KR20190070248A - Thermoplastic resin composition for laser direct structuring process and article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, which comprises: 100 parts by weight of a thermoplastic resin; 1 to 30 parts by weight of a laser direct structuring additive; 0.01 to 5 parts by weight of a hindered phenol-based compound; 0.01 to 10 parts by weight of sodium phosphate salt; 0.01 to 5 parts by weight of a phosphite-based compound; 0.01 to 5 parts by weight of a sulfonate-based compound; and 0.01 to 10 parts by weight of metal oxide. A weight ratio of the hindered phenol-based compound, the sodium phosphate salt, the phosphite-based compound, and the sulfonate-based compound to the metal oxide is 2 : 1 to 10 : 1. The thermoplastic resin composition of the present invention has excellent plating reliability, thermal stability (discoloration resistance), etc., and has excellent injection stability since gas generation is less during injection molding.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition for a laser direct structuring process and a molded article including the thermoplastic resin composition. [0002]

The present invention relates to a thermoplastic resin composition for laser direct structuring process and a molded article comprising the same. More particularly, the present invention relates to a thermoplastic resin composition for laser direct structuring, which is excellent in plating reliability, thermal stability, and is excellent in injection stability due to less generation of gas during injection molding, and a molded article comprising the thermoplastic resin composition.

A laser direct structuring process (LDS process) may be used to plate a metal layer on at least a part of the surface of the molded article formed from the thermoplastic resin composition. The laser direct structuring step is a step performed before the plating step, and means a step of modifying a region to be plated on the surface of a molded article by irradiating a laser beam onto the region to be plated on the surface of the molded article to have properties suitable for plating. For this purpose, the thermoplastic resin composition for producing a molded article should contain a direct laser structuring additive (LDS additive) capable of forming a metal nucleus by a laser. The additive decomposes upon receiving a laser to produce metal nuclei. In addition, the area irradiated with the laser has a roughened surface. Due to such metal nuclei and surface roughness, the laser modified area becomes suitable for plating.

By using the laser direct structuring process, it is possible to form an electric / electronic circuit on a three-dimensional shape of a molded article quickly and economically. For example, the laser direct structuring process can be utilized in the manufacture of antennas for portable electronic devices, radio frequency identification (RFID) antennas, and the like.

In recent years, there has been a demand for a thermoplastic resin composition having excellent mechanical properties and molding processability (appearance characteristics) in accordance with the trend of weight reduction and thinning of products. Further, as the thickness of a fine pattern (plating area) of an electric / electronic circuit such as a portable electronic device is reduced, plating peeling phenomenon may occur and plating reliability may deteriorate.

In addition, in the case of a conventional LDS additive, there is a problem that the thermoplastic resin is decomposed at a temperature at which the thermoplastic resin composition is processed to lower the thermal stability, thereby causing discoloration, gas generation, carbonization and the like.

Therefore, it is necessary to develop a thermoplastic resin composition for laser direct structuring process, which is excellent in plating reliability, thermal stability, and the like and capable of reducing gas generation in injection molding without deteriorating mechanical properties, and a molded article containing the thermoplastic resin composition.

The background art of the present invention is disclosed in Korean Patent Publication No. 2011-0018319.

An object of the present invention is to provide a thermoplastic resin composition for laser direct structuring process which is excellent in plating reliability, heat stability (discoloration resistance) and the like, and is excellent in injection stability with less gas generation during injection molding.

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

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

One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin; 1 to 30 parts by weight of an additive for laser direct structuring; 0.01 to 5 parts by weight of a hindered phenol-based compound; 0.01 to 10 parts by weight of a sodium phosphate salt; 0.01 to 5 parts by weight of a phosphite-based compound; 0.01 to 5 parts by weight of a sulfonate compound; And 0.01 to 10 parts by weight of a metal oxide, wherein the weight ratio of the hindered phenol compound, the sodium phosphate salt, the phosphite compound and the sulfonate compound to the metal oxide is 2: 1 to 10: 1 .

In a specific example, the thermoplastic resin may include at least one of a polycarbonate resin, a rubber-modified aromatic vinyl resin, a polyester resin, a polyamide resin, and a polyarylene ether resin.

