Thermoplastic resin composition for laser direct structuring process and molded product including the same
阅读说明：本技术 用于激光直接结构化工艺的热塑性树脂组合物和包括其的模塑产品 (Thermoplastic resin composition for laser direct structuring process and molded product including the same ) 是由 金男炫 金桢淇 洪尚铉 于 2018-12-05 设计创作，主要内容包括：本发明涉及一种用于激光直接结构化工艺的热塑性树脂组合物和包括其的模塑产品。在一个具体的实施方式中,热塑性树脂组合物包括：约100重量份的基础树脂；约0.1-20重量份的用于激光直接结构化的添加剂；以及约1-20重量份的抗冲击改性剂,其中所述基础树脂包括聚碳酸酯树脂、聚碳酸酯-聚硅氧烷共聚物和聚酯树脂。(The present invention relates to a thermoplastic resin composition for a laser direct structuring process and a molded product including the same. In one embodiment, a thermoplastic resin composition comprises: about 100 parts by weight of a base resin; about 0.1 to about 20 parts by weight of an additive for laser direct structuring; and about 1 to 20 parts by weight of an impact modifier, wherein the base resin comprises a polycarbonate resin, a polycarbonate-polysiloxane copolymer, and a polyester resin.)
1. A thermoplastic resin composition comprising:
100 parts by weight of a base resin comprising about 20 to about 70 wt% of a polycarbonate resin, about 10 to about 70 wt% of a polycarbonate-polysiloxane copolymer, and about 5 to about 30 wt% of a polyester resin containing an alicyclic group in the main chain;
about 0.1 to about 20 parts by weight of an additive for laser direct structuring; and
about 1 to about 20 parts by weight of an impact modifier.
2. The thermoplastic resin composition of claim 1, wherein said polyester resin comprises poly (1, 4-cyclohexanedimethanol terephthalate) (PCT).
3. The thermoplastic resin composition of claim 1 or 2, wherein said polycarbonate-polysiloxane copolymer comprises about 80 wt% to about 95 wt% polycarbonate block and about 5 wt% to about 20 wt% polysiloxane block.
4. The thermoplastic resin composition of any of claims 1-3, wherein said polycarbonate-polysiloxane copolymer has a weight average molecular weight of about 10,000g/mol to about 50,000 g/mol.
5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the additive for laser direct structuring comprises at least one selected from the group of heavy metal complex oxide spinels and copper salts.
6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the impact modifier comprises an impact modifier of a core-shell structure obtained by grafting an unsaturated compound to a rubber polymer, the unsaturated compound comprising at least one selected from the group consisting of an acrylic monomer, an aromatic vinyl monomer, an unsaturated nitrile monomer, and a polymer thereof, the rubber polymer being obtained by polymerization of a diene monomer, or the rubber polymer being obtained by copolymerization of at least one monomer selected from the group consisting of a diene monomer, an acrylic monomer, a siloxane monomer, and a styrene monomer.
7. The thermoplastic resin composition of any of claims 1-6, wherein the impact modifier and the polycarbonate-polysiloxane copolymer are present in a weight ratio of about 1:5 to about 1: 10.
8. The thermoplastic resin composition of any of claims 1-7, wherein the additive for laser direct structuring and the impact modifier are present in a weight ratio of about 1:1 to about 1: 3.
9. The thermoplastic resin composition of any of claims 1-8, having a weight-drop height of about 60cm or greater at which cracks develop on a specimen of the thermoplastic resin composition when a metal tip weighing 500g is dropped onto the specimen according to the dupont drop test method, the specimen being prepared by immersing an injection molded specimen having a size of 100mm × 100mm × 3.2.2 mm in a diluting solution (T-280,
10. A molded product formed from the thermoplastic resin composition according to any one of claims 1 to 9.
11. The molded product of claim 10, wherein the molded product comprises a metal layer formed on at least a portion of its surface by a laser direct structuring and plating process.
Technical Field
The present invention relates to a thermoplastic resin composition for laser direct structuring and a molded product comprising the same.
