Polyamide resin composition for laser direct structuring process and molded article comprising same

Abstract

A polyamide resin composition of the present invention comprises: about 100 parts by weight of a base material including about 60 to about 95 wt% of a semi-aromatic polyamide resin having two melting points (Tm) and satisfying formula 1 and about 5 to about 40 wt% of glass fibers; about 1 to about 10 parts by weight of an additive for laser direct structuring; and about 0.1 to about 2 parts by weight of a phosphorus-based compound having a molecular weight of about 500 to about 1,500 g / mol. The polyamide resin composition is excellent in terms of plating reliability, rigidity, fluidity, and the like.

Description

Polyamide resin composition for laser direct structuring process and molded article comprising the same

[0001] The present invention relates to a polyamide resin composition for a laser direct structuring process and a molded article comprising the same. More specifically, the present invention relates to a polyamide resin composition for a laser direct structuring process having excellent plating reliability, rigidity, fluidity, etc., and a molded article comprising the same.

[0002]

[0003] A laser direct structuring process (LDS process) can be used to plate a metal layer on at least a portion of the surface of a molded article formed from a thermoplastic resin composition. The LDS process is a process performed prior to the plating step, in which a laser is irradiated on the target area of ​​the molded article surface to modify the target area of ​​the molded article surface to provide properties suitable for plating. To this end, the thermoplastic resin composition for manufacturing the molded article must contain a laser direct structuring additive (LDS additive) capable of forming metal nuclei by the laser. The additive decomposes upon exposure to the laser to generate metal nuclei. In addition, the area irradiated with the laser has a roughened surface. Due to these metal nuclei and surface roughness, the area modified by the laser becomes suitable for plating.

[0004] The laser direct structuring process allows for the rapid and economical formation of electrical and electronic circuits on the three-dimensional shape of a molded product. For example, the laser direct structuring process can be used to manufacture antennas for portable electronic devices and radio frequency identification (RFID) antennas.

[0005] With the recent trend toward lighter and thinner products, there is a growing demand for thermoplastic resin compositions with superior mechanical properties and moldability. Furthermore, as the micropatterns (plating areas) of electrical / electronic circuits in portable electronic devices become thinner, there is a risk of plating peeling, potentially reducing plating reliability.

[0006] Therefore, there is a need to develop a polyamide resin composition for a laser direct structuring process with excellent plating reliability, rigidity, fluidity, etc., and a molded product including the same.

[0007] The background technology of the present invention is disclosed in Korean Patent Publication No. 2011-0018319, etc.

[0008]

[0009] The purpose of the present invention is to provide a polyamide resin composition having excellent plating reliability, rigidity, fluidity, etc.

[0010] Another object of the present invention is to provide a molded product formed from the polyamide resin composition.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below.

[0012]

[0013] 1. One aspect of the present invention relates to a polyamide resin composition. The polyamide resin composition comprises: about 100 parts by weight of a base material comprising about 60 to about 95 wt% of a semi-aromatic polyamide resin having two melting points (Tm) and satisfying the following formula 1, and about 5 to about 40 wt% of glass fiber; about 1 to about 10 parts by weight of an additive for laser direct structuring; and about 0.1 to about 2 parts by weight of a phosphorus compound having a molecular weight of about 500 to about 1,500 g / mol:

[0014] [Formula 1]

[0015] ΔH(Tm 1st ) < ΔH(Tm2nd )

[0016] In the above equation 1, ΔH(Tm 1st ) is the first melting point (Tm 1st ) is the size of the endothermic peak, and ΔH(Tm 2nd ) is the second melting point (Tm 2nd ) is the size of the endothermic peak, and the first melting point (Tm 1st ) is the second melting point (Tm 2nd ) is lower in temperature.

[0017] 2. In the above 1 specific example, the semi-aromatic polyamide resin may be a polymer of an aromatic dicarboxylic acid and an aliphatic diamine.

[0018] 3. In the above 1 or 2 specific examples, the semi-aromatic polyamide resin may include at least one of polyamide 10T, polyamide 11T, and polyamide 12T.

[0019] 4. In the above 1 to 3 specific examples, the glass fiber may have a cross-sectional diameter of about 3 to about 8 ㎛.

