KR20190082660A - Polyamide resin composition and article comprising the same - Google Patents

Abstract

A polyamide resin composition of the present invention comprises: 40 to 60 wt% of a polyamide resin including a repeating unit represented by chemical formula 1 and a repeating unit represented by chemical formula 2; 1 to 10 wt% of a maleic acid anhydride modified olefin-based copolymer; 5 to 20 wt% of calcium carbonate surface-treated with a silane-based compound; and 20 to 40 wt% of glass fiber. The silane-based compound contains one or more functional groups of an amino group, an epoxy group and a (meth)acrylic oxy group. The polyamide resin composition and a molded article formed therefrom have excellent plating adhesion, impact resistance, thermal resistance and appearance properties.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyamide resin composition,

The present invention relates to a polyamide resin composition and a molded article containing the same. More specifically, the present invention relates to a polyamide resin composition excellent in plating adhesion, impact resistance, heat resistance, appearance and the like, and a molded article containing the same.

Aromatic polyamide resin such as polyphthalamide resin has a lower specific gravity than glass or metal and is excellent in heat resistance, abrasion resistance, chemical resistance, etc., and is useful for a housing of an electric / electronic product, an automobile interior / exterior material, a building exterior material Do. Particularly, in recent years, due to the weight reduction and thinning trend of products, plastic products using thermoplastic resins are rapidly replacing existing glass and metal areas.

In addition, a technique of plating a polyamide resin on a polyamide resin has been developed so as to realize excellent merits of the polyamide resin while maintaining the beauty of the metal-like appearance. The plating treatment on the polyamide resin is intended for decorative or corrosion resistance, and the appearance characteristics after plating and the adhesiveness (plating adhesion, plating ability) between the plating film and the resin are important characteristics.

To this end, a method of improving the plating ability by adding a polyolefin having an inorganic or epoxy group to a polyamide resin composition has been developed. However, such a method has a problem that the impact strength of the resin composition may be lowered, there was. Further, a method of improving the plating property by freezing a polyamide resin and an acrylonitrile-butadiene-styrene (ABS) resin or a polycarbonate resin has been proposed, but in this case, the heat resistance And the like may be deteriorated.

Therefore, development of a polyamide resin composition excellent in plating adhesion (plating ability), impact resistance, heat resistance, appearance and the like is required.

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2010-0123178.

An object of the present invention is to provide a polyamide resin composition excellent in plating adhesion, impact resistance, heat resistance, appearance and the like.

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

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

1. One aspect of the present invention relates to a polyamide resin composition. Wherein the polyamide resin composition comprises 40 to 60% by weight of a polyamide resin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); 1 to 10% by weight of a maleic anhydride modified olefin-based copolymer; 5 to 20% by weight of calcium carbonate surface-treated with a silane-based compound; And 20 to 40% by weight of glass fibers, wherein the silane-based compound comprises at least one functional group selected from an amino group, an epoxy group and a (meth) acryloxy group,

[Chemical Formula 1]

(2)

Wherein R ₁ and R ₃ are each independently a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R ₂ and R ₄ are each independently a linear or branched alkylene group having 6 to 12 carbon atoms, n ₁ and n ₂ are each independently an integer of 0 to 4;

2. In one embodiment, the polyamide resin may include 60 to 80 mol% of the repeating unit represented by the formula (1) and 20 to 40 mol% of the repeating unit represented by the formula (2).

3. In the above-mentioned one or two embodiments, the maleic anhydride-modified olefin-based copolymer includes a maleic anhydride-modified ethylene -? - olefin copolymer obtained by graft polymerizing maleic anhydride in an ethylene -? - olefin copolymer .

4. In the above-mentioned first to third embodiments, the maleic anhydride-modified olefin-based copolymer may include a maleic anhydride-modified ethylene-octene copolymer.

5. In the first to fourth embodiments, the calcium carbonate surface-treated with the silane-based compound may have an average particle size of 40 to 150 nm.

