Thermoplastic composition for laser direct structuring

Abstract

The present invention relates to a thermoplastic composition comprising an aromatic polycarbonate and a copper chromite spinel laser direct structuring additive. The composition comprises a) 85 to 95% by weight of an aromatic polycarbonate, b) 2 to 15% by weight of a copper chromite spinel laser direct structuring additive, c) 0.05 to 5% by weight of a flame retardant which is a flame retardant salt or an organic flame retardant, d) 0.1 to 2% by weight of an acid-modified polymer, and e) optionally 0 to 5% by weight of a siloxane-based rubber. The present invention also relates to a molded part comprising this composition, a method for manufacturing a circuit carrier using this molded part, and a circuit carrier obtainable by this method.

Description

Technical Field

[0001] The present invention relates to a thermoplastic composition comprising an aromatic polycarbonate and a copper chromite spinel laser direct structuring additive. The present invention also relates to a molded part comprising this composition, a method for manufacturing a circuit carrier using this molded part, and a circuit carrier obtainable by this method.

Background Art

[0002] For example, U.S. Patent No. B2-7060421 and International Publication No. A-2009024496 pamphlet describe a polymer composition comprising a polymer and a laser direct structuring (LDS) additive that can be activated by laser radiation to thereby form elemental metal nuclei. Such a polymer composition advantageously irradiates a region of the part with laser radiation in order to activate the plastic surface at the location where the conductive path is located and decompose the LDS additive to release metal nuclei, and then metallizes the irradiated region to accumulate metal on these regions, and can be used in an LDS process for manufacturing a non-conductive part on which conductive tracks are formed.

[0003] International Publication No. A-2009024496 pamphlet describes an aromatic polycarbonate composition containing a metal compound that can be activated by electromagnetic radiation to form elemental metal nuclei and 2.5 to 50% by mass of a rubbery polymer. The rubbery polymer is added to reduce the degradation of polycarbonate due to the presence of such metal compounds in the aromatic polycarbonate composition. However, the presence of a substantial amount of the rubbery polymer is disadvantageous in some applications, especially high-temperature applications such as parts that require soldering. In such applications, for example, a high softening temperature as represented by the Vicat softening temperature is required. Furthermore, the presence of the rubbery polymer results in high viscosity, which is incompatible with modern requirements that objects made from these compositions be thin-walled, for example, having a wall thickness of ≤ 1.5 mm or even ≤ 1 mm. Therefore, the flow characteristics of these compositions must be sufficient to fill a thin-walled mold. In practice, this requires appropriately low melt viscosity values. Finally, the presence of some rubbery polymers and too high a loading of the rubbery polymer reduce the flame retardancy of objects made from these compositions, which is also undesirable.

[0004] However, as shown in International Publication No. A-2009024496 pamphlet, a composition containing an aromatic polycarbonate and a laser direct structuring additive, which does not contain or contains only a small amount of a rubbery polymer, is prone to polycarbonate degradation, resulting in, for example, a decrease in toughness as represented by the Izod notch impact strength performance of molded articles from the composition.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Therefore, an object of the present invention is to provide an aromatic polycarbonate composition containing a laser direct structuring additive and not containing or containing only a small amount of a rubbery polymer, which has improved toughness and a sufficiently high softening temperature.

[0006] A further object of the present invention is to provide an aromatic polycarbonate composition containing a laser direct structuring additive having good melt flow characteristics.

[0007] Finally, flame retardancy is important. Therefore, a further object of the present invention is to provide an aromatic polycarbonate composition capable of producing a molded article having a conductive track and having good flame retardancy.

Means for Solving the Problems

[0008] Therefore, the present invention provides a) 85 to 95% by weight of an aromatic polycarbonate, b) 2 to 15% by weight of a copper chromite spinel laser direct structuring additive, c) 0.05 to 5% by weight of a flame retardant which is a flame retardant salt or an organic flame retardant, d) 0.1 to 2% by weight of an acid-modified polymer, e) Optionally, 0 to 5% by weight of an Si modifier and provides a thermoplastic composition containing the same.

[0009] The amounts shown for components a), b), c), d) and e) are based on the total weight of the composition.

[0010] Surprisingly, the combination of components c) and d) in an aromatic polycarbonate (sometimes referred to herein as PC) composition containing a copper chromite spinel laser direct structuring additive (sometimes referred to herein as an LDS additive) provides an appropriate melt viscosity, and thus good processability of the composition for providing thin-walled articles and good Izod strength, high Vicat softening temperature and excellent flame retardancy of the molded parts made from the composition have been found.

[0011] The composition according to the present invention can be formed into a molded part, and a conductive track can be provided thereon by laser radiation and subsequent metallization steps.

