KR20200034381A - Thermoplastic resin composition, method for preparing thereof and molding products comprising thereof - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition for plating, a method for manufacturing the same, and a molded article comprising the same. More particularly, the present invention relates to a thermoplastic resin composition for plating, a method for manufacturing the same, and a molded article comprising the same, wherein the composition includes two types of graft copolymers having different average particle diameters of conjugated diene rubber, and an aromatic vinyl compound-vinyl cyan compound copolymer in a specific ratio, and includes a dialkanolamine-based compound within a specific content range, thereby providing advantages of having improved plating adhesion under the same process conditions compared to the conventional thermoplastic resin composition while maintaining high mechanical properties and physical properties such as processability, and having an excellent appearance quality.

Description

Thermoplastic resin composition, method for manufacturing the same, and molded article containing the same {THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THEREOF AND MOLDING PRODUCTS COMPRISING THEREOF}

The present invention relates to a thermoplastic resin composition, a method of manufacturing the same, and a molded article containing the same, more specifically, while maintaining high mechanical properties, processability, thermal properties, etc., the adhesion of plating in the same process as the conventional thermoplastic resin composition for plating and It relates to a thermoplastic resin composition for plating and the like that can provide the advantage of improving the appearance quality.

In general, resin molded products applied to automobiles, home appliances, etc. are used by plating the surface to improve the external characteristics of the product in addition to improving physical properties such as corrosion resistance, chemical resistance, abrasion resistance, or mechanical strength, for example, acrylonitrile- This includes molded products based on butadiene-styrene resin (Acrylonitrile-Butadiene-Styrene, hereinafter referred to as 'ABS resin').

ABS resin is widely used in automotive supplies, electrical / electronic products, and office equipment due to its stiffness and chemical resistance of acrylonitrile, processability of butadiene and styrene, mechanical strength, and beautiful appearance characteristics. Plating of ABS resin materials is generally Degreasing, etching, neutralization, catalysis, activation, chemical plating, and electroplating are performed.

The etching process is a process of melting the rubber part in the ABS-based resin to impart unevenness to the surface. Through this process, the hole formed by the melt of the rubber acts as an anchoring site that has physical bonding strength with the plating film, resulting in adhesion to the plating. It is the process required to secure it. Particularly, the ABS resin has a low polarity, so the catalyst adsorption rate is low, so this process must be performed. When the surface is formed through etching, an uneven structure is formed and the polarity is imparted to facilitate catalyst adsorption.

On the other hand, even if plating is performed in the same process, the etching effect is different depending on the type of ABS resin, and if the concavo-convex structure is not well formed in the etching process, the catalyst adsorption rate decreases and the adhesion of the plating falls, and the plating is not partially formed. Problems such as phenomenon occur. Therefore, the etching efficiency is increased by increasing the time and temperature of the etching process, or by changing the composition or changing the concentration of the etching solution. However, this method increases the overall process time, resulting in a decrease in production efficiency and an increase in cost.

Accordingly, there is a need to develop an ABS-based material capable of improving the adhesion rate and plating quality by increasing the catalyst adsorption rate without reducing the etching process efficiency.

Japanese Patent Publication 2017-206752A

In order to solve the problems of the prior art as described above, the present invention is a thermoplastic resin for plating that can improve plating adhesion and appearance quality while maintaining mechanical properties, thermal properties, processability, etc. at the same level as the conventional thermoplastic resin composition for plating. It is an object to provide a composition.

Furthermore, the present invention aims to contribute to improving the plating process efficiency by improving the plating adhesion compared to the prior art, shortening the process time or temperature during the plating process.

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

In order to achieve the above object, the present invention is a first graft copolymer 5 to 30% by weight of an aromatic vinyl compound and a vinyl cyan compound grafted to a conjugated diene rubber having an average particle diameter of 0.03 μm to 0.2 μm; 10 to 40 wt% of a second graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of more than 0.2 μm to 0.5 μm; And 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; provides a thermoplastic resin composition characterized in that it comprises 0.25 to 3.5 parts by weight of a dialkanolamine-based compound.