6. In the above-mentioned Embodiments 1 to 5, the calcium carbonate surface-treated with the silane-based compound may be calcium carbonate whose surfaces are partially or wholly treated with an aminosilane compound.

7. In the above-mentioned Embodiments 1 to 6, the weight ratio of the maleic anhydride-modified olefin-based copolymer and the calcium carbonate surface-treated with the silane-based compound may be 1: 1 to 1: 5.

8. In the above-mentioned Embodiments 1 to 7, the polyamide resin composition is prepared by chrome plating an injection-molded specimen of 10 cm x 10 cm x 3.2 cm in size to a thickness of 30 m according to JIS C6481, The adhesion strength of the plating layer measured at a peeling rate of 50 mm / min may be 15 to 30 N / cm.

9. The polyamide resin composition according to any one of 1 to 8 above, wherein the notched Izod impact strength of the 1/8 "thick specimen measured according to ASTM D256 may be 8 kgf · cm / cm or more.

10. In the above items 1 to 9 embodiment, the polyamide resin composition has a heat distortion temperature (HDT) greater than or equal to 280 ℃ measured under a load of 18.56 kgf / cm ^2, rate of temperature increase of 120 ℃ / hr in accordance with ASTM D648 have.

11. Another aspect of the invention relates to a molded article. The molded article comprising a substrate layer; And a plated layer formed on at least one surface of the base layer, wherein the base layer is formed from a polyamide resin composition according to any one of the above-mentioned 1 to 10. [

INDUSTRIAL APPLICABILITY The present invention provides a polyamide resin composition excellent in plating adhesion, impact resistance, heat resistance, flowability and appearance, and a molded article formed therefrom.

1 schematically shows a cross section of a molded article according to one embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The polyamide resin composition according to the present invention comprises (A) a polyamide resin; (B) a maleic anhydride modified olefin-based copolymer; (C) calcium carbonate surface-treated with a silane-based compound; And (D) glass fibers.

In the present specification, "a to b" representing numerical ranges are defined as "? A and? B".

(A) a polyamide resin

The polyamide resin of the present invention is capable of improving the rigidity, heat resistance and the like of a polyamide resin composition (molded article), and includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

[Chemical Formula 1]

(2)

Wherein R ₁ and R ₃ are each independently a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R ₂ and R ₄ are each independently a linear or branched alkylene group having 6 to 12 carbon atoms, n ₁ and n ₂ are each independently an integer of 0 to 4;

In a specific example, the polyamide resin may contain 60 to 80 mol%, for example, 65 to 75 mol% of the repeating unit represented by the formula (1) and 20 to 40 mol% of the repeating unit represented by the formula (2) 25 to 35 mol%. Within the above range, the plating adhesion, heat resistance, etc. of the polyamide resin composition can be excellent. Here, the polyamide resin is R ₁ as a phenyl group is substituted or terephthalic acid or its alkyl of 60 to 80 mol% of ester is unsubstituted, for example, 65 to 75 mol%, and R ₃ as isopropyl phenyl group is optionally substituted acid Or an alkyl ester thereof in an amount of 20 to 40 mol%, for example, 25 to 35 mol%, and an aliphatic diamine component (1, 2, 3 or 4) containing a linear or branched alkylene group having 6 to 12 carbon atoms Hexanediamine (HMDA), 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, , 11-undecanediamine, 1,12-dodecanediamine, etc.) according to a known polymerization method.

In an embodiment, the polyamide resin may have a glass transition temperature measured by a differential scanning calorimeter (DSC) of 100 to 150 ° C, for example, 120 to 140 ° C. Within the above range, the polyamide resin composition may have excellent heat resistance, plating adhesion, and the like.