In an embodiment, the additive for direct laser structuring may comprise at least one of heavy metal complex oxide spinel and copper salt.

In an embodiment, the metal oxide may include at least one of magnesium oxide, zinc oxide, calcium oxide, and aluminum oxide.

In an embodiment, the thermoplastic resin composition may further include an inorganic filler.

In an embodiment, the inorganic filler may include at least one of glass fiber, talc, wollastonite, whisker, silica, mica, and basalt fiber.

In the specific example, the thermoplastic resin composition is prepared by aging a 50 mm x 90 mm x 3.2 mm injection molded specimen at 25 ° C for 6 hours and then subjecting the surface of the specimen to stripe- And a copper layer having a thickness of 35 탆 was formed on the activated surface through a plating process (copper electroless plating). Then, the plated sample was left in a chamber at 85 캜 and 85% RH for 72 hours, The number of undegraded grid grids may be 90 or more when 100 grid grids of 1 mm in size are stamped on the plated layer (copper layer) and then desorbed with tape.

In the specific example, the thermoplastic resin composition is prepared by measuring the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) in a colorimetric system on a 50 mm × 90 mm × 3.2 mm size injection molding specimen, After staying for 10 minutes, the hue (L ₁ ^* , a ₁ ^* , b ₁ ^* ) may be measured in the same manner and then the color change (ΔE) calculated according to the following formula 1 may be 4 or less:

[Formula 1]

Color change (ΔE) =

In the formula 1, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the residence, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after a stay, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the stay.

Another aspect of the present invention relates to a molded article formed from the thermoplastic resin composition.

In an embodiment, the shaped article may comprise a metal layer formed on at least a portion of the surface by a laser direct structuring process and a plating process.

INDUSTRIAL APPLICABILITY The present invention has an effect of providing a thermoplastic resin composition for laser direct structuring process excellent in plating reliability, heat stability (discoloration resistance) and the like and having less occurrence of gas during injection molding and excellent injection stability and a molded article containing the same .

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

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention can be used in a laser direct structuring process (LDS process), and comprises (A) a thermoplastic resin; (B) Additives for direct laser structuring (LDS); (C) a hindered phenol-based compound; (D) sodium phosphate salt; (E) phosphite-based compounds; (F) a sulfonate-based compound; And (G) a metal oxide.

(A) a thermoplastic resin

The thermoplastic resin used in the present invention may be a thermoplastic resin used for a resin composition for a direct laser structuring process, and examples thereof include a polycarbonate resin, a rubber modified aromatic vinyl resin, a polyester resin, a polyamide resin, a poly And an arylene ether resin. In one embodiment, the thermoplastic resin comprises a polycarbonate resin; A blend of a polycarbonate resin and a rubber-modified aromatic vinyl resin; Or a blend of a polycarbonate resin and a polyester resin.

(A1) Polycarbonate resin

The polycarbonate resin may be a polycarbonate resin used in a conventional thermoplastic resin composition. For example, an aromatic polycarbonate resin prepared by reacting a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, or carbonic acid diester can be used.

Examples of the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-methylphenyl) Bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and the like. Bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl- Hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane. More specifically, bisphenol 2,2-bis (4-hydroxyphenyl) propane called -A can be used.

The above-mentioned polycarbonate resin may be used with a branched chain. For example, 0.05 to 2 mol% of trifunctional or more polyfunctional compounds, specifically trivalent or more, A phenol group-containing compound may be added.

The polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin or a blend thereof.

The polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor such as a bifunctional carboxylic acid.

In an embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 200,000 g / mol, for example, 15,000 to 80,000 g / mol, no.

(A2) Rubber-modified aromatic vinyl resin

Wherein the rubber-modified aromatic vinyl resin comprises 10 to 50% by weight of a graft copolymer (a1) in which an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer are graft copolymerized with a rubbery polymer; And 50 to 90% by weight of an aromatic vinyl-based copolymer (a2) in which an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer are copolymerized.