In addition, the present invention is an aromatic vinyl compound and a vinyl cyan compound grafted to the first graft copolymer 5 to 30% by weight of a conjugated diene rubber having an average particle diameter of 0.03㎛ to 0.2㎛; 10 to 40 wt% of a second graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of more than 0.2 μm to 0.5 μm; And 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; blending 0.25 to 3.5 parts by weight of a dialkanolamine-based compound, and then melt-kneading and extruding it. It provides a method for producing a thermoplastic resin composition characterized in that.

In addition, the present invention provides a molded article, which is molded from the composition and has a metal plating layer formed on at least one surface.

According to the present invention, while maintaining the mechanical properties, thermal properties, processability, etc. of the same level as the conventional thermoplastic resin composition for plating, it is possible to provide an advantage that the plating adhesion is improved and the appearance quality is superior to that of the prior art.

In particular, the resin composition according to the present invention has a melt index (220 ° C., load 10 kg) of 10 to 30 g / 10 min, and is easy to mold and process, but has an impact strength of 20 kgfcm / cm ² As described above, the mechanical properties are excellent, and the plating adhesion is 9 N / m or more, so that the plating process efficiency can be improved, and unplated or swelling does not occur, thereby providing an excellent appearance quality.

1 is a schematic view showing a process in which a catalyst is adsorbed on a surface of a material in an activation step during a plating process of a molded article made of a resin composition.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method for manufacturing the same, and a molded article containing the same will be described in detail.

The present inventors, while maintaining the same level of mechanical properties, formability and the like as the above-mentioned conventional thermoplastic resin composition for plating, to further improve the adhesion and appearance quality of the plating, two types of graft copolymers having different average particle diameters of the conjugated diene, When the aromatic vinyl compound-vinyl cyan compound copolymer is blended at a specific ratio, and a dialkanolamine-based compound is added within a specific content range, plating adhesion is improved while maintaining high mechanical properties, etc. Since the plating phenomenon did not occur, it was confirmed that the appearance quality could also be improved and the present invention was completed based on this.

The thermoplastic resin composition of the present invention includes, for example, 5 to 30 wt% of a first graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of 0.03 μm to 0.2 μm; 10 to 40 wt% of a second graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of more than 0.2 μm to 0.5 μm; And 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; and 0.25 to 3.5 parts by weight of a dialkanolamine-based compound, including mechanical properties and moldability of the composition. While maintaining high, the adhesion to plating can be improved, contributing to the improvement of the efficiency of the plastic plating process and the quality of plating products.

Hereinafter, each constituent component constituting the resin composition of the present description will be described in detail.

Graft  Copolymer

The composition of the present base material includes two types of graft copolymers having different average particle diameters of the conjugated diene rubber, and in this case, it is possible to simultaneously secure mechanical properties such as impact resistance of the composition and processing and moldability, but also has better plating adhesion. It provides an advantage.

The composition of the present disclosure is, for example, a conjugated diene having an average particle diameter of 0.03 μm to 0.2 μm, a first graft copolymer having an aromatic vinyl compound and a vinyl cyan compound grafted to rubber, and a conjugated diene having an average particle diameter of more than 0.2 μm to 0.5 μm. The rubber includes a second graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted, and in this case, the composition has excellent mechanical properties and moldability while improving plating adhesion.

When the two types of graft copolymer are not mixed, and only one of the first graft copolymer and the second graft copolymer is included, physical bonding strength between the material surface and the plating layer during plating is inferior, particularly relative As a result, when the first graft copolymer having a small particle diameter is applied alone, the impact resistance of the material is lowered, and when the second graft copolymer is applied alone, the melt index is lowered and moldability may be lowered. .

The average particle diameter of the polymer in the present description indicates a value measured using an intensity Gaussian distribution in a dynamic light skating method using a particle size distribution analyzer (Nicomp 380), unless otherwise specified.

For example, the first graft copolymer may be included in a proportion of 5 to 30% by weight, 10 to 25% by weight, or 10 to 20% by weight based on the total weight of the base resin of the present substrate, and within this range, the composition Both mechanical properties and formability are excellent.

The first graft copolymer is, for example, 20 to 80% by weight of a conjugated diene rubber having an average particle diameter of 0.03 to 0.2 µm, 10 to 70% by weight of an aromatic vinyl compound, and 1 to 30% by weight of a vinyl cyan compound. It may be a copolymer, and within this range, there is an advantage in that the balance of physical properties such as mechanical properties and moldability of the composition is excellent.