The first polyamide resin was dissolved in a concentrated sulfuric acid solution (98%) at a concentration of 0.5 g / dL, and then an intrinsic viscosity [?] Measured by a Ubbelohde viscometer at 25 ° C was 0.7 to 1.2 dL / g, for example 0.8 to 1.0 dL / g. Within the above range, the processability and appearance characteristics of the polyamide resin composition can be excellent.

In an embodiment, the polyamide resin may be contained in an amount of 40 to 60% by weight, for example, 45 to 58% by weight in 100% by weight of the total polyamide resin composition. If the content of the polyamide resin is less than 40% by weight, the plating adhesion, heat resistance and appearance characteristics of the polyamide resin composition may be deteriorated. When the content of the polyamide resin exceeds 60% by weight, , Processability, injection moldability and the like may be lowered.

(B) a maleic anhydride modified olefin-based copolymer

The maleic anhydride modified olefin-based copolymer of the present invention is a reactive olefin-based copolymer obtained by graft-polymerizing maleic anhydride, which is a functional group capable of reacting with a polyamide resin, onto an olefin-based copolymer, (Plating ability) between the plated film and the molded product when plated on a molded article produced from the polyamide resin composition, and the impact resistance and the like of the polyamide resin composition can be improved.

In an embodiment, the maleic anhydride modified olefin-based copolymer may be one obtained by graft-polymerizing maleic anhydride in an olefin-based copolymer in which two or more olefin-based monomers are copolymerized. As the olefinic monomer, alkylene having 1 to 19 carbon atoms can be used, and examples thereof include ethylene, propylene, isopropylene, butylene, isobutylene, octene, and combinations thereof.

In an embodiment, the maleic anhydride-modified olefin-based copolymer may include a maleic anhydride-modified ethylene -? - olefin copolymer obtained by graft-polymerizing maleic anhydride on an ethylene -? - olefin copolymer.

In an embodiment, the maleic anhydride modified olefin-based copolymer may include a maleic anhydride modified ethylene-octene copolymer.

In an embodiment, the maleic anhydride modified olefin-based copolymer may be obtained by graft-polymerizing 0.1 to 5 parts by weight, for example, 0.5 to 2 parts by weight, of maleic anhydride in 100 parts by weight of the olefin-based copolymer. In this range, compatibility with the polyamide resin can be excellent, and the plating adhesion of the polyamide resin composition can be excellent.

In an embodiment, the polyamide resin composition may comprise 1 to 10% by weight, for example 3 to 9% by weight, of the total 100% by weight of the composition. If the content of the olefin-based copolymer is less than 0.5% by weight, the plating adhesion and impact resistance of the polyamide resin composition may deteriorate. If the content exceeds 10% by weight, the heat resistance and rigidity of the polyamide resin composition There is a risk of degradation.

(C) calcium carbonate surface-treated with a silane-based compound

The calcium carbonate surface-treated with the silane compound of the present invention can effectively cause anchoring of the catalyst during the plating process, thereby remarkably improving the plating adhesion of the polyamide resin composition and improving the appearance characteristics As the calcium carbonate having a spherical or granular surface treated with a silane compound, there can be used.

In an embodiment, the calcium carbonate surface-treated with the silane-based compound may have an average particle size (D50, particle size at the point where the distribution ratio is 50%) of 40 to 150 nm, for example, 50 to 90 nm. If the average particle size of the calcium carbonate surface treated with the silane-based compound is less than 40 nm, dispersion during processing can be very difficult, and if it exceeds 150 nm, blistering can occur at rapid temperature changes such as thermal cycle evaluation have.