In an embodiment, the graft copolymer (a1) may be obtained by graft copolymerizing an aromatic vinyl monomer, a monomer copolymerizable with the aromatic vinyl monomer, and the like to a rubbery polymer, and the aromatic vinyl copolymer (a2) Can be copolymerized by adding an aromatic vinyl monomer, a monomer copolymerizable with the aromatic vinyl monomer, and the like. The copolymerization can be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization and bulk polymerization. In the case of the above-mentioned bulk polymerization, the graft copolymer (a1) is a matrix in which the graft copolymer (a1) and the aromatic vinyl copolymer (a2) ) In the form of a rubber-modified aromatic vinyl resin. Here, the rubber (rubbery polymer) content in the final rubber-modified aromatic vinyl resin component is preferably 5 to 40% by weight. In addition, the particle size of the rubber may be 0.05 to 6 탆 in Z-average. In the above range, properties such as impact resistance and appearance can be excellent.

In a specific example, non-limiting examples of the rubber-modified aromatic vinyl resin include copolymers obtained by graft copolymerizing styrene, which is an aromatic vinyl monomer, and acrylonitrile, which is an unsaturated nitrile monomer copolymerizable with styrene, (a-1), which is a copolymer of styrene, which is an aromatic vinyl monomer, and acrylonitrile, which is an unsaturated nitrile monomer capable of copolymerizing with styrene, such as an aromatic vinyl copolymer (SAN) butadiene rubber-styrene copolymer resin (ABS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer resin (AES resin), acrylonitrile-acrylic rubber-styrene copolymer Resin (AAS resin), and the like.

In the specific example, when the thermoplastic resin is a combination (blend) of the polycarbonate resin and the rubber-modified aromatic vinyl resin, the polycarbonate resin is contained in an amount of 50 wt% or more, for example, 60 To 95% by weight, and the rubber-modified aromatic vinyl resin may be contained in an amount of 50% by weight or less, for example, 5 to 40% by weight, based on 100% by weight of the total thermoplastic resin. The impact resistance and mechanical properties of the thermoplastic resin composition may be excellent in the above range.

(A3) Polyester resin

The polyester resin may be a glycol-modified polyester resin. For example, a glycol-modified polyester resin having a 1,4-cyclohexane dimethanol (CHDM) content of 20 to 100 mol% in the whole diol component can be used. In this case, it is possible to improve plating reliability, molding processability and the like while maintaining the rigidity and the like of the thermoplastic resin composition.

In an embodiment, the glycol-modified polyester resin comprises 20 to 100 mol%, for example, 35 to 100 mol% of 1,4-cyclohexanedimethanol (CHDM) and 2 to 20 mol% of a dicarboxylic acid component containing terephthalic acid. , And 0 to 80 mol%, for example, 0 to 65 mol%, of an alkylene glycol having 1 to 6 carbon atoms. Within the above range, the plating reliability and moldability of the thermoplastic resin composition can be excellent.

In an embodiment, the glycol-modified polyester resin has an intrinsic viscosity of 0.5 to 0.8 dl / g, for example, 0.55 to 0.75 dl / g, as measured at 35 DEG C using an o-chlorophenol solution (concentration: 1.2 g / g. In the above range, miscibility between components of the thermoplastic resin composition is improved, and the mechanical properties and molding processability (appearance characteristics) of the thermoplastic resin composition can be excellent.

In the specific example, when the thermoplastic resin is a combination (blend) of the polycarbonate resin and the polyester resin, the polycarbonate resin is contained in an amount of 50 wt% or more, for example, 60 to 95 wt% %, And the polyester resin may be contained in an amount of 50% by weight or less, for example, 5 to 40% by weight, based on 100% by weight of the total thermoplastic resin. Within the above range, the thermoplastic resin composition may have excellent mechanical properties, plating reliability, molding processability, and the like.

(B) Additives for direct laser structuring

The additive for laser direct structuring (LDS) according to one embodiment of the present invention is capable of forming a metal nucleus by a laser, and can be used as an additive for direct laser structuring used in a resin composition for direct laser structuring Can be used. Herein, the laser refers to light (induced emission light) amplified by inductive emission, and the laser is an ultraviolet ray having a wavelength of 100 to 400 nm, a visible ray having a wavelength of 400 to 800 nm or an infrared ray having a wavelength of 800 to 25,000 nm For example, infrared rays having a wavelength of 1,000 to 2,000 nm.

In embodiments, the additive for direct laser structuring may comprise a heavy metal mixture oxide spinel and / or a copper salt.