In another example, the first graft copolymer is 30 to 75 wt% of a conjugated diene rubber having an average particle size of 0.03 μm to 0.2 μm, 15 to 65 wt% of an aromatic vinyl compound, and 3 to 25 wt% of a vinyl cyan compound. It may be a copolymer, in this case provides excellent mechanical properties of the composition, yet easy molding.

In another example, the first graft copolymer comprises 45 to 65 wt% of a conjugated diene rubber having an average particle size of 0.03 μm to 0.2 μm, 20 to 55 wt% of an aromatic vinyl compound, and 5 to 20 wt% of a vinyl cyan compound. It may be a graft copolymer, and the physical property balance of the composition is excellent within this range.

The first graft copolymer has, for example, an aromatic vinyl compound and a vinyl cyan compound in a conjugated diene rubber having an average particle diameter of 0.03 μm to 0.2 μm, 0.05 μm to 0.2 μm, 0.05 μm to 0.15 μm, or 0.08 μm to 0.12 μm. It may be a grafted graft copolymer.

For example, the second graft copolymer may be included in a ratio of 10 to 40% by weight, 15 to 30% by weight, or 15 to 25% by weight based on the total weight of the base resin of the present substrate, and within this range, the composition Both mechanical properties and formability can be satisfied.

The second graft copolymer is, for example, a graft containing 20 to 80% by weight of a conjugated diene rubber having an average particle diameter of more than 0.2 μm to 0.5 μm, 10 to 70% by weight of an aromatic vinyl compound, and 1 to 30% by weight of a vinyl cyan compound. It may be a copolymer, and within this range, there is an advantage that the physical properties such as mechanical properties and moldability of the composition are excellent.

In another example, the second graft copolymer is a graft air containing 30 to 75% by weight of a conjugated diene rubber having an amount of more than 0.2 μm to 0.5 μm, 15 to 65% by weight of an aromatic vinyl compound, and 3 to 25% by weight of a vinyl cyan compound. It may be a coalescence, and in this case, the composition has excellent mechanical properties while providing an advantage of easy molding.

In another example, the second graft copolymer is a graft containing 45 to 65 wt% of a conjugated diene rubber having a thickness of more than 0.2 μm to 0.5 μm, 20 to 55 wt% of an aromatic vinyl compound, and 5 to 20 wt% of a vinyl cyan compound. It may be a copolymer, and within this range, the composition has excellent physical property balance.

The second graft copolymer is, for example, an average particle diameter of more than 0.2㎛ to 0.5㎛, 0.25㎛ to 0.5㎛, 0.25㎛ to 0.3㎛ or 0.3㎛ to 0.35㎛ conjugated diene rubber, aromatic vinyl compounds and vinyl cyan compounds It may be a grafted graft copolymer.

The composition of the present disclosure may include the first graft copolymer and the second graft copolymer in a weight ratio of 1: 1 to 1: 3, 1: 1.5 to 1: 3 or 1: 1.5 to 1: 2.5, , It can satisfy all of the mechanical properties, moldability, etc. of the composition within this range, it provides an advantage that the physical property balance is excellent and the adhesion to plating is further improved.

The conjugated diene rubber contained in the first graft copolymer and the second graft copolymer may be the same or different, for example, butadiene rubber, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and ethylene-propylene It may be at least one selected from copolymers, preferably butadiene rubber or butadiene-styrene copolymer, and most preferably, butadiene rubber.

The aromatic vinyl compounds included in the first graft copolymer and the second graft copolymer may be the same as or different from each other, for example, styrene, alpha-methylstyrene, para-methylstyrene, ortho-ethylstyrene, and vinyl It may be one or more selected from toluene, preferably styrene.

The vinyl cyan compound contained in the first graft copolymer and the second graft copolymer may be the same or different from each other, and preferably, one or more selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile. It may be, and more preferably it may be acrylonitrile.

Each of the first graft copolymer and the second graft copolymer may be prepared by, for example, emulsion polymerization, bulk polymerization, solution polymerization, or suspension polymerization, and preferably those prepared by emulsion polymerization advantageous for reaction control can be used. have.