In an embodiment, the calcium carbonate surface-treated with the silane-based compound is a surface treatment agent to which a silane-based compound is applied and includes a functional group such as an amino group, an epoxy group (glycidoxy group), a (meth) acryloxy group, A silane-based compound (silane coupling agent) may be used. The surface treatment of the silane compound with the silane compound can be carried out by a conventional method. The surface treated with the silane compound may be calcium carbonate. The surface of the calcium carbonate may be entirely or partially covered with a silane compound Lt; / RTI >

Examples of the silane compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Methacryloxypropylmethyldimethoxysilane,? -Methacryloxypropyltri Methacryloxypropylmethyldiethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Acryloxypropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyl (Aminoethyl) -? - aminopropyltriethoxysilane,? -Aminopropyltrimethoxysilane,? - (aminoethyl) -? - aminopropyltrimethoxysilane, N- -Aminopropyltriethoxysilane, N-phenyl-gamma -aminopropyltrimethoxysilane and the like can be used. The.

In an embodiment, the calcium carbonate surface-treated with the silane-based compound may include 100 parts by weight of calcium carbonate and 0.01 to 1.0 parts by weight, for example, 0.02 to 0.5 parts by weight, of the silane compound. Within the above range, the plating adhesion and heat resistance of the polyamide resin composition can be excellent.

In an embodiment, the calcium carbonate surface-treated with the silane-based compound may be contained in an amount of 5 to 20% by weight, for example 8 to 15% by weight, of 100% by weight of the entire polyamide resin composition. When the content of the calcium carbonate surface-treated with the silane compound is less than 5% by weight, the plating adhesion and mechanical properties of the polyamide resin composition may be deteriorated. When the content of the calcium carbonate exceeds 20% by weight, The impact resistance and the like may be lowered.

In a specific example, the weight ratio (B: C) of the maleic anhydride modified olefin-based copolymer (B) and the calcium carbonate (C) surface-treated with the silane-based compound is from 1: 1 to 1: 5, : 1 to 1: 2. Within the above range, the occurrence of blisters of the polyamide resin composition is small and the plating adhesion, heat resistance and appearance can be more excellent.

(D) glass fiber

The glass fiber according to one embodiment of the present invention can improve the mechanical properties such as rigidity of the polyamide resin composition, and glass fibers used in a conventional thermoplastic resin composition can be used.

In an embodiment, the glass fibers may be in the form of fibers and may have cross-sections of various shapes such as circular, elliptical, rectangular, and the like. For example, it may be preferable from the viewpoint of mechanical properties to use a fibrous glass fiber having a circular and / or rectangular cross section.

In a specific example, the glass fiber of the circular cross section may have a cross-sectional diameter of 5 to 20 탆 and a length before shaping of 2 to 20 mm, the glass fiber of the rectangular cross-section has an aspect ratio of 1.5 to 10, May be between 2 and 20 mm. Within the above range, the rigidity, workability and the like of the polyamide resin composition can be improved.

In an embodiment, the glass fibers may comprise 20 to 40 wt%, for example 25 to 35 wt%, of 100 wt% of the total polyamide resin composition. If the content of the glass fiber is less than 20% by weight, the mechanical properties of the polyamide resin composition may deteriorate. If the content of the glass fiber exceeds 40% by weight, the appearance properties, extrusion processability, And the like may be deteriorated.

The polyamide resin composition according to one embodiment of the present invention may further include an additive contained in a conventional thermoplastic resin composition. Examples of the additives include, but are not limited to, flame retardants, lubricants, plasticizers, heat stabilizers, antioxidants, light stabilizers or colorants, and mixtures thereof. When the additive is used, the content thereof may be 0.001 to 40 parts by weight, for example, 0.1 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin.

The polyamide resin composition according to one embodiment of the present invention may be in the form of a pellet obtained by melt-extruding at 200 to 350 ° C, for example, 250 to 300 ° C using a conventional twin-screw extruder by mixing the above components.

In the specific examples, the polyamide resin composition was prepared by chrome plating an injection molded specimen of 10 cm x 10 cm x 3.2 cm in size to a thickness of 30 m according to JIS C6481, and then peeling off at 50 mm / min using a tensile tester The adhesion strength of the plating layer measured at a speed of 15 to 30 N / cm, for example, 19 to 25 N / cm.