In an embodiment, the heavy metal complex oxide spinel may be represented by the following formula (1).

[Chemical Formula 1]

AB ₂ O ₄

In the above formula (1), A may be a metal cation having a valence of 2, for example, magnesium, copper, cobalt, zinc, tin, iron, manganese, nickel or a combination thereof and B is a metal cation having a valence of 3, Manganese, nickel, copper, cobalt, tin, titanium, iron, aluminum, chromium, combinations thereof, and the like.

The heavy metal complex oxide spinel represented by the above formula (1) is such that A provides a monovalent cation component of a metal oxide cluster and B provides a monovalent cation component of a metal cation cluster. For example, a metal oxide cluster containing A may have a tetrahedral structure, and a metal oxide cluster including B may have an octahedral structure. Specifically, the heavy metal complex oxide of Formula 1 may be a structure in which oxygen is arranged in a nearly cubic closest packing, B in a gap in an octahedral shape, and A in a gap in a slant shape.

In an embodiment, the heavy metal complex oxide spinel may be at least one selected from the group consisting of magnesium aluminum oxide (MgAl ₂ O ₄ ), zinc aluminum oxide (ZnAl ₂ O ₄ ), iron aluminum oxide (FeAl ₂ O ₄ ), copper iron oxide (CuFe ₂ O ₄ ) (CuCr ₂ O ₄ ), manganese iron oxide (MnFe ₂ O ₄ ), nickel iron oxide (NiFe ₂ O ₄ ), titanium iron oxide (TiFe ₂ O ₄ ), iron chromium oxide (FeCr ₂ O ₄ ) , Magnesium chromium oxide (MgCr ₂ O ₄ ), combinations of these, and the like. For example, copper chromium oxide (CuCr ₂ O ₄ ) can be used. Since the copper chromium oxide (CuCr ₂ O ₄ ) has a dark color, it can be applied to a case where the color required for a final molded product is a dark color such as black or gray.

In an embodiment, the copper salt is selected from the group consisting of copper hydroxide phosphate, copper phosphate, copper sulfate, cuprous thiocyanate, Combinations thereof, and the like, but the present invention is not limited thereto. For example, copper hydroxide phosphate may be used. The copper hydroxide phosphate is a compound having copper phosphate and copper hydroxide bonded thereto. Specifically, Cu ₃ (PO ₄ ) ₂ .2Cu (OH) ₂ , Cu ₃ (PO ₄ ) ₂ Cu (OH) ₂ , and the like. The copper hydroxide phosphate does not lower the color reproducibility of the added colorant, and thus a molded article of a desired color can be easily obtained.

In an embodiment, the additive for direct laser structuring may have an average particle size of 0.01 to 50 탆, for example, 0.1 to 30 탆, specifically 0.5 to 10 탆. In the above range, the plating surface can be formed uniformly during plating through direct laser structuring.

In the present invention, unless otherwise stated, the average particle diameter means a number average diameter, which means that D50 (particle diameter at the point where the distribution ratio is 50%) is measured.

In an embodiment, the laser direct structuring additive may be included in an amount of 1 to 30 parts by weight, for example 5 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the content of the laser direct structuring additive is less than 1 part by weight with respect to 100 parts by weight of the thermoplastic resin, a sufficient amount of metal nuclei can not be formed in the thermoplastic resin composition (molded product) by laser irradiation, If the amount is more than 30 parts by weight, the impact resistance and heat resistance of the thermoplastic resin composition may be lowered.

(C) Hindered phenol compound

The hindered phenol-based compound according to one embodiment of the present invention is capable of reducing the decomposition of the thermoplastic resin and improving the thermal stability (discoloration resistance) and the like of the thermoplastic resin composition. The hindered phenol- A hindered phenol-based compound may be used.

