.
[194]
In addition, Comparative Example 8, which includes only ABS resin having a large rubber particle diameter, significantly reduced plating adhesion, and also caused swelling or cracking of the plating film after thermal shock evaluation, resulting in poor thermal properties, and a) ABS resin having a small rubber particle diameter In Comparative Examples 9 and 10 including a) ABS resin as much as b) ABS resin, it was confirmed that the fluidity was inferior, and swelling or cracking of the plated film was generated after thermal shock evaluation, resulting in poor thermal properties.
[195]
In addition, c) Comparative Example 11 containing 85% by weight of a styrene-acrylonitrile copolymer resin exceeding the content range according to the present invention, significantly lowered the impact strength and plating adhesion, and unplated was generated. The thermal properties were poor due to swelling or cracking, and on the contrary, c) 40% by weight of a styrene-acrylonitrile copolymer resin was less than the content range according to the present invention. It was confirmed that the thermal properties were poor due to the occurrence of swelling or cracking of the plating film.
[196]
In conclusion, only when a) ABS resin, b) ABS resin, c) SAN resin and d) siloxane resin satisfy the scope according to the present invention, such as plating adhesion, non-plating, thermal characteristics and plating appearance quality, etc. It was confirmed that all of the plating properties were excellent and the processability was excellent and suitable for the resin composition for plating.
[197]
Claims
[Claim 1]
a) 5 to 40 wt% of a vinyl cyan compound having a conjugated diene rubber particle diameter of 0.05 µm to 0.2 µm-conjugated diene rubber-aromatic vinyl compound graft copolymer, b) a vinyl cyan having a conjugated diene rubber particle diameter of more than 0.2 µm to 0.5 µm 100 parts by weight of a base resin comprising 5 to 40% by weight of a compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and c) 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; And the following Formula 1 [Chemical Formula 1] (wherein X is hydrogen or a hydroxy group, Y is hydrogen or , and R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independently It is a C6-C12 aryl group or a C1-C10 alkyl group, and R 5 and R 6Is independently an alkyl group having 1 and 10 carbon atoms, wherein Z is hydrogen or a hydroxy group, wherein n is an integer of 1 to 100, and m is an integer of 0 to 100) Less than a part; Including, the a) graft copolymer is included in an amount less than that of the b) graft copolymer, and the compound represented by Formula 1 has a kinematic viscosity (25°C) of more than 5 cSt to less than 200 cSt. Thermoplastic resin composition, characterized in that.
[Claim 2]
The thermoplastic resin composition of claim 1, wherein the a) graft copolymer and b) the graft copolymer have a weight ratio of 1:1.5 to 1:4.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein the compound represented by Formula 1 has a kinematic viscosity (25°C) of 10 to 100 cSt.
[Claim 4]
The method of claim 1, wherein the a) vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is 30 to 70% by weight of a conjugated diene rubber having a particle diameter of 0.05 μm to 0.2 μm, 5 to 30% by weight of a vinyl cyan compound, and A thermoplastic resin composition comprising 15 to 50% by weight of an aromatic vinyl compound and graft polymerization.
[Claim 5]
The method of claim 1, wherein the b) vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer has a particle diameter of more than 0.2 µm to 0.5 µm by weight of a conjugated diene rubber of 40 to 80% by weight, and 3 to 20% by weight of a vinylcyan compound. And 10 to 50% by weight of an aromatic vinyl compound and graft polymerization.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the c) aromatic vinyl compound-vinyl cyan compound copolymer comprises 55 to 85% by weight of an aromatic vinyl compound and 15 to 45% by weight of a vinylcyan compound.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a plating adhesion (10mm/80mm) of 10 N/cm or more.
[Claim 8]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a melt index (220° C., 10 kg) of 10 to 40 g/10min.
[Claim 9]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a resin composition for plating.
[Claim 10]
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition further comprises at least one selected from the group consisting of a heat stabilizer, an antioxidant, an impact modifier, a light stabilizer, a plasticizer, a lubricant and an antistatic agent.
[Claim 11]
a) 5 to 40% by weight of a vinyl cyan compound having a conjugated diene rubber particle diameter of 0.05 μm to 0.2 μm-conjugated diene rubber-aromatic vinyl compound graft copolymer, b) a vinyl cyan having a conjugated diene rubber particle diameter greater than 0.2 μm to 0.5 μm 100 parts by weight of a base resin comprising 5 to 40% by weight of a compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and c) 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; And the following Formula 1 [Chemical Formula 1] (wherein X is hydrogen or a hydroxy group, Y is hydrogen or , and R 1 and R 2 are independently an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independently It is a C6-C12 aryl group or a C1-C10 alkyl group, and R 5 and R 6Is independently an alkyl group having 1 and 10 carbon atoms, Z is hydrogen or hydroxy group, n is an integer of 1 to 100, and m is an integer of 0 to 100) Less than part; including the step of melt-kneading and extruding by introducing a twin screw extruder, wherein the a) graft copolymer is contained in a smaller amount than that of the b) graft copolymer, and the compound represented by Formula 1 has a kinematic viscosity ( 25 ℃) is a method for producing a thermoplastic resin composition, characterized in that more than 5 cSt to less than 200 cSt.
[Claim 12]
A metal plated molded article, characterized in that it is molded from the thermoplastic resin composition according to any one of claims 1 to 10 and a metal plated layer is formed on the surface.
[Claim 13]
The metal plated molded article of claim 12, wherein the metal plated layer comprises at least one selected from the group consisting of copper, nickel, and chromium.
[Claim 14]
The metal plated molded article according to claim 12, wherein the metal plated molded article is an automobile interior material or an automobile exterior material.
[Claim 15]
A step of injecting the thermoplastic resin composition of any one of claims 1 to 10 to obtain an injection product, etching the injection product using an etching solution, and plating the etched injection product. Method of manufacturing a metal plated molded article.