In embodiments, the polyamide resin composition may have a notched Izod impact strength of at least 8 kgf · cm / cm, eg, from 8.2 to 15 kgf · cm / cm, measured according to ASTM D256 have.

In a specific example, the polyamide resin composition has a heat distortion temperature (HDT) measured at a temperature of 18.56 kgf / cm ² and a temperature raising rate of 120 ° C / hr according to ASTM D648 of 280 ° C or higher, for example, 282 to 300 Lt; 0 > C.

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

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

In an embodiment, the plating layer 20 may be formed according to a conventional method for manufacturing a plated plastic product. For example, the base layer 10 may be etched and an anchor may be formed on the etched portion And then performing plating, for example, electroless plating and electroplating. However, the present invention is not limited thereto.

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

In the plating process of the present invention, the plating process used for the substrate layer formed from ordinary ABS, PC / ABS, etc. can be applied as it is. Usually, the substrate layer formed from the polyamide resin composition has a disadvantage that the use of a conventional etchant increases the percentage of defects and requires a dedicated etching solution and requires a plating line dedicated to the polyamide resin composition base layer to increase the cost burden . However, the substrate layer formed of the polyamide resin composition of the present invention can be plated using existing plating lines, an etching solution, or the like without such a problem.

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

The molded article of the present invention is excellent in plating adhesion of the base layer and the plating layer, and is excellent in external appearance characteristics, impact resistance, heat resistance, and the like of the base layer and is useful as an internal and external material for metallic exterior such as automobile, electric and electronic office automation equipment and the like.

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

Example

The specifications of each component used in the following examples and comparative examples are as follows.

(A) a polyamide resin

(A1) polyamide 6T / 6I (manufactured by Solvay, product name: A8002, 6T: 6I (molar ratio) = 70: 30, intrinsic viscosity [?]: 0.88 dL / g) was used.

(A2) polyamide 6T / 66 (manufactured by Solvay, product name: A6000, 6T: 66 (molar ratio) = 55:44, intrinsic viscosity [?]: 0.85 dL / g) was used.

(B) an olefin-based copolymer

(B1) maleic anhydride-modified ethylene-octene copolymer (manufactured by DuPont, product name: Fusabond N493D) was used.

(B2) ethylene-octene copolymer (manufactured by DuPont, product name: Engage 8842) was used.

(C) Calcium carbonate

(C1) calcium carbonate (average particle size (D50): 70 nm) surface-treated with aminopropyltrimethoxysilane was used. The calcium carbonate surface-treated with the aminopropyltrimethoxysilane was dried in an oven at 80 ° C for 12 hours, and the dried calcium carbonate was mixed with ethanol and distilled water Followed by adding a certain amount of an aminopropyltrimethoxysilane coupling agent and stirring at 40 to 80 ° C for 12 to 24 hours.

(Average particle size (D50): 70 nm) surface-treated with (C2) glycidoxypropyltrimethoxysilane was used. The calcium carbonate surface-treated with glycidoxypropyltrimethoxysilane was dried in an oven at 80 ° C. for 12 hours in a non-surface-treated calcium carbonate according to a conventional surface treatment method, and then dried calcium carbonate was mixed with ethanol and distilled water Mixed and dispersed, and then a predetermined amount of glycidoxypropyltrimethoxysilane coupling agent was added thereto, followed by stirring at 40 to 80 ° C for 12 to 24 hours.

(C3) calcium carbonate (average particle size (D50): 70 nm) surface-treated with 3-methacryloxypropyltrimethoxysilane was used. The surface-untreated calcium carbonate was dried in an oven at 80 ° C for 12 hours according to a conventional surface treatment method. The dried calcium carbonate was mixed with ethanol and distilled water and dispersed. Then, 3-methacryloxypropyltrimethoxysilane A certain amount of a coupling agent was added, and the mixture was stirred at 40 to 80 DEG C for 12 to 24 hours.