Background
A Laser Direct Structuring (LDS) process may be used to form a metal layer on at least a portion of a surface of a molded product produced from the thermoplastic resin composition. The LDS process is a pretreatment method for modifying a plating target area to have appropriate plating properties by irradiating the surface of a molded product with a laser beam. For this reason, the thermoplastic resin composition needs to contain an additive for laser direct structuring (LDS additive) that can form a metal core under irradiation with a laser beam. The LDS additive decomposes under irradiation with a laser beam to produce metal nuclei. Further, the area irradiated with the laser beam has a rough surface. Due to this metal core and surface roughness, the laser modified area becomes suitable for the plating process.
The LDS process allows electronic devices/circuits to be quickly and economically formed on three-dimensional molded products. For example, the LDS process may be advantageously used in the manufacture of antennas for portable electronic devices, Radio Frequency Identification (RFID) antennas, and the like.
On the other hand, an antenna for a mobile electronic device such as a smartphone requires a separate electrode corresponding to a frequency band, and it is important to realize a fine pattern corresponding to the frequency band. The LDS process can realize a fine pattern at a desired position, thereby ensuring a high degree of freedom in design.
Typical LDS additives decompose a thermoplastic resin composition at the processing temperature of the thermoplastic resin composition, thereby causing discoloration, gas generation, carbonization, and the like through deterioration of thermal stability. Therefore, there is a need to develop a thermoplastic resin composition for laser direct structuring having good properties in terms of durability, plating reliability and thermal stability under high temperature/high humidity conditions and capable of suppressing gas generation at the time of injection molding, and a molded product including the same.
Disclosure of Invention
[ problem ] to provide a method for producing a semiconductor device
An aspect of the present invention provides a thermoplastic resin composition for laser direct structuring having good plating reliability under high temperature/high humidity conditions.
Another aspect of the present invention provides a thermoplastic resin composition for laser direct structuring having good impact resistance and heat resistance.
A further aspect of the present invention provides a molded product formed from the thermoplastic resin composition for laser direct structuring.
[ technical solution ] A
1. One aspect of the present invention relates to a thermoplastic resin composition for laser direct structuring. In one embodiment, the thermoplastic resin composition may include: 100 parts by weight of a base resin comprising about 20% by weight (wt%) to about 70 wt% of a polycarbonate resin, about 10 wt% to about 70 wt% of a polycarbonate-polysiloxane copolymer, and about 5 wt% to about 30 wt% of a polyester resin containing an alicyclic group in the main chain; about 0.1 to about 20 parts by weight of an additive for laser direct structuring; and about 1 to about 20 parts by weight of an impact modifier.
2. In embodiment 1, the polyester resin may include poly (1, 4-cyclohexanedimethanol terephthalate) (PCT).
3. In embodiments 1 and 2, the polycarbonate-polysiloxane copolymer can comprise about 80 wt% to about 95 wt% polycarbonate blocks and about 5 wt% to about 20 wt% polysiloxane blocks.
4. In embodiments 1 to 3, the polycarbonate-polysiloxane copolymer may have a weight average molecular weight of about 10,000g/mol to about 50,000 g/mol.
5. In embodiments 1 to 4, the additive for laser direct structuring may include at least one selected from the group consisting of a heavy metal composite oxide spinel and a copper salt.
6. In embodiments 1 to 5, the impact modifier may include an impact modifier of a core-shell structure obtained by grafting an unsaturated compound including at least one selected from the group consisting of an acrylic monomer, an aromatic vinyl monomer, an unsaturated nitrile monomer, and a polymer thereof to a rubber polymer obtained by polymerization of a diene monomer, or a rubber polymer obtained by copolymerization of at least one selected from the group consisting of a diene monomer, an acrylic monomer, a siloxane monomer, and a styrene monomer.
7. In embodiments 1 to 6, the impact modifier and the polycarbonate-polysiloxane copolymer may be present in a weight ratio of about 1:5 to about 1: 10.
8. In embodiments 1 to 7, the additive for laser direct structuring and the impact modifier may be present in a weight ratio of about 1:1 to about 1: 3.
9. In embodiments 1 through 8, the thermoplastic resin composition may have a weight-drop height of about 60cm or greater at which cracks develop on a specimen of the thermoplastic resin composition when a metal tip weighing 500g is dropped onto the specimen according to the dupont drop test method, wherein the specimen is prepared by: will have the size of100mm × 100mm × 3.2.2 mm injection molded specimens were immersed in a dilute solution (T-280, Nanlu (Noroo)) For 2 minutes, the sample was dried at 80 ℃ for 20 minutes and left at room temperature for 24 hours.