[0012] Accordingly, the present invention further relates to a molded part comprising a thermoplastic composition according to the present invention. In particular, the present invention relates to a molded part produced by injection molding of the composition according to the present invention. The present invention further relates to an article comprising a molded part produced from the composition according to the present invention and a conductive track provided thereon, in particular a circuit carrier. In one embodiment, such a circuit carrier is used to manufacture an antenna.

[0013] The present invention further relates to a method for manufacturing such a circuit carrier, the method comprising the steps of providing a molded part comprising a thermoplastic composition according to the present invention, irradiating a region of the part where a conductive track is to be formed with laser radiation, and then metallizing the irradiated region. In a preferred embodiment, the laser radiation is used to simultaneously release metal nuclei and ablate the part while forming an adhesion-promoting surface. This provides a simple means of achieving excellent adhesion strength of the deposited metal conductor track. The wavelength of the laser is preferably 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm or even 10600 nm. The deposition of further metal onto the metal nuclei generated by the laser radiation is preferably carried out by an electroplating process. The metallization is preferably carried out by immersing the molded part in at least one electroless plating bath to form a conductive path in the irradiated region of the molded part. Non-limiting examples of electroless plating processes are copper plating processes, gold plating processes, nickel plating processes, silver plating processes, zinc plating processes and tin plating processes. Preferably, the first plating is copper plating. The conductive track may have one or more layers. The first layer may be, for example, a copper layer and may be 8 - 16 μm, more typically 8 - 12 μm. If present, the second layer may be, for example, a nickel layer and may be 2 - 4 μm. If present, the third layer may be, for example, a gold layer and may be 0.05 - 0.2 μm.

Embodiments for Carrying Out the Invention

[0014] Irradiation of the shaped part can be carried out, for example, under conditions including a power of 2 to 15 W, a frequency of 20 to 100 kHz, and a speed of 1 to 5 m / s.

[0015] Irradiation of the shaped part can be carried out, for example, by 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. Other preferred forms of radiation are X-rays, gamma rays, and particle beams (electron beams, alpha particle beams, and beta particle beams).

[0016] When irradiating the molded article with ultraviolet light having a wavelength of 100 to 400 nm, in order to improve the peel resistance, it may be preferable to perform a heat treatment on the shaped part having a metallized region. The heat treatment can be carried out by causing the shaped part to receive microwaves, for example, by placing the shaped part in a microwave oven. Preferably, the irradiation of the shaped part is performed by visible light having a wavelength of 400 to 800 nm, infrared light having a wavelength of 800 to 25,000 nm, or X-rays, gamma rays, or particle beams. These types of laser radiation are advantageous in that they do not require a heat treatment after the plating step and the metal layer of the irradiated portion has a relatively strong adhesion strength.

[0017] More preferably, the irradiation of the shaped part is performed by visible light having a wavelength of 400 to 800 nm or infrared light having a wavelength of 800 to 25,000 nm. Most preferably, the irradiation of the shaped part is performed by infrared light having a wavelength of 800 to 25,000 nm.

[0018] Preferably, the method for manufacturing the circuit carrier does not include a heat treatment step after the step of metallizing the irradiation region. This is advantageous from the viewpoint of enabling an efficient process.

[0019] Preferably, the molded part of the composition according to the present invention can achieve a UL94 V1 or V0 rating at a thickness of 1.5 mm (±10%). More preferably, the molded part of the composition according to the present invention can achieve a UL94 V0 rating at a thickness of 1.5 mm (±10%).

[0020] Preferably, the composition has a melt viscosity according to ASTM D 3835 at 300 °C and 1500 s of less than 230 Pa·s, more preferably less than 210 Pa·s, even more preferably less than 190 Pa·s. Preferably, the composition has a melt viscosity according to ASTM D 3835 at 300 °C and 1500 s of -1 greater than 40 Pa·s, more preferably greater than 70 Pa·s, and most preferably greater than 100 Pa·s. -1 Preferably, the composition has a melt viscosity according to ASTM D 3835 at 300 °C and 1500 s of greater than 40 Pa·s, more preferably greater than 70 Pa·s, and most preferably greater than 100 Pa·s.

[0021] Preferably, the Izod notched impact strength at 23 °C (measured with a sample thickness of 3.2 mm or less according to ISO 180 / 4A) of the molded part of the composition, optionally provided with conductive tracks created by laser radiation and subsequent metallization, is 2 a value greater than 60 kJ / m², preferably a value greater than 65 kJ / m², even more preferably a value greater than 70 kJ / m². Typically, this value is less than 90 or 80 kJ / m².

[0022] Preferably, the Izod notched impact strength at -20 °C (measured with a sample thickness of 3.2 mm or less according to ISO 180 / 4A) of the molded article of the composition, optionally provided with conductive tracks created by laser radiation and subsequent metallization, is 2 a value greater than 15 kJ / m², preferably a value greater than 20 kJ / m², even more preferably a value greater than 25 kJ / m². Typically, this value is less than 70 or 60 kJ / m².