Aromatic vinyl compound-vinyl cyan compound copolymer

In the present disclosure, the aromatic vinyl compound-vinyl cyan compound copolymer may be included in a ratio of 50 to 80% by weight, 60 to 75% by weight, or 65 to 75% by weight based on the total weight of the base resin, and the moldability of the composition within this range This excellent yet sufficient adhesion to the surface of the material in the etching step during the plating process can be improved plating adhesion.

For example, the aromatic vinyl compound-vinyl cyan compound copolymer may be a copolymer containing 55 to 85% by weight of an aromatic vinyl compound and 15 to 45% by weight of a vinyl cyan compound, in which case, the moldability and impact resistance of the composition are excellent. However, in the plating process, unevenness is sufficiently provided on the surface of the material, thereby contributing to the improvement of plating adhesion.

In another example, the aromatic vinyl compound-vinyl cyan compound copolymer may be a copolymer containing 60 to 85% by weight of an aromatic vinyl compound and 15 to 40% by weight of a vinyl cyan compound, and impact resistance and moldability within this range. While excellent, sufficient unevenness may be provided on the surface in the etching process during plating.

In another example, the aromatic vinyl compound-vinyl cyan compound copolymer may be a copolymer comprising 65 to 80% by weight of the aromatic vinyl compound and 20 to 35% by weight of the vinyl cyan compound, in which case the mechanical strength and molding of the composition The plating adhesion can be further improved by providing sufficient unevenness to the surface of the material in the etching step during plating while having excellent properties.

The aromatic vinyl compound included in the aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, one or more selected from styrene, alpha-methylstyrene, para-methylstyrene, ortho-ethylstyrene, and vinyl toluene, preferably May be styrene.

The vinyl vinyl compound included in the aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, one or more selected from acrylonitrile, ethacrylonitrile, and methacrylonitrile, and preferably acrylonitrile.

The aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by emulsion polymerization, bulk polymerization, or solution polymerization, and preferably, those prepared by bulk polymerization may be used. In this case, residues such as unreacted monomers and emulsifiers may be used. Less, the appearance quality of the plated molded article provides a better advantage.

The aromatic vinyl compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight of 50,000 to 200,000 g / mol, 60,000 to 190,000 g / mol, or 70,000 to 180,000 g / mol, and impact strength and processability within this range. It provides excellent advantages.

In the present description, the weight average molecular weight is a value measured at 25 ° C using gel permeation chromatography by dissolving the resin in tetrahydrofuran (THF), unless otherwise specified, and polystyrene was used as a standard.

Dialkanolamine  compound

In the present description, the dialkanolamine-based compound is added to improve plating adhesion and appearance quality. The operation of the dialkanolamine-based compound will be described with reference to FIG. 1. 1 (a) shows a process in which a catalyst is adsorbed in an activation step when plating a molded article made of a resin composition according to the prior art that does not contain a dialkanolamine-based compound, and FIG. 1 (b) is When plating a molded article made of a thermoplastic resin composition containing a diethanol amine-based compound, it is a schematic diagram showing a process in which a catalyst is adsorbed in an activation step. As shown in FIG. 1, the dialkanolamine-based compound may act as a surface modifier in the step of activating the etched surface during the plating process to improve the catalyst adsorption rate, thereby improving the plating adhesion compared to the prior art, and It provides an excellent appearance quality effect without bulging or unplated parts.

The dialkanolamine-based compound may be included as a base resin 100 parts by weight, 0.25 to 3.5 parts by weight, 0.3 to 3 parts by weight or 0.3 to 2 parts by weight, and within this range, the mechanical properties and moldability of the composition are kept high In spite of this, there is an effect that the plating adhesion and the appearance quality are improved, and when the amount used thereof exceeds 3.5 parts by weight, the corresponding component is eluted, and the plating adhesion and the appearance quality may be deteriorated.

The dialkanolamine-based compound may be, for example, a compound represented by the following Chemical Formula 1, in this case, while maintaining high mechanical properties and moldability of the ABS-based resin composition, the adhesion of plating, the appearance quality of the plated article is improved. to provide.

[Formula 1]

In Chemical Formula 1, R ₁ is selected from chain alkyl having 5 to 25 carbon atoms, branched alkyl having 5 to 25 carbon atoms, or alkenyl having 5 to 25 carbon atoms, and R ₂ and R ₂ ′ may be the same or different from each other. And each independently selected from ethyl, propyl, and isopropyl.