Examples of the hindered phenolic compound include pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxy-hydrocinnamate), triethylene glycol-bis [3- (3- Butyl-5-methyl-4-hydroxyphenyl) propionate, 4,4'-butylidenebis (3-methyl- Di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-di (3,5-di-t-butyl-4-hydroxyphenyl) propionate], ethylenebis [3- (3,5-di-t-butyl-4-hydroxy-hydroxycinnamic acid), 2,2-thiobis ), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl Ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-butyl-4-hydroxybenzyl) benzene, bis (3,5- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di-t-butyl-p-cresol, butylated hydroxyanis (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl- butylphenol), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -O-cresol, isooctyl-3- (3,5- Phenyl) propionate, 4,4'-butylidenebis (3-methyl-6-t-butylphenol, 3,9-bis [1,1- Methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl- Hydroxy-5-t-butylphenyl) butane, (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis [3,3'-bis- (4'- (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -sec-triazine- 4,6- (1H, 3H, 5H) trione, d-? -Tocopherol, and combinations thereof. Examples of commercially available hindered phenol compounds include Irganox ^® 1010 and Irganox ^® 1098 from BASF.

In an embodiment, the hindered phenolic compound may be included in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the content of the hindered phenol compound is less than 0.01 part by weight based on 100 parts by weight of the thermoplastic resin, there is a fear that the thermostability and the like of the thermoplastic resin composition may be deteriorated. When the content of the hindered phenolic compound exceeds 5 parts by weight, And impact resistance may be lowered.

(D) Sodium phosphate salt

The sodium phosphate salt according to one embodiment of the present invention is excellent in water stability and thermal stability and can reduce decomposition of the thermoplastic resin upon exposure to high temperature and high humidity conditions for a long period of time, ) And the like can be improved.

In an embodiment, the sodium phosphate salt is selected from the group consisting of disodium pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, combinations thereof And the like.

In an embodiment, the sodium phosphate salt may be contained in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the content of the sodium phosphate salt is less than 0.01 part by weight based on 100 parts by weight of the thermoplastic resin, the thermoplastic resin composition may be deteriorated in thermal stability and heat resistance. When the content is more than 10 parts by weight, The impact resistance and the like may be lowered.

(E) Phosphite compound

The phosphite-based compound according to one embodiment of the present invention is capable of reducing the decomposition of the thermoplastic resin and improving the thermal stability (discoloration resistance) and the like of the thermoplastic resin composition, and is used for a general thermoplastic resin composition A phosphite-based antioxidant may be used.

In an embodiment, the phosphite-based compounds include triphenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trinonyl phenyl phosphite, diphenyl isodecyl phosphite, bis (2,6- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol (Tridecyl-4,4'-isopropylidenediphenyl diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, combinations thereof, etc.) .

In an embodiment, the phosphite compound may be contained in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the content of the phosphite compound is less than 0.01 part by weight based on 100 parts by weight of the thermoplastic resin, the thermoplastic resin composition may have poor thermal stability and heat resistance. If the content of the phosphite compound exceeds 5 parts by weight, Rigidity, impact resistance, and the like may be lowered.

(F) sulfonate compound

The sulfonate compound according to one embodiment of the present invention is capable of reducing the decomposition of the thermoplastic resin and improving the thermal stability (discoloration resistance) and the like of the thermoplastic resin composition, and is used for a general thermoplastic resin composition And aromatic sulfonic acid metal salts.

In an embodiment, the sulfonate-based compounds include disodium diphenylsulfide-4,4'-disulfonate, dipotassium sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, Sodium phthalate, polyethylene terephthalate, polysodium polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethyldiphenyloxide) Sodium, poly (1,3-phenylene oxide) polysulfonate, poly (1,4-phenylene oxide) polysulfonate, poly (2,6-diphenylphenylene oxide) (2-fluoro-6-butylphenylene oxide) lithium polysulfonate, potassium benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, p-benzenedisulfonic acid Dipotassium salt of diphenylmethane diisocyanate, dipotassium dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonic acid, Sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone-3,4'-disulfonic acid dipotassium, benzophenol-3,3'-disulfonic acid Disodium thiophene-2,4-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, and sodium benzothiophene sulfonate. They may be used alone or as a mixture. Among them, potassium diphenylsulfone-3-sulfonate is preferably used.

In an embodiment, the sulfonate compound may be included in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the content of the sulfonate compound is less than 0.01 part by weight with respect to 100 parts by weight of the thermoplastic resin, the thermoplastic resin composition may be deteriorated in thermal stability and heat resistance. When the content of the sulfonate compound exceeds 5 parts by weight, Rigidity, impact resistance, and the like may be lowered.