[0023] Preferably, moulded parts of the composition, optionally provided with conductive tracks made by laser radiation and subsequent metallisation, have a Vicat B50 (Vicat softening temperature measured at a rate of 50°C / h and a load of 50N according to ISO 306) of greater than 130°C, preferably greater than 135°C, more preferably greater than 139°C.

[0024] Particularly preferably, the composition according to the invention comprises - Less than 230 Pa.s, 300℃ and 1500s -1 and having a melt viscosity according to ASTM D 3835 at A moulded part of the composition, optionally provided with conductive tracks produced by laser radiation and subsequent metallisation, - have an Izod notch impact strength at -20 °C (measured according to ISO 180 / 4A with a specimen thickness of 3.2 mm or less) of more than 25 kJ / m2, - have an Izod notch impact strength at 23 °C (measured according to ISO 180 / 4A with a specimen thickness of 3.2 mm or less) of more than 70 kJ / m2, - Able to achieve UL94 V0 or V1 rating at a thickness of 3.2mm (±10%), and - have a Vicat B50 (measured according to ISO 306 at a rate of 50°C / h and a load of 50N) of more than 139°C.

[0025] Component a) The concentration of the a) aromatic polycarbonate in the composition of the present invention is 85% by weight to 95% by weight, preferably 86% by weight to 94% by weight, more preferably 87% by weight to 93% by weight, and even more preferably 88% by weight to 92% by weight, based on the total weight of the composition.

[0026] The aromatic polycarbonate can be an aromatic polycarbonate homopolymer or an aromatic polycarbonate copolymer.

[0027] The polycarbonates containing aromatic carbonate chain units have the formula (I): -R 1 -O-CO-O- (I) (wherein R 1 is an aromatic, aliphatic or alicyclic group) and a composition having a structural unit of. Advantageously, R 1 is an aromatic organic group, and in another embodiment, formula (II): -A 1 -Y 1 -A 2 - (II) (wherein each of A 1 and A 2 is a monocyclic divalent aryl group, and Y 1 is a bridging group having 0, 1 or 2 atoms separating A 1 from A 2 )( is a group of. In an exemplary embodiment, one atom separates A 1 from A 2 . Exemplary examples of this type of group are -O-, -S-, -S(O)-, -S(O2)-, -C(O)-, methylene, cyclohexylmethylene, 2-[2,2,1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, adamantylidene, etc. In another embodiment, 0 atoms separate A 1 from A 2 , and an exemplary example is bisphenol. The bridging group Y 1 can be a hydrocarbon group or a saturated hydrocarbon group, such as methylene, cyclohexylidene or isopropylidene.

[0028] Suitable aromatic polycarbonates include, for example, polycarbonates produced from at least a dihydric phenol and a carbonate precursor by a generally known interfacial polymerization process or melt polymerization method. Suitable dihydric phenols that can be applied are compounds having one or more aromatic rings containing two hydroxy groups, each of which is directly bonded to a carbon atom forming part of the aromatic ring. Examples of such compounds are 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 4,4-bis(4-hydroxyphenyl)heptane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, 2,2-(3,5,3',5'-tetrachloro-4,4'-dihydroxydiphenyl)propane, 2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)propane, (3,3'-dichloro-4,4'-dihydroxyphenyl)methane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, bis-4-hydroxyphenylsulfone, bis-4-hydroxyphenylsulfide.

[0029] The carbonate precursor can be a carbonyl halide, a halogenoformate or a carbonate ester. Examples of carbonyl halides are carbonyl chloride and carbonyl bromide. Examples of suitable halogenoformates are bis-halogenoformates of dihydric phenols such as hydroquinone or glycols such as ethylene glycol. Examples of suitable carbonate esters are diphenyl carbonate, di(chlorophenyl) carbonate, di(bromophenyl) carbonate, di(alkylphenyl) carbonate, phenyltolyl carbonate, etc., and mixtures thereof. Other carbonate precursors can be used, but it is preferred to use a carbonyl halide, especially carbonyl chloride also known as phosgene.

[0030] The aromatic polycarbonate in the composition according to the invention can be prepared using a catalyst, an acid acceptor and a compound for controlling the molecular weight.

[0031] Examples of catalysts are tertiary amines such as triethylamine, tripropylamine and N,N-dimethylaniline, quaternary ammonium compounds such as tetraethylammonium bromide and quaternary phosphonium compounds such as methyltriphenylphosphonium bromide.

[0032] Examples of organic acid acceptors are pyridine, triethylamine, dimethylaniline, etc. Examples of inorganic acid acceptors are hydroxides, carbonates, hydrogencarbonates and phosphates of alkali metals or alkaline earth metals.