(C4) Surface-treated calcium carbonate (manufacturer: Solvay, product name: UP, average particle size (D50): 70 nm) was used.

(C5) Calcium carbonate (manufactured by Solvay, product name: U1S1, average particle size (D50): 70 nm) surface-treated with a stearate compound was used.

(D) glass fiber (manufacturer: Nippon Electric Glass, product name: T-251H) was used.

Examples 1 to 5 and Comparative Examples 1 to 6

The above components were added in the amounts shown in Tables 1 and 2, and then extruded at 300 ° C to prepare pellets. The extrudate was a biaxial extruder having an L / D of 36 and a diameter of 45 mm. The pellets were dried at 80 to 100 ° C. for 4 hours or more, and then dried in a 6 oz injection molding machine at a molding temperature of 320 ° C. and a mold temperature of 130 ° C. The specimens were prepared by injection molding. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Tables 1 and 2 below.

Property evaluation method

(1) Adhesion strength of plating layer (unit: N / cm): An injection-molded specimen of 10 cm x 10 cm x 3.2 cm in size was chrome plated to a thickness of about 30 mu m in accordance with JIS C6481, The central portion of the plated layer was cut and bite into a jig of a tensile tester, and then the bonding strength between the base layer and the plated layer was measured by pulling at a peeling speed of 50 mm / min in the 90 占 direction of the surface of the plated layer.

(2) Notch Izod impact strength (unit: kgf · cm / cm): Measured by making a notch on a 1/8 "thick Izod (IZOD) specimen according to the evaluation method specified in ASTM D256.

(3) Heat distortion temperature (HDT, unit: 占 폚): Measured under the conditions of a load of 18.56 kgf / cm ² and a temperature increase rate of 120 占 폚 / hr in accordance with ASTM D648.

(4) Thermal cycle evaluation: The injection molded specimen of 10 cm x 10 cm x 3.2 cm in size prepared in the above Examples and Comparative Examples was aged in a low-temperature oven at -40 DEG C for 1 hour and left at room temperature for 30 minutes , And the negated specimen was again aged in a constant temperature oven at 250 DEG C for 2 hours and left at room temperature for 30 minutes. The above procedure was repeated three times to visually confirm whether a blister occurred on the outer surface of the specimen.

(5) Surface roughness (unit: GU): A gloss meter (manufactured by BYK, device name: micro gloss) was applied to the injection molded specimen of 10 cm × 10 cm × 3.2 cm size prepared in the above Examples and Comparative Examples And the reflection angle was measured at 75 DEG.

Example One 2 3 4 5 (A1) (% by weight) 54 52 47 52 52 (B1) (% by weight) 8 8 8 8 8 (C1) (% by weight) 8 10 15 - - (C2) (% by weight) - - - 10 - (C3) (% by weight) - - - - 10 (D) (% by weight) 30 30 30 30 30 Coating strength 20 21 19 18 20 Notch Izod impact strength 9.1 8.3 8.5 9.1 8.9 Heat distortion temperature 283 282 283 283 282 Blister occurrence Not occurring Not occurring Not occurring Not occurring Not occurring Surface roughness 102 102 102 102 102

Comparative Example One 2 3 4 5 6 (A1) (% by weight) 54 52 47 - 52 52 (A2) (% by weight) - - - 52 - - (B1) (% by weight) 8 8 8 8 - 8 (B2) (% by weight) - - - - 8 - (C1) (% by weight) - - - 10 10 - (C4) (% by weight) 8 10 15 - - - (C5) (% by weight) - - - - - 10 (D) (% by weight) 30 30 30 30 30 30 Coating strength 9 9 9 One 10 13 Notch Izod impact strength 8.7 7.2 9.4 9.7 8.1 8.5 Heat distortion temperature 284 282 279 288 280 282 Blister occurrence Occur Occur Occur Occur Occur Occur Surface roughness 85 83 88 94 92 85

From the above results, it can be seen that the polyamide resin composition of the present invention has excellent plating adhesion, impact resistance, heat resistance, appearance and the like, and does not change appearance such as blister formation.