In another example, in Formula 1, R ₁ is a chain alkyl or alkenyl having 6 to 20 carbon atoms, and R ₂ and R ₂ ′ may be diethanolamine-based compounds that are ethyl.

In a specific example, the diethanolamine-based compounds include cocamide diethanolamine, lauramide diethanolamine, oleamide diethanolamine, myristicamide diethanolamine, stearamide diethanolamine, palmitamide diethanolamine and linol. It may be at least one selected from reamide diethanolamine, preferably cocamide diethanolamine or lauramide diethanolamine, and most preferably cocamide diethanolamine.

The composition of the present substrate may optionally further contain additives as necessary, and additives include, for example, antioxidants, heat stabilizers, fillers, lubricants, dyes, pigments, colorants, mold release agents, flame retardants, antistatic agents, antibacterial agents, processing aids, etc. It may be one or more selected from, but is not limited thereto.

The additive may be included, for example, 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 part by weight based on 100 parts by weight of the composition, and within this range, the thermoplastic resin composition of the present disclosure is inherent The function of the additive can be realized without degrading the base physical properties.

The composition of the present disclosure is suitable as a resin composition for plating as it contains a dialkanolamine-based compound capable of improving the catalyst adsorption rate by acting as a surface modifier in the step of activating the etched surface during the plating process. In addition, since the composition of the present substrate provides a higher catalyst adsorption rate compared to the prior art, it provides an advantage that a plating adhesion of the same level as that of the conventional composition can be secured even if the plating process time is shortened or the temperature is decreased.

For example, the composition of the present substrate provides an excellent plating quality of 9 N / cm or more, 10 N / cm or more, 9 N / cm to 12 N / cm, or 10 N / cm to 11 N / cm for plating adhesion.

The composition of the present substrate has an excellent melt index (220 ° C., load 10 kg) of 10 to 30 g / 10 min, 15 to 30 g / 10 min, or 20 to 25 g / 10 min, for example, and provides advantages in easy processing and molding in various shapes. .

The composition of the present substrate has an impact strength measured according to ASTM D256 of 20 kgfcm / cm ² The above or 20 to 40 kgfcm / cm ² provides excellent impact resistance.

Hereinafter, a method of manufacturing the thermoplastic resin composition of the present disclosure will be described in detail, and since it shares all the technical features with the thermoplastic resin composition described above, a description overlapping with the above description will be omitted.

The method of manufacturing the thermoplastic resin composition of the present disclosure includes, for example, 5 to 30% by weight of a first graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of 0.03 μm to 0.2 μm; 10 to 40 wt% of a second graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of more than 0.2 μm to 0.5 μm; And 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; blending 0.25 to 3.5 parts by weight of a dialkanolamine-based compound, and then melt-kneading and extruding it. It is characterized in that, while providing excellent mechanical properties, molding and processability of the final product within this range, the adhesion to plating is improved, and the appearance quality after plating is excellent.

The dialkanolamine-based compound may be a compound represented by Formula 1, more preferably cocamide diethanolamine, lauramide diethanolamine, oleamide diethanolamine, myristicamide diethanolamine, stear It may be at least one diethanolamine-based compound selected from amide diethanolamine, palmitamide diethanolamine and linoleamide diethanolamide.

The melt kneading and extrusion is not particularly limited as long as it is equipment and conditions commonly used in the art, and preferably, a barn kneader, a single screw extruder, a twin screw extruder, and a booth kneader may be used.

The melt-kneading and extrusion may be performed at 150 to 280 ° C or 200 to 250 ° C, for example, but it is not limited thereto.

The composition prepared through the melt kneading and extrusion may be provided as a pellet having a desired shape or size using a pelletizer.

Furthermore, the thermoplastic resin composition of the present disclosure can be provided as a molded article for various uses.

The molded article of the substrate may include, for example, a substrate molded from the composition and a metal plating layer formed on at least one surface of the substrate, but is not limited thereto. The molded article comprising the composition of the present substrate has excellent plating adhesion, yet has no swelling or unplated portion of the metal plating layer, thereby providing excellent appearance quality.