[0033] Examples of compounds for controlling the molecular weight are monohydric phenols such as phenol, p-alkylphenol and para-bromophenol and secondary amines.

[0034] When the aromatic polycarbonate is an aromatic polycarbonate copolymer, the copolymer is preferably a polysiloxane-polycarbonate copolymer.

[0035] Examples of polysiloxane-polycarbonate copolymers are described, for example, in U.S. Patent No. 5,380,795 and International Publication No. WO 90 / 040772, which are hereby incorporated herein by reference.

[0036] The polysiloxane (also referred to as "polydiorganosiloxane") block of the copolymer has the formula (1):

Chemical formula

[0037] The value of E in formula (1) can vary widely depending on the type and relative amounts of each component in the thermoplastic composition, the desired properties of the composition, and similar considerations. Generally, E can have an average value of from 2 to 1,000, specifically from 2 to 500, more specifically from 5 to 100. In one embodiment, E has an average value of from 10 to 75, and in yet another embodiment, E has an average value of from 20 to 60. When E is a lower value, for example less than 40, it may be desirable to combine siloxane-based rubbers and, optionally, use them in higher amounts. For example, a composition containing a polysiloxane-polycarbonate copolymer can contain a low amount of aromatic polycarbonate and a high amount of siloxane-based rubber. Conversely, when E is a higher value, for example greater than 40, a composition containing a polysiloxane-polycarbonate copolymer may desirably contain a high amount of aromatic polycarbonate and a low amount of siloxane-based rubber, or more preferably no siloxane-based rubber.

[0038] Combinations of first and second (or more) polysiloxane-polycarbonate copolymers can be used, and the average value of E of the first copolymer is less than the average value of E of the second copolymer.

[0039] In one embodiment, the polydiorganosiloxane block has the formula (2):

Chemical formula

[0040] The unit of formula (2) corresponds to the corresponding formula (3):

Chemical formula

[0041] In another embodiment, the polydiorganosiloxane block has the formula (4):

Chemical formula

Chemical formula

[0042] In one embodiment, M is bromo or chloro, an alkyl group such as methyl, ethyl or propyl, an alkoxy group such as methoxy, ethoxy or propoxy or an aryl group such as phenyl, chlorophenyl or tolyl, and R 5 is a dimethylene, trimethylene or tetramethylene group, and R is Ci_s alkyl, a haloalkyl such as trifluoropropyl, cyanoalkyl or an aryl such as phenyl, chlorophenyl or tolyl. In another embodiment, R is methyl or a mixture of methyl and trifluoropropyl or a mixture of methyl and phenyl. In yet another embodiment, M is methoxy, n is 1, R 5 is a divalent C1-C3 aliphatic group, and R is methyl.

[0043] The unit of formula (5) corresponds to the corresponding dihydroxypolydiorganosiloxane (6):

Chemical formula

[0044] In an exemplary embodiment, the polysiloxane block is a poly(dimethylsiloxane) (PDMS) block.

[0045] The polysiloxane-polycarbonate may contain 85 to 99 weight percent carbonate units and 1 to 15 weight percent siloxane units. Within this range, the polysiloxane-polycarbonate copolymer may contain 88, 90, 92, 94, 96 or 98 weight percent carbonate units and, correspondingly, 2, 4, 6, 8, 10 or 12 weight percent siloxane units. In a specific embodiment, the polysiloxane-polycarbonate contains 85 to 98 weight percent carbonate units and 2 to 15 weight percent siloxane units. In another specific embodiment, the polysiloxane-polycarbonate contains 90 to 98 weight percent carbonate units and 2 to 10 weight percent siloxane units.

[0046] In one embodiment, the polysiloxane-polycarbonate may include polysiloxane units and carbonate units derived from bisphenol A. When measured by gel permeation chromatography using a crosslinked styrene-divinylbenzene column at a sample concentration of 1 milligram per milliliter and calibrated with a polycarbonate standard, the polysiloxane-polycarbonate may have a weight average molecular weight of 2,000 to 100,000, specifically 5,000 to 50,000.

[0047] The polysiloxane-polycarbonate may have a melt volume flow rate of 1 to 50 cubic centimeters per 10 minutes (cc / 10 min), specifically 2 to 30 cc / 10 min, when measured at 300 degrees Celsius under a load of 1.2 kg. Mixtures of polysiloxane-polycarbonates with different flow characteristics can be used to achieve the desired flow characteristics overall. In one embodiment, an exemplary polysiloxane-polycarbonate is sold under the trade name LEXAN® EXL polycarbonate and is available from Sabic Innovative Plastics.

[0048] In one embodiment, the aromatic polycarbonate is or includes recycled polycarbonate.