On the other hand, in the case of Comparative Examples 1 to 3 in which calcium carbonate (C4) not subjected to surface treatment was used in place of calcium carbonate (C1) to (C3) surface-treated with the silane compound of the present invention, In the case of Comparative Example 4 in which polyamide 6T / 66 (A2) was applied in place of the polyamide resin (A1) of the present invention, plating was almost impossible, (B2) was used instead of the maleic anhydride-modified olefin-based copolymer (B1) of the maleic anhydride-modified olefin-based copolymer (B1), blisters were generated in the evaluation of the heat cycle, Is lowered. In the case of Comparative Example 6 in which calcium carbonate (C5) surface-treated with a stearate compound was used instead of the calcium carbonate (C1) to (C3) surface-treated with the silane compound of the present invention, It was found that blisters were generated in all of them, and heat resistance and appearance characteristics were deteriorated.

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

Claims (11)

40 to 60% by weight of a polyamide resin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2);
1 to 10% by weight of a maleic anhydride modified olefin-based copolymer;
5 to 20% by weight of calcium carbonate surface-treated with a silane-based compound; And
20 to 40% by weight of glass fibers;
Wherein the silane-based compound comprises at least one functional group selected from an amino group, an epoxy group and a (meth) acryloxy group.
[Chemical Formula 1]

(2)

Wherein R ₁ and R ₃ are each independently a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R ₂ and R ₄ are each independently a linear or branched alkylene group having 6 to 12 carbon atoms, n ₁ and n ₂ are each independently an integer of 0 to 4;
The polyamide resin composition according to claim 1, wherein the polyamide resin comprises 60 to 80 mol% of the repeating unit represented by the formula (1) and 20 to 40 mol% of the repeating unit represented by the formula (2).
The olefin-based copolymer according to claim 1, wherein the maleic anhydride-modified olefin-based copolymer comprises a maleic anhydride-modified ethylene -? - olefin copolymer obtained by graft-polymerizing maleic anhydride on an ethylene -? - olefin copolymer Polyamide resin composition.
The polyamide resin composition according to claim 1, wherein the maleic anhydride-modified olefin-based copolymer comprises a maleic anhydride-modified ethylene-octene copolymer.
The polyamide resin composition according to claim 1, wherein the calcium carbonate surface-treated with the silane-based compound has an average particle size of 40 to 150 nm.
The polyamide resin composition according to claim 1, wherein the calcium carbonate surface-treated with the silane-based compound is calcium carbonate whose surface is entirely or partially coated with the silane-based compound.
The polyamide resin composition according to claim 1, wherein the weight ratio of the maleic anhydride modified olefin-based copolymer to the calcium carbonate surface-treated with the silane-based compound is 1: 1 to 1: 5.
The polyamide resin composition according to claim 1, wherein the polyamide resin composition is chrome plated with an injection molded specimen of 10 cm x 10 cm x 3.2 cm in size to a thickness of 30 m according to JIS C6481, Wherein the coating layer has an adhesion strength of 15 to 30 N / cm as measured by the peeling speed of the polyamide resin composition.
The polyamide resin composition according to claim 1, wherein the polyamide resin composition has a notched Izod impact strength of at least 8 kgf / cm / cm in a 1/8 "thick specimen measured according to ASTM D256.
The method of claim 1, wherein the polyamide resin composition is polyester, characterized in that at least one heat distortion temperature (HDT) is 280 ℃ measured under the conditions of a load of 18.56 kgf / cm ^2, rate of temperature increase 120 ℃ / hr in accordance with ASTM D648 Amide resin composition.
A base layer; And
And a plating layer formed on at least one surface of the substrate layer,
Wherein the base layer is formed from the polyamide resin composition according to any one of claims 1 to 10.

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