10. Another aspect of the present invention relates to a molded product formed from the thermoplastic resin composition of embodiments 1 to 9.
11. In embodiment 10, the molded product may include a metal layer formed on at least a portion of a surface thereof by a laser direct structuring and plating process.
[ PROBLEMS ] the present invention
The molded product produced using the thermoplastic resin composition according to the present invention has good plating reliability under high temperature/high humidity conditions, good impact resistance after plating process, and good heat resistance.
Drawings
Fig. 1 is a diagram of a molded product according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Descriptions of well-known functions and constructions that may unnecessarily obscure the subject matter of the present invention will be omitted herein.
Terms used herein are defined by considering functions of the present invention and can be changed according to custom or intention of a user or an operator. Accordingly, the definition of terms should be made in light of the overall disclosure set forth herein.
Thermoplastic resin composition for laser direct structuring
One aspect of the present invention relates to a thermoplastic resin composition for laser direct structuring. In one embodiment, a thermoplastic resin composition includes a base resin, an LDS additive, and an impact modifier.
Base resin
The base resin includes a polycarbonate resin, a polycarbonate-polysiloxane copolymer, and a polyester resin containing an alicyclic group in the main chain.
Polycarbonate resin
According to the present invention, the polycarbonate resin may be selected from any polycarbonate resins used in typical thermoplastic resin compositions. For example, the polycarbonate resin may be an aromatic polycarbonate resin prepared by reacting a diphenol (an aromatic diol compound) with a precursor such as phosgene, a haloformate or a carbonic diester:
[ formula 1]
Wherein A is a single bond, substituted or unsubstituted C1To C30Straight or branched alkylene, substituted or unsubstituted C2To C5Alkenylene, substituted or unsubstituted C2To C5Alkylidene, substituted or unsubstituted C1To C30Straight or branched chain haloalkylene, substituted or unsubstituted C5To C6Cycloalkylene, substituted or unsubstituted C5To C6Cycloalkenylene, substituted or unsubstituted C5To C10Cycloalkylidene radical, substituted or unsubstituted C6To C30Arylene, substituted or unsubstituted C1To C20Linear or branched alkyleneoxy groups, ester groups of halogenated acids, carbonate groups, CO, S or SO2；R1And R2Are identical or different from each other and are substituted or unsubstituted C1To C30Alkyl or substituted or unsubstituted C6To C30An aryl group; and a and b are each independently an integer of 0 to 4.
Examples of the diphenol represented by formula 1 may include 4,4' -biphenol, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (3-chloro-4-hydroxyphenyl) propane and 2, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, but are not limited thereto. For example, the diphenol may be 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane or 1, 1-bis (4-hydroxyphenyl) cyclohexane, in particular 2, 2-bis- (4-hydroxyphenyl) propane, which is also referred to as bisphenol a.
The polycarbonate resin may be a mixture of copolymers obtained from two or more bisphenols. For example, the polycarbonate resin may include a linear polycarbonate resin. The linear polycarbonate resin may be a bisphenol a type polycarbonate resin.
In some embodiments, the polycarbonate resin may be a branched polycarbonate resin. For example, the polycarbonate resin may be a branched polycarbonate resin obtained by adding about 0.05 mol% to about 2 mol% of a trifunctional compound or higher multifunctional compound (particularly, a compound having a trivalent or higher phenolic group), based on the total moles of diphenols used in the polymerization.
The polycarbonate resin may be a homopolycarbonate resin, a copolymeric polycarbonate resin, or a blend thereof.
The polycarbonate resin may be partially or fully replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor (e.g., a difunctional carboxylic acid).
The polycarbonate resin may have a weight average molecular weight (Mw) of about 10,000g/mol to about 200,000g/mol as measured by Gel Permeation Chromatography (GPC). For example, the weight average molecular weight (Mw) of the polycarbonate resin may be about 15,000g/mol to about 80,000g/mol, but is not limited thereto.
In one embodiment, the polycarbonate resin may be present in an amount of about 20 wt% to about 70 wt%, based on 100 wt% of the base resin. If the content of the polycarbonate resin is less than about 20 wt%, the processability and appearance of the thermoplastic resin composition may suffer from deterioration, and if the content of the polycarbonate resin exceeds about 70 wt%, the plating reliability and impact resistance of the thermoplastic resin composition may suffer from deterioration. For example, the polycarbonate resin may be present in an amount of about 30 wt% to about 65 wt%.