[0049] Component b) The term "laser direct structuring additive" or "LDS additive" is known and has been used, for example, in European Patent No. 2291290 B1, US Patent Application Publication No. 2005064711, International Publication No. 2005103113 Pamphlet, and International Publication No. 2009024496 Pamphlet. In the laser direct structuring process, a thermoplastic composition comprising a thermoplastic resin and a laser direct structuring additive is provided, and the thermoplastic composition is irradiated with laser radiation in areas where conductive tracks are to be formed. Thereafter, the irradiated areas are selectively metallized to form conductive tracks. In areas not irradiated with the laser, metallization does not occur. Metallization can be carried out by standard electroless plating processes such as, for example, a copper plating process.

[0050] Without wishing to be bound by any theory, it is believed that the laser direct structuring additive is activated by laser radiation and thereby can form elemental metal particles. These metal particles are believed to form the basis for forming conductive tracks, which serve as nuclei for copper deposition in a standard electroless copper plating process. It is also possible that the radiation is not directly absorbed by the laser direct structuring additive but is absorbed by other substances and the absorbed energy is transmitted to the laser direct structuring additive, releasing elemental metal.

[0051] The laser radiation can be ultraviolet light (wavelength of 100 - 400 nm), visible light (wavelength of 400 - 800 nm) or infrared light (wavelength of 800 - 25000 nm). Other preferred forms of radiation are X-rays, gamma rays and particle beams (electron beams, alpha particle beams and beta particle beams). The laser radiation is preferably infrared light radiation, more preferably having a wavelength of 1064 nm.

[0052] The LDS additive used in the present invention is, for example, copper chromite spinel such as CuCr2O4 or copper chromite manganese oxide spinel (also called copper-chromium-manganese oxide spinel). Preferably, the LDS additive is CuCr2O4. Examples of copper chromite spinel that can be used as the LDS additive include those sold under the trade name LD5 by Shepherd Technologies.

[0053] The concentration of component b) present in the composition of the present invention is preferably 2% to 15% by weight, more preferably 4% to 13% by weight, even more preferably 6% to 10% by weight, and particularly preferably 7% to 9% by weight based on the total weight of the composition.

[0054] Component c) The flame retardant is preferably a flame retardant salt or an organic flame retardant.

[0055] The flame retardant salt is preferably a sulfonate, more preferably an alkali and / or alkaline earth metal sulfonate. In one embodiment, the composition contains an alkali metal sulfonate as the sulfonate. Preferably, the composition contains potassium sulfonate as the sulfonate. More preferably, the composition contains potassium perfluorobutane sulfonate (PFBS) and / or potassium diphenyl sulfone sulfonate (KSS) as the sulfonate. Even more preferably, the composition contains potassium perfluorobutane sulfonate as the sulfonate.

[0056] The organic flame retardant is preferably an organic phosphate or a phosphazene compound.

[0057] Examples of organic phosphates are aromatic phosphates of the formula (GO)3P=O, where each G is independently an alkyl, cycloalkyl, aryl, alkaryl or aralkyl group, provided that at least one G is an aromatic group. Two of the G groups may be joined together to provide a cyclic group, such as diphenyl pentaerythritol diphosphate, which is described in U.S. Patent No. 4,154,775 by Axelrod. Other suitable aromatic phosphates are, for example, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like. Specific aromatic phosphates are those in which each G is aromatic, such as triphenyl phosphate, tricresyl phosphate, isopropylphenylated triphenyl phosphate, and the like.

[0058] Bifunctional or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, of the following formula:

Chemical formula

[0059] Examples of suitable difunctional or polyfunctional aromatic phosphorus-containing compounds include resorcinol tetraphenyl diphosphate (RDP), bis(diphenyl) phosphate of hydroquinone, and bis(diphenyl) phosphate of bisphenol A, their oligomeric and polymeric counterparts, and the like. The method for preparing the aforementioned difunctional or polyfunctional aromatic compounds is described in British Patent No. 2,043,083.

[0060] Phosphazene compounds are organic compounds containing -P=N bonds. Particularly preferred phosphazene compounds include phenoxyphosphazene oligomers (also known as poly(bis(phenoxy)phosphazene)). Examples of phenoxyphosphazene oligomers include FP-110 (registered trademark) manufactured by Fushimi Pharmaceutical Co., Ltd. Other commercially available preferred phosphazene compounds include SPB-100 (registered trademark) of Otsuka Chemical Co., Ltd. and LY202 (registered trademark) of Lanyin Chemical Co., Ltd.

[0061] The concentration of component c) in the composition is 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.1 to 2.5% by weight, based on the total weight of the composition. When component c) is a flame retardant salt, the concentration is most preferably 0.1 to 0.3% by weight. When component c) is a phosphazene compound, the concentration is most preferably 1.5 to 2.5% by weight.

[0062] The weight ratio of sulfonate to laser direct structuring additive in the composition according to the present invention is preferably at least 0.01:1, more preferably at least 0.015:1, and even more preferably at least 0.020:1. The weight ratio of sulfonate to laser direct structuring additive in the composition according to the present invention is preferably at most 0.35:1, more preferably at most 0.30:1.