(G) Metal oxide

The metal oxide according to one embodiment of the present invention can be used together with the hindered phenol compound, sodium phosphate salt, phosphite compound and sulfonate compound to reduce the decomposition of the thermoplastic resin and improve the thermal stability of the thermoplastic resin composition (MgO), zinc oxide (ZnO), calcium oxide (CaO), aluminum oxide (Al ₂ O ₃ ), combinations thereof and the like, which can improve the coloring resistance For example, magnesium oxide (MgO) and / or zinc oxide (ZnO) can be used.

In an embodiment, the metal oxide may be included in an amount of 0.01 to 10 parts by weight, for example 0.02 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the content of the metal oxide is less than 0.01 part by weight based on 100 parts by weight of the thermoplastic resin, the thermoplastic resin composition may be deteriorated in thermal stability and heat resistance. If the content of the metal oxide exceeds 10 parts by weight, The impact resistance and the like may be lowered.

(C + D + E + F) of the hindered phenolic compound, the sodium phosphate salt, the phosphite compound and the sulfonate compound (C, D, E, F) F): (G)) may be from 2: 1 to 10: 1, for example from 3: 1 to 6: 1. If the weight ratio is less than 2: 1, the fluidity and impact resistance of the thermoplastic resin composition may be deteriorated. If the weight ratio is more than 10: 1, the thermal stability and the like may be lowered.

The thermoplastic resin composition according to one embodiment of the present invention may further include an inorganic filler to improve mechanical properties and the like. The inorganic filler may include an additive for direct laser structuring and a conventional inorganic filler except for the above components. Examples of the inorganic filler include glass fiber, talc, wollastonite, whisker, silica, mica, basalt fiber, mixtures thereof, and the like. Specifically, glass fiber can be used.

In an embodiment, the inorganic filler may be a glass fiber having a circular cross section having an average cross-sectional area of 5 to 20 탆 and a length of 2 to 5 mm measured by an optical microscope, or an aspect ratio Short diameter) of 1.5 to 10, and a length before processing of 2 to 5 mm. Within the above range, the mechanical properties and the surface hardness can be improved without deteriorating the physical properties such as the appearance characteristics of the thermoplastic resin composition.

In an embodiment, the inorganic filler may be included in an amount of 1 to 40 parts by weight, for example 5 to 30 parts by weight, based on 100 parts by weight of the thermoplastic resin. Within the above range, the impact resistance, rigidity, surface hardness, and external appearance characteristics of the thermoplastic resin composition can be excellent.

If necessary, the thermoplastic resin composition according to one embodiment of the present invention may further contain any additive conventionally used in the thermoplastic resin composition, so long as the effect of the present invention is not impaired. Examples of the additives include, but are not limited to, lubricants, colorants, antistatic agents, and flame retardants. When the additive is used, it may be included in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the base resin.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of a pellet obtained by melt-extruding the above components at a temperature of 200 to 300 ° C, for example, 250 to 280 ° C, using a conventional twin-screw extruder.

In the specific example, the thermoplastic resin composition is prepared by aging a 50 mm x 90 mm x 3.2 mm injection molded specimen at 25 ° C for 6 hours and then subjecting the surface of the specimen to stripe- And a copper layer having a thickness of 35 탆 was formed on the activated surface through a plating process (copper electroless plating). Then, the plated sample was left in a chamber at 85 캜 and 85% RH for 72 hours, The number of unetched grid lattices may be 90 or more, for example, 92 to 100, when 100 grid lattices of size 1 mm in size are impressed on the plated layer (copper layer) and then desorbed with tape.

In the specific example, the thermoplastic resin composition is prepared by measuring the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) in a colorimetric system on a 50 mm × 90 mm × 3.2 mm size injection molding specimen, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) is measured by the same method after staying for 10 minutes, and then the color change (ΔE) calculated according to the following formula 1 is 4 or less, for example, 0.1 to 3 days Can:

[Formula 1]

Color change (ΔE) =

In the formula 1, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the residence, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after a stay, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the stay.

The molded article according to the present invention is formed from the thermoplastic resin composition. For example, the thermoplastic resin composition can be used to produce a molded article by a molding method such as injection molding, compression molding, blow molding, or extrusion molding. The molded article can be easily formed by a person having ordinary skill in the art to which the present invention belongs.