[0020] 5. In the above 1 to 4 specific examples, the additive for laser direct structuring may include at least one of a heavy metal complex oxide spinel and a copper salt.

[0021] 6. In the above 1 to 5 specific examples, the weight ratio of the semi-aromatic polyamide resin and the additive for laser direct structuring may be about 1:0.01 to about 1:0.2.

[0022] 7. In the above 1 to 6 specific examples, the weight ratio of the semi-aromatic polyamide resin and the phosphorus compound may be about 1:0.001 to about 1:0.03.

[0023] 8. In the above 1 to 7 specific examples, the polyamide resin composition is aged at 25°C for 6 hours on an injection-molded specimen having a size of 50 mm × 90 mm × 3.2 mm, and then the surface of the specimen is activated in a stripe shape through a laser direct structuring process, and a copper layer having a thickness of 35 μm is formed on the activated surface through a plating process (electroless copper plating), and then the plated specimen is left in a chamber under conditions of 85°C and 85% RH for 72 hours, and 100 grids having a size of 1 mm × 1 mm are imprinted on the plating layer (copper layer), and then the number of grids that are not peeled off when the specimen is removed with tape may be about 90 to about 100.

[0024] 9. In the above 1 to 8 specific examples, the polyamide resin composition may have a tensile strength of about 750 to about 1,600 MPa of a 3.2 mm thick specimen measured under conditions of 5 mm / min according to ASTM D638.

[0025] 10. In the above 1 to 9 specific examples, the polyamide resin composition may have a spiral flow length of about 99 to about 150 mm when measured after injection molding in a spiral-shaped mold having a width of 15 mm and a thickness of 0.5 mm under conditions of a molding temperature of 340°C, a mold temperature of 100°C, an injection pressure of 100 MPa, and an injection speed of 100 mm / s.

[0026] 11. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from a thermoplastic resin composition according to any one of 1 to 10.

[0027] 12. In the above 11 specific examples, the molded product may include a metal layer formed by a laser direct structuring process and a plating process on at least a portion of the surface.

[0028]

[0029] The present invention has the effect of providing a polyamide resin composition having excellent plating reliability, rigidity, fluidity, etc., and a molded article formed therefrom.

[0030]

[0031] Figure 1 schematically illustrates a molded product according to one specific example of the present invention.

[0032]

[0033] Hereinafter, the present invention will be described in detail as follows.

[0034] A polyamide resin composition according to the present invention is usable in a laser direct structuring process (LDS process), and comprises (A) a semi-aromatic polyamide resin; (B) glass fiber; (C) an additive for laser direct structuring; and (D) a phosphorus compound.

[0035] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0036]

[0037] (A) Semi-aromatic polyamide resin

[0038] According to one specific example of the present invention, a semi-aromatic polyamide resin can be applied together with glass fiber, an additive for laser direct structuring, a phosphorus compound, etc., to improve the plating reliability, rigidity, fluidity, etc. of a polyamide resin composition. A semi-aromatic polyamide resin having two melting points (Tm) and satisfying the following formula 1 can be used.

[0039] [Formula 1]

[0040] ΔH(Tm 1st ) < ΔH(Tm 2nd )

[0041] In the above equation 1, ΔH(Tm 1st ) is the first melting point (Tm 1st ) is the size of the endothermic peak, and ΔH(Tm 2nd) is the second melting point (Tm 2nd ) is the size of the endothermic peak, and the first melting point (Tm 1st ) is the second melting point (Tm 2nd ) is lower in temperature.

[0042] If the semi-aromatic polyamide resin does not satisfy the above formula 1, there is a concern that the plating reliability of the polyamide resin composition may be reduced.

[0043] In a specific example, the ΔH(Tm 1st ) and the above ΔH(Tm 2nd ) may be about 1:1.1 to about 1:1.6. In the above range, the plating reliability of the polyamide resin composition may be excellent.

[0044] In a specific example, the semi-aromatic polyamide resin may be a polymer of an aromatic dicarboxylic acid and an aliphatic diamine produced by reacting them according to a known polymerization method.