[0063] Component d) The acid-modified polymer can be a polymer obtained by modifying a polymer with a compound having a functional group such as an unsaturated carboxylic acid.

[0064] Preferably, the acid-modified polymer is an acid-modified olefin polymer or an acid-modified styrene polymer, more preferably an acid-modified olefin polymer.

[0065] The olefin polymer is preferably polyethylene or polypropylene.

[0066] The olefin polymer preferably has a weight average molecular weight of 1,000 to 5,000 g / mol.

[0067] Preferably, the acid-modified polymer is a polymer modified with an unsaturated carboxylic acid preferably selected from the group consisting of acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic monoamide.

[0068] Most preferably, the acid-modified olefin polymer is maleic anhydride-modified polyethylene. Suitable examples include commercially available Mitsui Hi-WAX 1105A (manufactured by Mitsui Chemicals, Inc., Mv1500, density 940 kg / m3, acid value: 60 KOHmg / g).

[0069] The amount of d) is 0.1 to 2.0% by weight, preferably 0.2 to 1.5% by weight, more preferably 0.4 to 1.5% by weight based on the total composition.

[0070] Component e) When a siloxane-based rubber is present in an aromatic polycarbonate composition containing a metal compound that can be activated by electromagnetic radiation to thereby form elemental metal nuclei, the deterioration of the polycarbonate in the composition is reduced or further prevented. This is manifested, for example, by an increase in melt flow stability and / or toughness. The presence of such a component in the composition of the present invention is not essential, but the properties of the composition can be further improved by the presence of such a siloxane-based rubber.

[0071] The siloxane-based rubber is preferably a polyorganosiloxane-containing graft copolymer prepared by polymerizing 5 to 60 parts by weight of a vinyl monomer (e-l) in the presence of 40 to 95 parts by weight of polyorganosiloxane particles (e-ll), as described, for example, in U.S. Patent Application Publication No. 2005 / 0143520 ((the total of (e-l) and (e-ll) is 100 parts by weight)). Examples of the vinyl monomer (e-l) include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, and p-butylstyrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; (meth)acrylate monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate; and carboxyl group-containing vinyl monomers such as itaconic acid, (meth)acrylic acid, fumaric acid, and maleic acid. The vinyl monomer (e-l) may optionally contain a polyfunctional monomer having at least two polymerizable unsaturated bonds in one molecule. Examples of the polyfunctional monomer include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. The vinyl monomer (e-l) can be used alone or in combination. The polyorganosiloxane particles (e-ll) are preferably prepared by emulsion polymerization of the constituents. Conventional seed emulsion polymerization can be applied to the graft copolymerization, which can be achieved by radical polymerization of the vinyl monomer (e-l) in the latex of the polyorganosiloxane particles (e-ll).

[0072] These polyorganosiloxane-containing graft copolymers are commercially available, for example, from Kaneka Corporation as Kane Ace MR01 and Kane Ace MR02.

[0073] Other suitable silicone-based rubbers include Metablen S-2001, Metablen S-2200, and Metablen SX-005 from Mitsubishi Rayon.

[0074] The composition according to the present invention does not contain methyl methacrylate-butadiene-styrene (MBS)-based rubber. Preferably, the composition according to the present invention does not contain rubbers other than the silicone-based rubbers as described above (i.e., component e).

[0075] Preferably, the silicone-based rubber as described above (i.e., component e) is in the range of 0 to 5% by weight based on the total weight of the composition. More preferably, the silicone-based rubber is in the range of 0 to 1.5% by weight.

[0076] Component f) The thermoplastic composition according to the present invention may further contain f) an anti-dripping agent.

[0077] Preferably, the amount of component f) is 0 to 2.0% by weight or 0.05 to 2.0% by weight, more preferably 0.1 to 1.5% by weight, even more preferably 0.2 to 1.0% by weight based on the total weight of the composition. The presence of component f) is optional, and thus, the composition according to the present invention may contain little or no component f). For example, the amount of component f) may be less than 0.05% by weight, less than 0.01% by weight, or 0% by weight based on the total composition.

[0078] Suitable examples of the anti-dripping agent include fluoropolymers such as polytetrafluoroethylene (PTFE). The fluoropolymer can be a fibril-forming fluoropolymer such as fibril-forming polytetrafluoroethylene (PTFE) or a non-fibril-forming fluoropolymer such as non-fibril-forming polytetrafluoroethylene.

[0079] The anti-drip agent can be in the form of an (aqueous) dispersion of a fluoropolymer. In this case, the dispersion contains a sufficient amount of fluoropolymer, for example, at least 30% by weight or at least 50% by weight of fluoropolymer of the dispersion.