1 schematically shows 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. 1, the molded article 10 according to one embodiment of the present invention may include a metal layer 20 formed on at least a part 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 or the like used for manufacturing an antenna. The molded article 10 may be formed of a thermoplastic resin composition, for example, 10); Irradiating a laser beam onto a specific region (a metal layer 20 portion) on the surface of the molded product 10; And then metallizing (plating) the irradiated region to form the metal layer 20.

In the embodiment, the laser direct structuring additive contained in the molded article 10 is decomposed by the laser irradiation to generate 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.

In an embodiment, the metallization process may be performed through a conventional plating process. For example, it is possible to form the metal layer 20 (electrically conductive path) on the laser-irradiated area of the surface of the molded article 10 by dipping the laser-irradiated molded article 10 into one or more electroless plating baths. Examples of the plating process include, but are not limited to, a copper plating process, a gold plating process, a nickel plating process, a silver plating process, a zinc plating process, and a tin plating process.

As described above, a molded product having a metal layer formed on at least a part of its 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 belongs.

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

Example

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

(A) a thermoplastic resin

(A1) Polycarbonate resin

A bisphenol-A polycarbonate resin having a weight average molecular weight of 23,000 g / mol (manufacturer: Lotte Hidan Material) was used.

(A2) Rubber-modified aromatic vinyl resin

Acrylonitrile-butadiene-styrene copolymer (ABS) resin (manufactured by LG Chem, product name: ABS ER400) was used.

(A3) Polyester resin

Glycol-modified polyester resin (a manufacturer:: SK chemicals, product name Skygreen ^® S2008) was used.

(B) Additives for direct laser structuring

Copper hydroxide phosphate (manufacturer:: Merck performance materials, product name Iriotec 8840 ^®) was used.

(C) Hindered phenol compound

Pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxy-hydrocinnamate) (manufacturer: BASF, product name: Irganox ^® 1010) was used.

(D) Sodium phosphate salt

Disodium pyrophosphate (manufacturer: Innophos) was used.

(E) Phosphite compound

Tris (2,4-di-tert-butylphenyl) phosphite (manufacturer: ADEKA, product name: ADK STAB PEP-36)

(F) sulfonate compound

Diphenyl sulfone-3-sulfonic acid potassium salt (manufactured by Seal Sands Chemicals) was used.

(G) Metal oxide

Magnesium oxide (manufacturer: KYOWA CHEMICAL, product name: KYOWA MAG 150) was used.

(H) inorganic filler

Glass fiber (manufacturer: Nittobo, product name: CSG 3PA-832) was used.

Examples 1 to 4 and Comparative Examples 1 to 5

The above components were added in the amounts shown in Table 1 and extruded at a barrel temperature of 250 to 300 DEG C using a twin-screw extruder having an L / D of 36 and a diameter of 45 mm to form a pellet, Type thermoplastic resin composition. The prepared pellets were dried at 80 to 100 ° C. for 4 hours or more and then injection molded at a molding temperature of 300 ° C. and a mold temperature of 60 ° C. to prepare test specimens. The properties of the prepared specimens were measured by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Plating reliability: 50 mm × 90 mm × 3.2 mm size After injection molding specimens were aged at 25 ° C. for 6 hours, the surface of the specimen was activated in stripe form through the laser direct structuring process, A copper layer having a thickness of 35 탆 was formed on the activated surface through a plating process (copper electroless plating), and then the plated sample was left in a chamber at 85 캜 and 85% RH for 72 hours, Size, 100 grid lattices were imprinted on the plated layer (copper layer), and then the number of undegraded grid lattices upon tape detachment was measured.

(2) Injection stability: The number of specimens with silver streaks around the gate of the specimen was measured by continuous injection molding of 10 specimens.

(L ₀ ^* , a ₀ ^* , b ₀ ^* ) with a colorimeter (manufacturer: Konica Minolta, product name: CM-3700A) for injection molding specimens of 50 mm × 90 mm × 3.2 mm size. (L ₁ ^* , a ₁ ^* , b ₁ ^* ) were measured by the same method and then the color change (ΔE) was calculated according to the following formula 1 :

[Formula 1]

Color change (ΔE) =

In the formula 1, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the residence, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after a stay, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the stay.