[0045] In this specification, the term dicarboxylic acid, etc. is used to mean dicarboxylic acid, its alkyl ester (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester), acid anhydride thereof, etc., and reacts with diamine, etc. to form a repeating unit derived from dicarboxylic acid (dicarboxylic acid moiety). In addition, in this specification, the repeating unit derived from dicarboxylic acid and the repeating unit derived from diamine (diamine moiety) mean a residue remaining when a hydrogen atom (removed from an amine group), a hydroxyl group or an alkoxy group (removed from a carboxylic acid group) is removed when dicarboxylic acid and diamine undergo a polymerization reaction.

[0046] In a specific example, the aromatic dicarboxylic acid may be a compound containing at least one aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxyphenylenic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4'-oxybis(benzoic acid), diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'dicarboxylic acid, 4,4'-diphenylcarboxylic acid, and mixtures thereof. Specifically, it may be terephthalic acid, isophthalic acid, or a mixture thereof.

[0047] In a specific example, the aliphatic diamine may be one or more aliphatic diamines having 4 to 20 carbon atoms. For example, linear or branched aliphatic diamines such as 1,4-butanediamine, 1,6-hexanediamine (hexamethylene diamine: HMDA), 1,7-heptanediamine, 1,8-octanediamine, 1,10-decanediamine (DDA), 1,12-dodecanediamine (DDDA), 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, 2,2-oxybis(ethylamine), bis(3-aminopropyl)ether, ethylene glycol bis(3-aminopropyl)ether (EGBA), 1,7-diamino-3,5-dioxoheptane, and mixtures thereof can be used.

[0048] In a specific example, the semi-aromatic polyamide resin may have a molar ratio (diamine / dicarboxylic acid) of repeating units derived from the dicarboxylic acid and repeating units derived from the diamine of about 0.95 to about 1.15, for example, about 1.00 to about 1.10. Within the above range, a polyamide resin having a polymerization degree suitable for molding can be produced, and deterioration of physical properties due to unreacted monomers can be prevented.

[0049] In specific examples, the semi-aromatic polyamide resin may include polyamide 10T, polyamide 11T, polyamide 12T, combinations thereof, and the like.

[0050] In a specific example, the aromatic polyamide resin may be dissolved in a concentrated sulfuric acid solution (98%) at a concentration of 0.5 g / dL, and then the intrinsic viscosity [η] measured at 25°C using an Ubbelohde viscometer may be about 0.7 to about 1.2 dL / g, for example, about 0.8 to about 1.0 dL / g. Within the above range, the polyamide resin composition may have excellent heat resistance, rigidity, impact resistance, etc.

[0051] In a specific example, the semi-aromatic polyamide resin may be included in an amount of about 60 to about 95 wt%, for example, about 65 to about 90 wt%, based on 100 wt% of the base material (semi-aromatic polyamide resin and glass fiber). If the content of the semi-aromatic polyamide resin is less than about 60 wt%, based on 100 wt% of the base material, there is a concern that the fluidity, etc. of the polyamide resin composition may be reduced, and if it exceeds about 95 wt%, there is a concern that the rigidity, etc. of the polyamide resin composition may be reduced.

[0052]

[0053] (B) Glass fiber

[0054] According to one specific example of the present invention, glass fibers can be applied together with the semi-aromatic polyamide resin, additives for laser direct structuring, and phosphorus compounds to improve plating reliability, rigidity, fluidity, etc. of a polyamide resin composition, and glass fibers used in conventional polyamide resin compositions can be used.

[0055] In specific embodiments, the glass fibers may be in the form of fibers and may have various cross-sections such as circular, oval, rectangular, etc. For example, the use of fibrous glass fibers having a circular or oval cross-section may be preferable in terms of mechanical properties.

[0056] In a specific example, the glass fiber may have an aspect ratio (major axis of the cross-section / minor axis of the cross-section) of about 1 to about 10 as measured by an optical microscope, a minor axis of about 3 to about 8 µm, and a length before processing of about 2 to about 20 mm. Within this range, the dimensional stability, rigidity, processability, etc. of the polyamide resin composition may be improved.

[0057] In a specific example, the glass fiber may be treated with a conventional surface treatment agent.

[0058] In a specific example, the glass fiber may be included in an amount of about 5 to about 40 wt%, for example, about 10 to about 35 wt%, based on 100 wt% of the base material (semi-aromatic polyamide resin and glass fiber). If the content of the glass fiber is less than about 5 wt%, based on 100 wt% of the base material, there is a concern that the rigidity, etc. of the polyamide resin composition may be reduced, and if it exceeds about 40 wt%, there is a concern that the fluidity, etc. of the polyamide resin composition may be reduced.