[0080] The anti-drip agent can be in the form of a mixture of a fluoropolymer and a further polymer, for example, an encapsulated fluoropolymer. In this case, the dispersion contains a sufficient amount of fluoropolymer, for example, at least 30% by weight or at least 50% by weight of fluoropolymer of the mixture. The further polymer can be, for example, an acrylate copolymer or styrene-acrylonitrile. An example of a mixture of a fluoropolymer and an acrylate polymer is commercially available from Mitsubishi Rayon as METABLEN A-3800. The encapsulated fluoropolymer can be produced by polymerizing a polymer in the presence of a fluoropolymer.

[0081] Preferably, the anti-drip agent is a mixture of a fluoropolymer and a further polymer such as an encapsulated fluoropolymer. Such an anti-drip agent can be more easily handled because it is easier to supply in an extruder and there is no need to remove water from the composition compared to an anti-drip agent in the form of a dispersion.

[0082] Component g) The thermoplastic composition according to the invention can further contain g) one or more other additives in an amount of 0 to 10% by weight based on the total weight of the composition. These include conventional additives such as stabilizers against thermal degradation or thermal oxidative degradation, stabilizers against hydrolysis degradation, stabilizers against degradation by light, especially UV light and / or photo-oxidative degradation, and processing aids such as release agents and lubricants. Appropriate examples of such additives and their customary amounts are described in Kunststoff Handbuch, 3 / 1. The total amount of the additives is usually 0 to 5% by weight, for example, 0.1 to 3% by weight or 0.3 to 1% by weight.

[0083] Although the present invention has been described in detail for illustrative purposes, it is understood that such details are for illustrative purposes only and that variations can be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the claims.

[0084] It should be further noted that the present invention relates to all possible combinations of the features described herein, and combinations of features present in the claims are particularly preferred.

[0085] Furthermore, it should be noted that the term "comprising" does not exclude the presence of other elements. However, it should also be understood that a description of a product containing certain components also discloses a product consisting of these components. Similarly, a description of a method containing certain steps also discloses a method consisting of these steps.

[0086] Here, the present invention will be clarified by the following examples, but the present invention is not limited thereto.

Example

[0087] Comparative experiments (CEx.) and example compositions (Ex.) summarized in Tables 2 to 5 were prepared from the components shown in Table 1.

[0088] All amounts are by weight %. In each experiment, the sample was extruded in a co-rotating twin-screw extruder at a temperature of 280 °C. The extrudate was granulated, and the recovered granules were injection molded into ASTM-sized Izod bars (64 * 12.7 < * > 3.2 mm) at a melt temperature of about 290 °C, and the Izod notch impact strength was measured at temperatures of 23 °C and 0 °C according to ISO 180 / 4A, and the limiting viscosity number (LVN, ISO 1628 / 4) of the molded parts was measured. To measure the Vicat B50 (Vicat softening temperature according to ISO 306 at a load of 50 N at a rate of 50 °C / hour), ISO-sized Izod bars (80 * 10 *(4 mm) was molded, and bars with thicknesses of 1.6 mm and 3.2 mm were molded to measure the UL94 V grade (according to IEC60695-11-10 standard). MV was measured at a temperature of 300 °C and an applied shear rate of 1500 s -1 according to ASTM D 3538.

[0089]

Table 1

[0090]

Table 2

[0091] As is apparent, all examples and comparative examples in Table 2 have a high Vicat softening temperature of 139.0 °C or higher, which is desirable for high-temperature applications. However, only in the examples according to the present invention, this is combined with a favorable combination of further properties, as will be explained below.

[0092] As is apparent from CEx.1, the MFI of the PC composition increases dramatically from a value of 16 dg / min for PC only to a value of 61.6 dg / min due to the addition of CuCr2O4. This is due to extensive decomposition of the polymer. Due to the decomposition, the average molecular weight of the polymer chains decreases, thereby increasing the melt flow and lowering the MV (melt viscosity) and LVN. As a result, the Izod strength is typically dramatically lower compared to the value of pure PC having an Izod notch value of >70 kJ / m2 at 23 °C and about 15 - 20 kJ / m2 at -20 °C.

[0093] As is apparent from CEx.2, decomposition can be prevented by adding Hi-Wax. When 0.5 wt% of Hi-Wax is added, a stable MFI of 16.1, a melt viscosity of 168, and an LVN of 47 are obtained, and a relatively high Izod value is also obtained. However, the flame retardancy (UL-V) in this case shows a grade of No Class.

[0094] In CEx.3, by increasing the amount of Hi-Wax, a high melt viscosity is obtained. This is somewhat disadvantageous but still an acceptable value. However, as expected, there is no UL-V flame retardant rating in this example either.

[0095] When only a flame retardant is added without using Hi-Wax, a flame retardant composition is obtained. For example, refer to CEx.4. However, as is clear from, for example, a high MFI value and a dramatically low Izod value, the degradation is also significant in this case.