In describing the thermoplastic resin composition of the present disclosure, a method for manufacturing the same, and a molded article containing the same, other conditions or equipment not explicitly described may be appropriately selected within a range generally practiced in the art, and is not particularly limited. Is indicated.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is no wonder that such variations and modifications fall within the scope of the appended claims.

Materials used in the following examples and comparative examples are as follows.

A. Graft  Copolymer

(A1) As an ABS resin grafted with 45 to 60% by weight of styrene, 25 to 40% by weight and 10 to 20% by weight of vinyl cyan compound, butadiene rubber having an average particle size of 0.1 µm, a DP229M product of LG Chem.

(A2) As an ABS resin grafted with 50 to 70% by weight of styrene and 20 to 40% by weight of styrene and 5 to 15% by weight of a vinyl cyan compound, a DP270M product manufactured by LG Chem.

B. Aromatic vinyl compound-vinyl cyan compound copolymer

As a SAN resin prepared by bulk polymerization and containing 55 to 85% by weight of styrene and 15 to 45% by weight of acrylonitrile, 95RF product of LG Chem was used.

C. Dialkanolamine  compound

Cocamide diethanolamine was used.

[Examples and Comparative Examples]

Example  1 to 4 and Comparative example  1 to 3

Each component was blended with the composition and content shown in Table 1 below, and melt-kneaded and extruded at 220 to 250 ° C using a twin-screw extruder to prepare a resin composition, and then pellets were obtained using a pelletizer. The thus prepared pellet was injected to prepare a specimen of a thermoplastic resin composition for measuring physical properties.

In addition, in order to check the plating properties, 100 mm X 100 mm X 3 mm standard square specimens and 150 mm x 80 mm x 3 mm standard cap-shaped specimens were manufactured through injection, and uniform thickness of 30 µm or more was performed as follows. One metal plating layer was formed.

First, the surface of the specimen was removed by using a surfactant at 55 ° C for 5 minutes, and the surface of the specimen was etched using chromic anhydride-sulfuric acid as an etchant at 65 ° C for 5 minutes to form an uneven structure on the surface. Then, treatment with an aqueous hydrochloric acid solution at 25 ° C. for 25 seconds removed the residual chromic acid, and anchoring of palladium with an anchor hole was promoted 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. Copper, nickel, and chromium were used in the electroplating performed after electroless plating, and copper electroplating using copper sulfate was performed at 3 A / dm ² for 35 minutes at 25 ° C. In addition, nickel electroplating using nickel sulfate was performed at 3 A / dm ² at 55 ° C for 15 minutes, and electroplating using anhydrous chromic acid solution was performed at 15 A / dm ² at 55 ° C for 3 minutes.

[Test Example]

The physical and chemical properties of the specimens prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

* Melt index (Melt Index, g / 10min): was measured in accordance with ASTM D1238 at 220 ℃, 10kg conditions.

* Notched Izod Impact Strength (kgfcm / cm ² ): The impact strength of a specimen with a thickness of 6.4 mm was measured at room temperature according to ASTM D256.

* Plating adhesion (N / cm): 10mm width is scratched on the front surface of the plated square specimen (standard: 100mm x 100mm x 3mm) and 80mm is vertically pushed using a push-pull gage. The average value of the measured values was shown while peeling.

* Evaluation of plating quality: When there is no swelling of the unplated area and the plating layer by visually observing the appearance of the plated cap-shaped specimen (specification: 150mm x 80mm x 3mm) ○, if any unplated or swelled part occurs Shown.

division Example Comparative example One 2 3 4 One 2 3 Base
Suzy A1 10 10 10 10 10 10 10 A2 20 20 20 20 20 20 20 B 70 70 70 70 70 70 70 C 0.3 One 2 3 0.1 5 0 Melt Index [g / 10min] 20 21 24 27 19 33 19 Impact strength [kgfcm / cm ² ] 25 25 24 22 25 17 25 Plating adhesion [N / cm] 10 11 10 9 9 6 8 Plating quality ○ ○ ○ ○ Χ Χ Χ

(In Table 1, the content units of each of A1, A2, and B are% by weight based on the total weight of the base resin, and C is parts by weight based on 100 parts by weight of the base resin.)