[0059]

[0060] (C) Additives for laser direct structuring

[0061] An additive for laser direct structuring (LDS) according to one specific example of the present invention forms a metal nucleus by a laser, and is applied together with the semi-aromatic polyamide resin, glass fiber, and phosphorus compound, etc., to improve the plating reliability, rigidity, fluidity, etc. of a polyamide resin composition, and an additive for laser direct structuring used in a typical resin composition for laser direct structuring can be used. Here, the laser means light amplified by stimulated emission (stimulated emission light), and the laser may be ultraviolet light having a wavelength of 100 to 400 nm, visible light having a wavelength of 400 to 800 nm, or infrared light having a wavelength of 800 to 25,000 nm, for example, infrared light having a wavelength of 1,000 to 2,000 nm.

[0062] In specific examples, the additive for laser direct structuring may include heavy metal mixture oxide spinel and / or copper salt.

[0063] In specific examples, the heavy metal composite oxide spinel may include magnesium aluminum oxide (MgAl2O4), zinc aluminum oxide (ZnAl2O4), iron aluminum oxide (FeAl2O4), copper iron oxide (CuFe2O4), copper chromium oxide (CuCr2O4), manganese iron oxide (MnFe2O4), nickel iron oxide (NiFe2O4), titanium iron oxide (TiFe2O4), iron chromium oxide (FeCr2O4), magnesium chromium oxide (MgCr2O4), and combinations thereof. For example, copper chromium oxide (CuCr2O4) can be used. Since the copper chromium oxide (CuCr2O4) has a dark color, it can be applied when the color required for the final molded product is a dark color such as black or gray.

[0064] In specific examples, examples of the copper salt include, but are not limited to, copper hydroxide phosphate, copper phosphate, copper sulfate, cuprous thiocyanate, and combinations thereof. For example, copper hydroxide phosphate may be used. The copper hydroxide phosphate is a compound in which copper phosphate and copper hydroxide are combined, and may be specifically Cu3(PO4)2·2Cu(OH)2, Cu3(PO4)2·Cu(OH)2, etc. The copper hydroxide phosphate does not lower the color reproducibility of an additionally added colorant, so that a molded product of a desired color can be easily obtained.

[0065] In a specific example, the additive for laser direct structuring may have an average particle diameter of about 0.01 to about 50 μm, for example, about 0.1 to about 30 μm, specifically about 0.5 to about 10 μm. Within this range, a uniform plating surface can be formed during plating via laser direct structuring. Here, the average particle diameter is a number average diameter, and means the diameter measured by D50 (the particle diameter at the point where the distribution ratio is 50%).

[0066] In a specific example, the additive for laser direct structuring may be included in an amount of about 1 to about 10 parts by weight, for example, about 2 to about 8 parts by weight, based on about 100 parts by weight of the base material. If the content of the additive for laser direct structuring is less than about 1 part by weight based on about 100 parts by weight of the base material, when the polyamide resin composition (molded product) is irradiated with a laser, a sufficient amount of metal nuclei may not be formed for plating, which may result in failure to perform plating, or the plating reliability of the polyamide resin composition may deteriorate. If the content exceeds about 10 parts by weight, there is a concern that the rigidity, fluidity, etc. of the polyamide resin composition may deteriorate.

[0067] In a specific example, the weight ratio (A:C) of the semi-aromatic polyamide resin and the additive for laser direct structuring may be from about 1:0.01 to about 1:0.2, for example from about 1:0.02 to about 1:0.15. Within this range, the plating reliability, rigidity, fluidity, etc. of the polyamide resin composition may be more excellent.

[0068]

[0069] (D) Inheritance compound

[0070] According to one specific example of the present invention, a phosphorus compound can be applied together with the semi-aromatic polyamide resin, glass fiber, and additives for laser direct structuring, etc., to improve the plating reliability, rigidity, fluidity, etc. of the polyamide resin composition. A phosphorus compound having a molecular weight of about 500 to about 1,500 g / mol can be used.