[0096] Surprisingly, the combination of a flame retardant and Hi-Wax results in an excellent V1 flame retardant rating, as is clear from Example 1 and Example 2. The combination of Hi-Wax and a flame retardant brings about a synergistic effect, enhancing the flame retardancy from the V2 rating of the individual compositions containing only the flame retardant or only Hi-Wax to the V1 rating of the combination of these components.

[0097] Thus, by combining and adding a flame retardant and an acid-modified polymer, a polycarbonate composition having a combination of melt viscosities suitable for producing thin-walled objects (<230 Pa·s) is obtained, and this polycarbonate composition can be molded into a molded article having a high Vicat temperature (>139.0 °C), good Izod strength (>15 kJ / m2 at -20 °C and >60 kJ / m2 at 23 °C), and excellent flame retardancy (V1 or V0).

[0098]

Table 3

[0099] Table 3 shows examples and comparative examples containing Si modifiers. The addition of Si modifiers increases the flame retardancy rating from V1 to V0 (comparing Example 3 with Example 1), and / or results in a V1 rating with improved Izod strength (Example 4). Table 3 further exemplifies the variation in results due to changes in the LDS additive. The V0 or V1 flame retardancy rating is achieved only when CuCr2O4 is used as the LDS additive.

[0100]

Table 4

[0101] Table 4 shows the results of various mixtures of virgin polycarbonate and recycled polycarbonate. The viscosity of the virgin polycarbonate was selected such that the MFI of the PC mixture was comparable to previous experiments. All samples have excellent flame retardancy, good fluidity and strength, indicating that recycled polycarbonate can be used.

[0102]

Table 5

[0103] Finally, as is apparent from Table 5, compositions containing other flame retardants also provide compositions with excellent flame retardancy as well as good fluidity and strength.

Claims

1. a) 85 to 95% by weight of an aromatic polycarbonate, b) 2 to 15% by weight of a copper chromite spinel laser direct structuring additive, c) 0.05 to 5% by weight of a flame retardant which is a flame retardant salt or an organic flame retardant, d) 0.1 to 2% by weight of an acid-modified polymer, e) optionally, 0 to 5% by weight of a siloxane-based rubber A thermoplastic composition comprising, wherein the amounts shown for components a), b), c), d) and e) are relative to the total weight of the composition.

2. The composition according to claim 1, wherein the copper chromite spinel laser direct structuring additive is CuCr₂O₄.

3. The composition according to claim 1 or 2, wherein the flame retardant salt is a sulfonate, preferably potassium sulfonate, more preferably potassium perfluorobutane sulfonate.

4. The composition according to any one of claims 1 to 3, wherein the organic flame retardant is a phosphazene compound, preferably phenoxyphosphazene.

5. The composition according to any one of claims 1 to 4, wherein the acid-modified polymer is an acid-modified olefin polymer, preferably maleic anhydride-modified polyethylene.

6. The composition according to any one of claims 1 to 5, wherein the molded part of the composition can achieve a UL94 V1 or V0 rating at a thickness of 1.5 mm (±10%).

7. Less than 230 Pa·s, preferably less than 210 Pa·s, more preferably less than 190 Pa·s, at 300 °C and 1500 s －１ The composition according to any one of claims 1 to 6, having a melt viscosity according to ASTM D 3538 at －１ .

8. Above 40 Pa·s, preferably above 70 Pa·s, more preferably above 100 Pa·s, at 300 °C and 1500 s －１ The composition according to any one of claims 1 to 7, having a melt viscosity according to ASTM D 3538 at －１ .

9. The composition according to any one of claims 1 to 8, wherein the molded part of the composition has an Izod notched impact strength according to ISO 180 / 4A at a temperature of 23 °C of more than 60 kJ / m², preferably more than 65 kJ / m², more preferably more than 70 kJ / m².

10. The composition according to any one of claims 1 to 9, wherein the molded part of the composition has an Izod notched impact strength according to ISO 180 / 4A at a temperature of -20 °C of more than 15 kJ / m², preferably more than 20 kJ / m², more preferably more than 25 kJ / m².

11. The composition according to any one of claims 1 to 10, wherein the molded part of the composition has a Vicat softening temperature according to ISO 306 at a rate of 50 °C / hour under a load of 50 N of more than 130 °C, preferably more than 135 °C, more preferably more than 139 °C.

12. A molded part comprising the composition according to any one of claims 1 to 11.

13. A method of manufacturing a circuit carrier, comprising providing a molded part according to claim 12, irradiating a region of the part where a conductive track is to be formed with laser radiation, and then metallizing the irradiated region.

14. A circuit carrier obtainable by the method according to claim 13.

15. An antenna comprising the circuit carrier according to claim 14.

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