Example Comparative Example One 2 3 4 One 2 3 4 5 (A)
(weight%) (A1) 100 100 80 80 100 100 100 100 100 (A2) - - 20 - - - - - - (A3) - - - 20 - - - - - (B) (parts by weight) 10 10 10 10 10 10 10 10 10 (C) (parts by weight) 0.5 0.5 0.5 0.5 - 0.5 0.5 0.5 0.5 (D) (parts by weight) One One One One One - One One One (E) (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.5 - 0.5 0.5 (F) (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - 0.5 (G) (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - (H) (parts by weight) - 20 - - - - - - - Number of unlabeled grid lattices 95 92 96 98 88 45 86 42 88 Number of gas generating specimens 0 0 0 0 7 8 5 7 0 Color change (ΔE) 2.0 1.7 2.2 2.5 5.8 8.5 5.4 9.7 11.2

Parts by weight based on 100 parts by weight of the thermoplastic resin (A)

From the results shown in Table 1, it can be seen that the thermoplastic resin composition of the present invention is excellent in plating reliability, injection stability and thermal stability.

On the other hand, in the case of Comparative Example 1 in which the hindered phenol compound (C) was not used, thermal stability was lowered, and gas silver was generated in the injection molding specimen. In the case of Comparative Example 2 in which the sodium phosphate salt (D) was not used, the plating reliability, thermal stability and injection stability were deteriorated. In Comparative Example 3 in which the phosphite compound (E) was not used, The injection stability was deteriorated. In Comparative Example 4 in which the sulfonate compound (F) was not used, the plating reliability, thermal stability and injection stability were found to be lowered. Comparative Example 5 , The thermal stability is remarkably lowered.

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

Claims (10)

100 parts by weight of a thermoplastic resin;
1 to 30 parts by weight of an additive for laser direct structuring;
0.01 to 5 parts by weight of a hindered phenol-based compound;
0.01 to 10 parts by weight of a sodium phosphate salt;
0.01 to 5 parts by weight of a phosphite-based compound;
0.01 to 5 parts by weight of a sulfonate compound; And
0.01 to 10 parts by weight of a metal oxide,
Wherein the weight ratio of the hindered phenol compound, the sodium phosphate salt, the phosphite compound and the sulfonate compound to the metal oxide is 2: 1 to 10: 1.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin comprises at least one of a polycarbonate resin, a rubber-modified aromatic vinyl resin, a polyester resin, a polyamide resin and a polyarylene ether resin.
The thermoplastic resin composition according to claim 1, wherein the additive for direct laser structuring comprises at least one of a heavy metal complex oxide spinel and a copper salt.
The thermoplastic resin composition according to claim 1, wherein the metal oxide comprises at least one of magnesium oxide, zinc oxide, calcium oxide, and aluminum oxide.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition further comprises an inorganic filler.
The thermoplastic resin composition according to claim 5, wherein the inorganic filler comprises at least one of glass fiber, talc, wollastonite, whisker, silica, mica, and basalt fiber.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is prepared by aging an injection molding specimen of 50 mm × 90 mm × 3.2 mm size at 25 ° C. for 6 hours and then subjecting the specimen to a stripe- After the surface was activated and a copper layer having a thickness of 35 탆 was formed on the activated surface through a plating process (copper electroless plating), the plated sample was left in a chamber at 85 캜 and 85% RH for 72 hours, Wherein 100 grid lattices having a size of 1 mm x 1 mm are imprinted on a plated layer (copper layer), and then the number of unetched grid lattices is 90 or more upon desorption with tape.
2. The method of claim 1, wherein the thermoplastic resin composition has an initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) measured by a colorimetric method on a 50 mm × 90 mm × 3.2 mm injection molded specimen, (L ₁ ^* , a ₁ ^* , b ₁ ^* ) is measured by the same method after staying in the chamber for 10 minutes, and the color change (ΔE) calculated according to the following formula 1 is 4 or less Composition:
[Formula 1]
Color change (ΔE) =

In the formula 1, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the residence, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after a stay, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the stay.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 8.
10. A molded article according to claim 9, wherein the molded article comprises a metal layer formed on at least a part of the surface by a laser direct structuring process and a plating process.

Images