[0071] In a specific example, the phosphorus compound may have a molecular weight of about 500 to about 1,500 g / mol, for example, about 700 to about 1,300 g / mol. If the phosphorus compound has a molecular weight of less than about 500 g / mol, there is a concern that the plating reliability of the polyamide resin composition may be reduced, and if it exceeds about 1,500 g / mol, there is a concern that the plating reliability of the polyamide resin composition may be reduced.

[0072] In specific examples, the phosphorus compound may include phosphite, phosphonite, bisphosphite, diphosphate, combinations thereof, and the like.

[0073] In a specific example, the phosphorus compound may be included in an amount of about 0.1 to about 2 parts by weight, for example, about 0.15 to about 1.7 parts by weight, relative to about 100 parts by weight of the base material. If the content of the phosphorus compound is less than about 0.1 parts by weight relative to about 100 parts by weight of the base material, there is a concern that the plating reliability, rigidity, etc. of the polyamide resin composition may be reduced, and if it exceeds about 2 parts by weight, there is a concern that the plating reliability, fluidity, etc. of the polyamide resin composition may be reduced.

[0074] In a specific example, the weight ratio (A:D) of the semi-aromatic polyamide resin and the phosphorus compound may be from about 1:0.001 to about 1:0.03, for example from about 1:0.0018 to about 1:0.024. Within this range, the plating reliability, rigidity, fluidity, etc. of the polyamide resin composition may be more excellent.

[0075]

[0076] A polyamide resin composition according to one embodiment of the present invention may further include conventional additives as needed, within a range that does not impair the effects of the present invention. Such additives include, but are not limited to, flame retardants, anti-drip agents, heat stabilizers, lubricants, release agents, nucleating agents, colorants, and mixtures thereof. When the additives are used, the content thereof may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 20 parts by weight, based on about 100 parts by weight of the base material.

[0077]

[0078] A polyamide resin composition according to one specific example of the present invention may be in the form of pellets obtained by mixing the above components and melt-extruding them at about 270 to about 330°C, for example, about 280 to about 320°C, using a conventional twin-screw extruder.

[0079] In a specific example, the polyamide resin composition is aged at 25°C for 6 hours on an injection-molded specimen measuring 50 mm × 90 mm × 3.2 mm, and then the surface of the specimen is activated in a stripe shape through a laser direct structuring process, and a copper layer having a thickness of 35 μm is formed on the activated surface through a plating process (electroless copper plating), and then the plated specimen is left in a chamber under conditions of 85°C and 85% RH for 72 hours, and 100 grids measuring 1 mm × 1 mm are imprinted on the plating layer (copper layer), and then the number of grids that are not peeled off when the specimen is removed with tape may be about 90 to about 100, for example, about 91 to about 100.

[0080] In a specific example, the polyamide resin composition may have a tensile strength of about 750 to about 1,600 MPa, for example, about 800 to about 1,500 MPa, of a 3.2 mm thick specimen measured under conditions of 5 mm / min according to ASTM D638.

[0081] In a specific example, the polyamide resin composition may have a spiral flow length of about 99 to about 150 mm, for example, about 100 to about 145 mm, measured after injection molding in a spiral-shaped mold having a width of 15 mm and a thickness of 0.5 mm under conditions of a molding temperature of 340°C, a mold temperature of 100°C, an injection pressure of 100 MPa, and an injection speed of 100 mm / s.

[0082]

[0083] The molded article according to the present invention is formed from the polyamide resin composition. For example, the molded article can be manufactured using the polyamide resin composition using a molding method such as injection molding, compression molding, blow molding, or extrusion molding. The molded article can be easily formed by a person skilled in the art to which the present invention pertains.

[0084] FIG. 1 schematically illustrates a molded article according to one embodiment of the present invention. The sizes of the components constituting the invention in the drawing are exaggerated for the sake of clarity of the specification and are not limited thereto. As illustrated in FIG. 1, a molded article (10) according to one embodiment of the present invention may include a metal layer (20) formed on at least a portion of the surface of the molded article (10) by a laser direct structuring process and a plating process. The molded article (10) according to one embodiment of the present invention may be a circuit carrier used for manufacturing an antenna, and the molded article (10) may be manufactured by, for example, manufacturing the molded article (10) by a method such as injection molding using the polyamide resin composition; irradiating a laser to a specific area (metal layer (20) portion) of the surface of the molded article (10); and metallizing (plating) the irradiated area to form the metal layer (20).