Polycarbonate-polysiloxane copolymers
The polycarbonate-polysiloxane copolymer comprises polycarbonate blocks and polysiloxane blocks.
In one embodiment, the polycarbonate block may comprise structural units derived from a polycarbonate resin, and the polysiloxane block may comprise structural units derived from formula 2:
[ formula 2]
Wherein R is3And R4Are identical or different from each other and are a hydrogen atom, a substituted or unsubstituted C1To C20Alkyl, substituted or unsubstituted C2To C20Alkenyl, substituted or unsubstituted C2To C20Alkynyl, substituted or unsubstituted C1To C20Alkoxy, substituted or unsubstituted C3To C30Cycloalkyl, substituted or unsubstituted C3To C30Cycloalkenyl, substituted or unsubstituted C3To C30Cycloalkynyl, substituted or unsubstituted C6To C30Aryl, substituted or unsubstituted C6To C30Aryloxy, substituted or unsubstituted C6To C30Aryl or NRR '(R and R' are the same or different from each other and are a hydrogen atom or a substituted or unsubstituted C1To C20Alkyl), and is a linking site.
In formula 2, n ranges from 2 to 10,000, for example from 2 to 1,000. Within this range, the thermoplastic resin composition exhibits good impact resistance and appropriate viscosity to allow efficient extrusion. For example, n ranges from 10 to 100, especially from 25 to 80.
In one embodiment, the polycarbonate-polysiloxane copolymer can comprise about 80 wt% to about 95 wt% polycarbonate blocks and about 5 to about 20 wt% polysiloxane blocks. Within these ranges, the thermoplastic resin composition may have good heat resistance and impact resistance.
In one embodiment, the polycarbonate-polysiloxane copolymer can have a weight average molecular weight (Mw) of about 10,000g/mol to about 50,000 g/mol. For example, the polycarbonate-polysiloxane copolymer can have a weight average molecular weight (Mw) of about 15,000g/mol to about 40,000 g/mol. Within this range, the thermoplastic resin composition may have good impact resistance.
In one embodiment, the polycarbonate-polysiloxane copolymer can have a melt flow index (MI) of about 3g/10min to about 100g/10min, measured at 300 ℃ and 1.2kgf according to ASTM D1238. Within this range, the thermoplastic resin composition may have good mechanical properties and flowability. For example, the polycarbonate-polysiloxane copolymer can have a melt flow index (MI) of about 10g/10min to about 70g/10 min.
The polycarbonate-polysiloxane copolymer can be present in an amount of about 10 wt% to about 70 wt% based on 100 wt% of the base resin. If the content of the polycarbonate-polysiloxane copolymer is less than about 10 wt%, plating reliability and impact resistance after plating process of the thermoplastic resin composition under high temperature/humidity conditions may suffer deterioration, and if the content of the polycarbonate-polysiloxane copolymer exceeds about 70 wt%, impact resistance, heat resistance and processability of the thermoplastic resin composition may suffer deterioration. For example, the polycarbonate-polysiloxane copolymer can be present in an amount of about 20 wt% to about 60 wt%.
Polyester resin
The polyester resin may contain an alicyclic group in its main chain. For example, the polyester resin may include a poly (1, 4-cyclohexanedimethanol terephthalate) resin (PCT) containing a repeating unit represented by formula 3:
[ formula 3]
Wherein m is an integer from 50 to 500, and x is a linking site.
The intrinsic viscosity [. eta. ] of the polyester resin may be about 0.4dl/g to about 1.5 dl/g. Intrinsic viscosity can be measured in o-chlorophenol solution at 35 ℃. Within this range of viscosity, the polyester resin can improve mechanical properties and molding processability of the thermoplastic resin composition. For example, the intrinsic viscosity of the polyester resin may be about 0.6dl/g to about 1.2 dl/g.
The polyester resin may be present in an amount of about 5 wt% to about 30 wt% based on 100 wt% of the base resin. If the content of the polyester resin is less than about 5 wt%, plating reliability and hydrolysis resistance of the thermoplastic resin composition under high temperature/humidity conditions may suffer from deterioration, and if the content of the polyester resin exceeds about 30 wt%, impact resistance of the thermoplastic resin composition may suffer from deterioration. For example, the polyester resin may be present in an amount of about 10 wt% to about 25 wt%.