As shown in Table 1, the specimens of Examples 1 to 4 containing cocamide diethanolamine within a specific content range, compared with Comparative Example 3 without it, the melt index and impact strength were maintained at the same level while plating. It can be seen that adhesion and plating quality have been greatly improved. In particular, it can be seen that the specimen according to the present invention has excellent plating adhesion, but does not exhibit poor appearance such as unplated areas or swelling of the plating layer, thereby providing a higher quality plating product.

On the other hand, in Comparative Example 1 in which a small amount of cocamide diethanolamine was applied compared to the scope of the present invention, the adhesion to plating was improved, but appearance defects such as unplating and swelling were observed. It was confirmed that the elution to the surface of the molded product lowered the adhesion of the plating rather, and appearance defects such as unplating / blowing were also observed, and thus the object of the present invention was not achieved.

Claims (13)

5 to 30% by weight of the first graft copolymer in which the aromatic vinyl compound and the vinyl cyan compound are grafted to the conjugated diene rubber having an average particle diameter of 0.03 μm to 0.2 μm;
10 to 40 wt% of a second graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of more than 0.2 μm to 0.5 μm; And
Aromatic vinyl compound-vinyl cyan compound copolymer 50 to 80% by weight; 100 parts by weight of the base resin containing,
Characterized in that it comprises 0.25 to 3.5 parts by weight of a dialkanolamine-based compound
Thermoplastic resin composition. According to claim 1,
The first graft copolymer is characterized in that it contains 20 to 80% by weight of a conjugated diene rubber having an average particle diameter of 0.03 μm to 0.2 μm, 10 to 70% by weight of an aromatic vinyl compound, and 1 to 30% by weight of a vinyl cyan compound. doing
Thermoplastic resin composition. According to claim 1,
The second graft copolymer is characterized in that it comprises 20 to 80% by weight of a co-ex diene rubber having an average particle diameter of more than 0.2㎛ to 0.5㎛, 10 to 70% by weight of an aromatic vinyl compound and 1 to 30% by weight of a vinyl cyan compound. To do
Thermoplastic resin composition. According to claim 1,
The dialkanolamine-based compound is represented by the following Chemical Formula 1
[Formula 1]

(In Chemical Formula 1, R ₁ is selected from chain alkyl having 5 to 25 carbon atoms, branched alkyl having 5 to 25 carbon atoms, or alkenyl having 5 to 25 carbon atoms, and R ₂ and R ₂ ′ may be the same or different from each other. And each independently selected from ethyl, propyl, and isopropyl.)
Thermoplastic resin composition. The method of claim 4,
The dialkanolamine-based compounds are cocamide diethanolamine, lauramide diethanolamine, oleamide diethanolamine, myristicamide diethanolamine, stearamide diethanolamine, palmitamide diethanolamine and linoleamide di Characterized in that it comprises at least one diethanolamine-based compound selected from ethanolamine
Thermoplastic resin composition. According to claim 1,
The aromatic vinyl compound-vinyl cyan compound copolymer is characterized in that it contains 55 to 85% by weight of the aromatic vinyl compound and 15 to 45% by weight of the vinyl cyan compound
Thermoplastic resin composition. According to claim 1,
The first graft copolymer and the second graft copolymer is characterized in that it is included in a weight ratio of 1: 1 to 1: 3
Thermoplastic resin composition. According to claim 1,
The composition is a thermoplastic resin composition, characterized in that the resin composition for plating. According to claim 1,
The composition is characterized in that the melt index (220 ℃, load 10kg) is 10 to 30g / 10min
Thermoplastic resin composition. According to claim 1,
The composition has an impact strength of 20 kgfcm / cm ² measured according to ASTM D256. Characterized by the above
Thermoplastic resin composition. According to claim 1,
The composition is characterized in that the plating adhesion is 9 N / cm or more
Thermoplastic resin composition. 5 to 30% by weight of the first graft copolymer in which the aromatic vinyl compound and the vinyl cyan compound are grafted to the conjugated diene rubber having an average particle diameter of 0.03 μm to 0.2 μm; 10 to 40 wt% of a second graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of more than 0.2 μm to 0.5 μm; And 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; blending 0.25 to 3.5 parts by weight of a dialkanolamine-based compound, and then melt-kneading and extruding it. Characterized by
Method for manufacturing a thermoplastic resin composition. It is molded from the composition according to any one of claims 1 to 11, characterized in that the metal plating layer is formed on at least one surface
Molded article.

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