[0085] In a specific example, the laser direct structuring additive included in the molded product (10) is decomposed by the laser irradiation, thereby generating metal nuclei. In addition, the area irradiated with the laser has a surface roughness suitable for plating. The wavelength of the laser may be 248 nm, 308 nm, 355 nm, 532 nm, 1,064 nm, or 10,600 nm.

[0086] In a specific embodiment, the metallization process may be performed through a conventional plating process. For example, a metal layer (20) (electrically conductive path) may be formed on the laser-irradiated area of ​​the surface of the molded product (10) by immersing the laser-irradiated molded product (10) in one or more electroless plating baths. Non-limiting examples of the plating process include copper plating, gold plating, nickel plating, silver plating, zinc plating, and tin plating.

[0087] In this way, a molded product having a metal layer formed on at least a portion of the surface by a laser direct structuring process can be easily formed by a person having ordinary skill in the art to which the present invention pertains.

[0088]

[0089] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0090]

[0091] Example

[0092] Below, the specifications of each component used in the examples and comparative examples are as follows.

[0093] (A) Semi-aromatic polyamide resin

[0094] (A1) It has two melting points (Tm) (wherein, the first melting point (Tm) 1st ) is the second melting point (Tm 2nd ) is lower than the first melting point (Tm1st ) size of the endothermic peak ΔH(Tm) 1st ) and second melting point (Tm 2nd ) size of the endothermic peak ΔH(Tm) 2nd ) Polyamide 10T (manufacturer: UNITIKA, product name: XN501) with a size ratio of approximately 1:1.43 was used.

[0095] (A2) It has two melting points (Tm) (wherein, the first melting point (Tm) 1st ) is the second melting point (Tm 2nd ) is lower than the first melting point (Tm 1st ) size of the endothermic peak ΔH(Tm) 1st ) and second melting point (Tm 2nd ) size of the endothermic peak ΔH(Tm) 2nd ) Polyamide 10T (manufacturer: EVONIK, product name: TGP3657) with a size ratio of approximately 1:0.45 was used.

[0096] (B) Glass fiber

[0097] Circular cross-section glass fiber (Manufacturer: NEG, Product name: T-289DE) was used.

[0098] (C) Additives for laser direct structuring

[0099] Copper hydroxide phosphate (manufacturer: Merck performance materials, product name: Iriotec 884X) was used.

[0100] (D) Inheritance compound

[0101] (D1) A phosphite compound (manufacturer: ADEKA, product name: PEP-8) with a molecular weight of approximately 733 g / mol was used.

[0102] (D2) A phosphonite compound (manufacturer: Ciba, product name: Irgafos P-EPQ) with a molecular weight of approximately 1,035 g / mol was used.

[0103] (D3) A bisphosphite compound (manufacturer: ADEKA, product name: STAB 1500) with a molecular weight of approximately 1,112 g / mol was used.

[0104] (D4) A phosphite compound (manufacturer: ADEKA, product name: 135A) with a molecular weight of approximately 375 g / mol was used.

[0105] (D5) A phosphite compound (manufacturer: Songwon Industrial, product name: SONGNOX DHOP) with a molecular weight of approximately 2,100 g / mol was used.

[0106]

[0107] Examples 1 to 9 and Comparative Examples 1 to 9

[0108] Each of the above components was added in the amounts shown in Tables 1, 2, 3, and 4 below, and then extruded at about 300°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 36 and a diameter of 45 mm. The manufactured pellets were dried at about 100°C for about 4 hours or more, and then injected using a 10 Oz injection molding machine (injection temperature of about 300°C) to produce test pieces. The physical properties of the manufactured test pieces were evaluated using the following methods, and the results are shown in Tables 1, 2, 3, and 4 below.

[0109]

[0110] Method of measuring physical properties

[0111] (1) Plating reliability evaluation: After aging an injection-molded specimen measuring 50 mm × 90 mm × 3.2 mm at 25°C for 6 hours, the surface of the specimen was activated in a stripe shape through a laser direct structuring process, and a copper layer with a thickness of 35 μm was formed on the activated surface through a plating process (copper electroless plating). The plated specimen was left in a chamber under conditions of 85°C and 85% RH for 72 hours, and 100 grids measuring 1 mm × 1 mm were imprinted on the plating layer (copper layer). The number of grids that were not peeled off when the tape was removed was measured.