Additive for laser direct structuring (LDS additive)
The LDS additive is used to form metal nuclei when irradiated with a laser beam, and may include any typical LDS additive used in a resin composition for LDS. Here, the term "laser beam" refers to light amplified by simulated emission (simulated luminescence), and may be ultraviolet light having a wavelength of about 100nm to about 400nm, visible light having a wavelength of about 400nm to about 800nm, or Infrared (IR) light having a wavelength of about 800nm to about 25,000nm, for example, IR light having a wavelength of about 1,000nm to 2,000 nm.
In one embodiment, the LDS additive may include at least one selected from the group consisting of a heavy metal composite oxide spinel and a copper salt.
In one embodiment, the heavy metal composite oxide spinel may be represented by formula 4:
[ formula 4]
AB2O4，
Wherein a is a metal cation having a valence of 2, for example, magnesium, copper, cobalt, zinc, tin, iron, manganese, nickel, and combinations thereof; and B is a metal cation having a valence of 3, for example, manganese, nickel, copper, cobalt, tin, titanium, iron, aluminum, chromium, and combinations thereof.
In the heavy metal composite oxide spinel represented by formula 4, a provides a monovalent cation component of the metal oxide cluster, and B provides a monovalent cation component of the metal cation cluster. For example, the metal oxide cluster including a may have a tetrahedral structure, and the metal oxide cluster including B may have an octahedral structure. Specifically, the heavy metal composite oxide spinel represented by formula 4 may have a structure in which oxygen atoms are arranged in a cubic close-packed lattice and B and a occupy octahedral sites and tetrahedral sites in the lattice, respectively.
In one embodiment, the heavy metal composite oxide spinel may include magnesium aluminum oxide (MgAl)2O4) Zinc aluminum oxide (ZnAl)2O4) Iron-aluminum oxide (FeAl)2O4) Copper iron oxide (CuFe)2O4) Copper chromium oxide (CuCr)2O4) Manganese iron oxide (MnFe)2O4) Nickel iron oxide (NiFe)2O4) Titanium iron oxide (TiFe)2O4) Iron chromium oxide (FeCr)2O4) Magnesium chromium oxide (MgCr)2O4) And combinations thereof. For example, the heavy metal composite oxide spinel may be copper chromium oxide (CuCr)2O4). Copper chromium oxide (CuCr)2O4) Has a dark color and is therefore advantageous when the final molded product is required to be black or gray.
In one embodiment, the copper salt may include, but is not limited to, copper hydroxide phosphate, copper sulfate, cuprous thiocyanate, and combinations thereof. For example, the copper salt may be a copper hydroxide phosphate. Copper hydroxide phosphate is a compound in which copper phosphate is combined with copper hydroxide, and may include Cu3(PO4)2·2Cu(OH)2、Cu3(PO4)2·Cu(OH)2And the like. As an additive, basic copper phosphate does not affect the color reproducibility of the colorant, thus making it easy to obtain a molded product having a desired color.
In one embodiment, the LDS additive may have an average particle size of from about 0.01 μm to about 50 μm, for example from about 0.1 μm to about 30 μm, and particularly from about 0.5 μm to about 10 μm. In this context, a uniform coating surface can be formed by direct structuring by means of a laser.
As used herein, unless otherwise specifically indicated, the term "average particle diameter" refers to D50 (diameter at 50% distribution), which is a number average particle diameter.
The LDS additive may be present in an amount of about 0.1 parts by weight to about 20 parts by weight relative to 100 parts by weight of the base resin. If the content of the LDS additive is less than about 0.1 parts by weight, a sufficient amount of metal nuclei is not formed in the coating layer during irradiation of the thermoplastic resin composition (molded product) with the laser beam, resulting in deterioration of plating adhesion, and if the content of the LDS additive exceeds about 20 parts by weight, impact resistance and heat resistance of the thermoplastic resin composition may suffer from deterioration. For example, the LDS additive can be present in an amount from about 0.1 parts by weight to about 10 parts by weight. Alternatively, the LDS additive can be present in an amount from about 1 part by weight to about 8 parts by weight.