[0112] (2) Stiffness evaluation: According to ASTM D638, the tensile strength (unit: MPa) of a 3.2 mm thick specimen was measured under the condition of 5 mm / min.

[0113] (3) Evaluation of fluidity (thin film formability): The spiral flow length (unit: mm) of the specimen after injection molding was measured in a spiral-shaped mold with a width of 15 mm and a thickness of 0.5 mm under the conditions of a molding temperature of 320°C, a mold temperature of 60°C, an injection pressure of 100 MPa, and an injection speed of 100 mm / s.

[0114]

[0115] Example 12345 (A) (% by weight) (A1) 7080908080 (A2)-----(B) (% by weight) 3020102020 (C) (parts by weight) 55528 (D1) (parts by weight) 0.20.20.20.20.2 (D2) (parts by weight)-----(D3) (parts by weight)-----(D4) (parts by weight)-----(D5) (parts by weight)-----Number of non-peeled grids (units) 9594969197 Tensile strength (MPa) 1,4901,2808501,3101,290 Spiral flow length (mm) 101119134124112

[0116] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B)

[0117]

[0118] Example 6789 (A) (% by weight) (A1) 80808080 (A2) ---- (B) (% by weight) 20202020 (C) (parts by weight) 5555 (D1) (parts by weight) 0.151.7--(D2) (parts by weight)--0.2-(D3) (parts by weight)--0.2 (D4) (parts by weight)----(D5) (parts by weight) ---- Number of non-exfoliated grids (units) 95949596 Tensile strength (MPa) 1,300 1,280 1,320 1,360 Spiral flow length (mm) 125 120 126 111

[0119] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B)

[0120]

[0121] Comparative Example 12345 (A) (% by weight) (A1) 5599-8080 (A2) --80-- (B) (% by weight) 451202020 (C) (parts by weight) 5550.511 (D1) (parts by weight) 0.20.20.20.20.2 (D2) (parts by weight)-----(D3) (parts by weight)-----(D4) (parts by weight)-----(D5) (parts by weight)-----Number of non-peeled grids (units) 9495796997 Tensile strength (MPa) 1,6106901,2501,340660 Spiral flow length (mm) 8914511012195

[0122] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B)

[0123]

[0124] Comparative Example 6789 (A) (% by weight) (A1) 80808080 (A2) ---- (B) (% by weight) 20202020 (C) (parts by weight) 5555 (D1) (parts by weight) 0.052.5--(D2) (parts by weight) ---- (D3) (parts by weight) ---- (D4) (parts by weight) -- 0.2-(D5) (parts by weight) -- 0.2 Number of non-exfoliated grids (units) 71807975 Tensile strength (MPa) 7101,3001,3001,340 Spiral flow length (mm) 11195118121

[0125] * Weight parts: Weight parts per 100 weight parts of basic materials (A+B)

[0126]

[0127] From the above results, it can be seen that the polyamide resin composition of the present invention has excellent plating reliability, rigidity, fluidity (thin film formability), etc.

[0128] On the other hand, in the case of Comparative Example 1, where a small amount of semi-aromatic polyamide resin was applied and an excessive amount of glass fiber was applied, it can be seen that fluidity, etc. were reduced, and in the case of Comparative Example 2, where an excessive amount of semi-aromatic polyamide resin was applied and a small amount of glass fiber was applied, it can be seen that rigidity, etc. were reduced, and in the case of Comparative Example 3, where a semi-aromatic polyamide resin (A2) was applied instead of the semi-aromatic polyamide resin of the present invention, it can be seen that plating reliability, etc. were reduced. In the case of Comparative Example 4, where a small amount of additive for laser direct structuring was applied, it can be seen that plating reliability, etc. were reduced, and in the case of Comparative Example 5, where an excessive amount of additive for laser direct structuring was applied, it can be seen that rigidity, fluidity, etc. were reduced. In addition, in the case of Comparative Example 6, where a small amount of a phosphorus compound was applied, it can be seen that plating reliability, rigidity, etc. were reduced, and in the case of Comparative Example 7, where an excessive amount of a phosphorus compound was applied, it can be seen that plating reliability, fluidity, etc. were reduced, and in the case of Comparative Example 8, where a phosphite-based compound (D4) having a molecular weight below the range of the present invention was applied instead of the phosphorus-based compound of the present invention, it can be seen that plating reliability, etc. were reduced, and in the case of Comparative Example 9, where a phosphite-based compound (D5) having a molecular weight exceeding the range of the present invention was applied, it can be seen that plating reliability, etc. were reduced.