Impact modifier
The impact modifier is used to improve the durability and impact resistance of the thermoplastic resin composition. In one embodiment, the impact modifier may include an impact modifier of a core-shell structure obtained by grafting an unsaturated compound including at least one selected from the group consisting of an acrylic monomer, an aromatic vinyl monomer, an unsaturated nitrile monomer, and a polymer thereof to a rubber polymer obtained by polymerization of a diene monomer, or a rubber polymer obtained by copolymerization of a monomer including at least one selected from the group consisting of a diene monomer, an acrylic monomer, a siloxane monomer, and a styrene monomer.
The diene monomer used to form the rubbery polymer may include butadiene, isoprene, and the like. In particular, butadiene may be used as the diene monomer.
The acrylic monomer used to form the rubbery polymer may include alkyl (meth) acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate. Here, alkyl means C1To C10An alkyl group. Here, crosslinking agents such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol dimethacrylate, allyl methacrylate and triallyl cyanurate may be used。
The siloxane monomers used to form the rubber polymer may include linear siloxane monomers such as dimethyl siloxane, methylethyl siloxane, methylphenyl siloxane, methylhydroxy siloxane, methylpropyl siloxane, methylbutyl siloxane, and the like; and cyclosiloxane monomers such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane and the like. These may be used alone or as a mixture thereof. Here, a crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, n-ethoxysilane, etc. can be used.
The styrene monomer used to form the rubbery polymer may include monomers selected from the group consisting of styrene, C1To C10One of the group consisting of alkyl substituted styrenes, halogen substituted styrenes, and combinations thereof.
The rubber polymer obtained by polymerization of diene monomers may include polybutadiene. Further, the rubber polymer obtained by copolymerization of a diene monomer and at least one monomer selected from the group consisting of an acrylic monomer, a siloxane monomer and a styrene monomer may include a copolymer of butadiene and an alkyl (meth) acrylate, a copolymer of butadiene, an alkyl (meth) acrylate and cyclosiloxane, and the like. These rubber polymers may be used alone or as a mixture thereof.
In one embodiment, the average particle diameter (Z-average) of the rubber polymer (rubber particles) may be about 0.05 μm to about 6 μm. Within this range, the thermoplastic resin composition may have good impact resistance and appearance. For example, the average particle diameter of the rubber polymer (rubber particles) may be about 0.15 μm to about 4 μm. Alternatively, the average particle diameter of the rubber polymer (rubber particles) may be about 0.25 μm to about 3.5 μm.
Among the unsaturated compounds, the acrylic monomer may include at least one selected from the group consisting of alkyl (meth) acrylates and (meth) acrylic esters. Here, alkyl means C1To C10An alkyl group. Alkyl (meth) acrylatesExamples of the alkyl ester may include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. For example, methyl (meth) acrylate may be used.
Among the unsaturated compounds, the aromatic vinyl monomer may include one selected from the group consisting of styrene, C1To C10Examples of the alkyl-substituted styrene may include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and α -methylstyrene.
In the unsaturated compound, the unsaturated nitrile monomer may include at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.
The impact modifier may be present in an amount of about 1 part by weight to about 20 parts by weight, relative to 100 parts by weight of the base resin. If the content of the impact modifier is less than about 1 part by weight, the thermoplastic resin composition exhibits insignificant impact reinforcement, and if the content of the impact modifier exceeds about 20 parts by weight, the thermoplastic resin composition may suffer from deterioration in heat resistance and moldability. For example, the impact modifier may be present in an amount of about 0.1 parts by weight to about 10 parts by weight. Alternatively, the impact modifier may be present in an amount of about 1 part by weight to about 8 parts by weight.
In one embodiment, the impact modifier and the polycarbonate-polysiloxane copolymer can be present in a weight ratio of about 1:5 to about 1: 10. Within this range, the thermoplastic resin composition may exhibit good properties in terms of impact resistance, flowability and appearance. For example, the impact modifier and the polycarbonate-polysiloxane copolymer can be present in a weight ratio of about 1:5 to about 1: 8.
In one embodiment, the LDS additive and the impact modifier can be present in a weight ratio of about 1:1 to about 1: 3. Within this range, the thermoplastic resin composition may exhibit good appearance and plating adhesion without deterioration in impact resistance and heat resistance. For example, the LDS additive and the impact modifier can be present in a weight ratio of about 1:1 to about 1: 2.
In one embodiment, the thermoplastic resin composition may be prepared in the form of pellets by mixing the aforementioned components followed by melt extrusion at about 200 ℃ to about 300 ℃ (e.g., at about 220 ℃ to about 260 ℃) in a typical twin screw extruder.
In one embodiment, the thermoplastic resin composition may have a notched izod impact strength of about 50kgf cm/cm or greater as measured according to ASTM D256 on 1/8 "thick test specimens. For example, the thermoplastic resin composition may have a notched Izod impact strength of from about 60 kgf-cm/cm to about 90 kgf-cm/cm.
In one embodiment, when the adhesive tape is attached to an injection-molded sample having a size of 50mm × 90mm × 3.2mm and left to stand at 25 ℃ for 6 hours, the surface of the sample in a stripe form is activated by laser direct structuring, a copper layer having a thickness of 35 μm is formed on the activated surface of the sample by a plating process (electroless copper plating), the sample is left in a room at 85 ℃ and 85% RH for 120 hours, and the adhesive tape is released from the sample after cutting 100 grid cells each having a size of 1mm × 1mm in the plating layer (copper layer), the thermoplastic resin composition may have about 90 or more grid cells remaining without being peeled. For example, the thermoplastic resin composition may have 92 to 100 mesh grids.
In one embodiment, the thermoplastic resin composition may have a weight-drop height of about 60cm or more at which cracks are generated on a test specimen of the thermoplastic resin composition when a metal tip having a weight of 500g is dropped on the test specimen according to the DuPont drop test method, wherein the test specimen is prepared by immersing an injection-molded test specimen having a size of 100mm × 100mm × 3.2.2 mm in a diluting solution (T-280,
In one embodiment, the thermoplastic resin composition may further include any typical additive commonly used in thermoplastic resin compositions, as necessary, without deteriorating the effects of the present invention. Examples of the additive may include, but are not limited to, lubricants, colorants, antistatic agents, and flame retardants. The additive may be present in an amount of 0.01 to 20 parts by weight, relative to about 100 parts by weight of the base resin.
The molded product produced using the thermoplastic resin composition according to the present invention has good heat resistance and plating reliability under high temperature/humidity conditions, and particularly good impact resistance after plating process.
Molded product produced using thermoplastic resin composition for laser direct structuring
Another aspect of the present invention relates to a molded product formed from the thermoplastic resin composition as described above. For example, the molded product may be prepared by any suitable molding method such as injection molding, double injection molding, blow molding, extrusion molding, hot molding, and the like using the thermoplastic resin composition. One of ordinary skill in the art can easily form a molded product.
Fig. 1 is a schematic view of a molded product according to an embodiment of the present invention. It should be noted that the drawings are exaggerated in line thickness or component size for ease of description and clarity only. Referring to fig. 1, a molded product 10 according to the present embodiment may include a metal layer 20 formed on at least a portion of a surface thereof by an LDS and plating process. The molded product 10 according to the embodiment may be a circuit carrier for manufacturing an antenna. For example, the molded product 10 may be manufactured by: the preform 10 is prepared by injection molding using a thermoplastic resin composition and a specific region (a portion where the metal layer 20 will be formed) on the surface of the preform 10 is irradiated with a laser beam and then the irradiated region is metalized (plating process) to form the metal layer 20.
In one embodiment, the LDS additive contained in the preform 10 decomposes under irradiation with a laser beam to form a metal core. In addition, the laser-irradiated area has a surface roughness suitable for the plating process. Here, the wavelength of the laser beam may be about 248nm, about 308nm, about 355nm, about 532nm, about 1,064nm, or about 10,600 nm.
In one embodiment, the metallization may be performed by any typical plating process. For example, metallization may include immersing the laser beam irradiated preform 10 in at least one electroless plating bath to form a metal layer 20 (conductive path) on the laser beam irradiated areas of the surface of the preform 10. Here, examples of the electroless plating may include copper plating, gold plating, nickel plating, silver plating, zinc plating, and tin plating.
One of ordinary skill in the art can readily produce a molded product having a metal layer formed on at least a portion of its surface by LDS.
[ MEANS FOR THE INVENTION ]
Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and are not to be construed as limiting the invention in any way.
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