[0129]

[0130] The present invention has been described with reference to exemplary embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

About 100 parts by weight of a base material comprising about 60 to about 95 wt% of a semi-aromatic polyamide resin having a melting point (Tm) of 1.2 and satisfying the following formula 1, and about 5 to about 40 wt% of glass fiber; About 1 to about 10 parts by weight of an additive for laser direct structuring; and A polyamide resin composition characterized by comprising about 0.1 to about 2 parts by weight of a phosphorus compound having a molecular weight of about 500 to about 1,500 g / mol; [Formula 1] ΔH(Tm 1st ) < ΔH(Tm 2nd ) In the above equation 1, ΔH(Tm 1st ) is the first melting point (Tm 1st ) is the size of the endothermic peak, and ΔH(Tm 2nd ) is the second melting point (Tm 2nd ) is the size of the endothermic peak, and the first melting point (Tm 1st ) is the second melting point (Tm 2nd ) is lower in temperature.

2. A polyamide resin composition according to claim 1, wherein the semi-aromatic polyamide resin is a polymer of an aromatic dicarboxylic acid and an aliphatic diamine.

3. A polyamide resin composition according to claim 1 or 2, characterized in that the semi-aromatic polyamide resin comprises at least one of polyamide 10T, polyamide 11T, and polyamide 12T.

4. A polyamide resin composition according to any one of claims 1 to 3, wherein the glass fiber has a cross-sectional diameter of about 3 to about 8 ㎛.

5. A polyamide resin composition according to any one of claims 1 to 4, wherein the additive for laser direct structuring comprises at least one of a heavy metal complex oxide spinel and a copper salt.

6. A polyamide resin composition according to any one of claims 1 to 5, wherein the weight ratio of the semi-aromatic polyamide resin and the additive for laser direct structuring is about 1:0.01 to about 1:0.

2.

7. A polyamide resin composition according to any one of claims 1 to 6, wherein the weight ratio of the semi-aromatic polyamide resin and the phosphorus compound is about 1:0.001 to about 1:0.

03.

8. A polyamide resin composition according to any one of claims 1 to 7, wherein the polyamide resin composition is characterized in that the number of grids that are not peeled off when the polyamide resin composition is formed by aging an injection-molded specimen measuring 50 mm × 90 mm × 3.2 mm at 25°C for 6 hours, activating the surface of the specimen in a stripe shape through a laser direct structuring process, forming a copper layer having a thickness of 35 μm on the activated surface through a plating process (electroless copper plating), leaving the plated specimen in a chamber under conditions of 85°C and 85% RH for 72 hours, and imprinting 100 grids measuring 1 mm × 1 mm on the plating layer (copper layer), and then removing the polyamide resin composition with tape is about 90 to about 100.

9. A polyamide resin composition according to any one of claims 1 to 8, characterized in that the polyamide resin composition has a tensile strength of about 750 to about 1,600 MPa of a 3.2 mm thick specimen measured under conditions of 5 mm / min according to ASTM D638.

10. A polyamide resin composition according to any one of claims 1 to 9, characterized in that the spiral flow length of a specimen measured after injection molding in a spiral-shaped mold having a width of 15 mm and a thickness of 0.5 mm under conditions of a molding temperature of 340°C, a mold temperature of 100°C, an injection pressure of 100 MPa, and an injection speed of 100 mm / s is about 99 to about 150 mm.

11. A molded product characterized by being formed from a polyamide resin composition according to any one of claims 1 to 10.

12. A molded product according to claim 11, characterized in that the molded product includes a metal layer formed by a laser direct structuring process and a plating process on at least a portion of the surface.

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