Thermoplastic compositions for laser direct structuring

Abstract

The present invention relates to a thermoplastic composition comprising: a) 20-90 wt. % of a thermoplastic resin; b) a laser direct structuring additive; c) optionally, ceramic filler particles without laser direct structuring additive functionality; and d) 0.1-5.0 wt. % of an acid-modified polymer, wherein b) comprises: b1) a conductive metal oxide having a resistivity of 5×10 Ω cm or less and including at least a metal from group n and a metal from group n+1 of the periodic table, where n is an integer from 3 to 13; and / or b2) copper calcium titanate.

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic composition suitable for use in a laser direct structuring process. The invention also relates to a molded part comprising the composition. The invention also relates to a process for producing a circuit carrier by providing a molded part with conductive tracks by laser irradiation and subsequent metallization, and to the circuit carrier obtainable thereby. [Background technology]

[0002] In recent years, with the development of mobile phones such as smartphones, much research has been conducted into the manufacturing methods of antennas inside mobile phones. In particular, there is a need for three-dimensional design of antennas inside mobile phones. Laser direct structuring (hereinafter sometimes referred to as "LDS") is a well-known method for forming such three-dimensional antennas. LDS is a technology in which a laser is irradiated onto the surface of a resin molded product, typically containing an LDS additive, thereby activating only the laser-irradiated areas. Then, a metal is deposited on the activated areas to form a plating layer. A desirable feature of this technology is that it allows metal structures such as antennas to be fabricated directly on the surface of a resin substrate without the use of adhesives or other materials.

[0003] The development of smartphones has led to a demand for high dielectric constant (DC) materials for fabricating antennas. A high DC allows for the size of the antenna to be reduced. Current prior art materials have yet to provide LDS materials with high DC. In particular, polycarbonate-based compositions have relatively low DC.

[0004] U.S. Patent Application Publication No. 2009 / 0292051 discloses a thermoplastic composition comprising 10-90 wt. % of a thermoplastic resin, 0.1-30 wt. % of a laser direct structuring additive, and 10-80 wt. % of a ceramic filler. According to U.S. Patent Application Publication No. 2009 / 0292051, the LDS additive helps increase the dielectric constant, thereby requiring less ceramic filler to achieve the same level of dielectric constant of the composition. The LDS additive is a heavy metal mixed oxide spinel or copper salt. The ceramic filler used in the examples is a mixture of BaTiO3 and TiO2 in a 39 / 21 ratio. In the examples, the thermoplastic resin is poly(acetylene ether), PA66, PPA, or PPO.

[0005] One of the most important properties of LDS compositions is their plateability. EP 2998361B1 describes a new LDS additive containing at least two metals and a conductive oxide having a resistivity of 5×103 Ω·cm or less, where the laser direct structuring additive contains at least a metal from group n of the periodic table, where n is an integer between 3 and 13, and a metal from group n+1. The conductive oxide was found to have high plateability.

[0006] Another important need is the prevention of polymer degradation. WO 2009 / 024496 shows that LDS additives degrade aromatic polycarbonates, as indicated by a decrease in Mw, resulting in a significant increase in MFI and a significant decrease in impact strength. WO 2009 / 024496 solves this problem by preventing degradation through the use of rubbery polymers.

[0007] Therefore, there is a need for LDS compositions with high DC that prevent polymer degradation.

[0008] WO 2020 / 126188 discloses a thermoplastic composition comprising a) a thermoplastic resin, b) a laser direct structuring additive, and c) ceramic filler particles without laser direct structuring additive functionality, wherein at least 80 wt% of c) is TiO2, and wherein the composition has a loss tangent of 0.014 or less measured at 40 GHz. Summary of the Invention [Problem to be solved by the invention]

[0009] It is an object of the present invention to provide an LDS composition in which the above and / or other needs are met. [Means for solving the problem]

[0010] Therefore, the present invention provides a) 20 to 90% by weight of a thermoplastic resin; b) a laser direct structuring additive; and c) optionally ceramic filler particles without laser direct structuring additive functionality; d) 0.1 to 5.0 wt % of an acid-modified polymer; a thermoplastic composition comprising: In this case, b) includes b1) a conductive metal oxide having a resistivity of 5×103 Ω cm or less and containing at least a metal from group n and group n+1 of the periodic table, where n is an integer from 3 to 13, and / or b2) copper calcium titanate. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present inventors have found that the LDS additives used in the present invention not only achieve good plating properties but also substantially increase the DC of the composition. However, the present inventors have also found that the LDS additives used in the present invention cause degradation of the thermoplastic resin. The present inventors have surprisingly found that the addition of an acid-modified polymer to such a composition prevents such degradation. Thus, according to the present invention, a high DC is achieved while preventing polymer degradation.

[0012] a) Thermoplastic resin Thermoplastic resins can include resins such as polycarbonates, especially aromatic polycarbonates, polyamides, polyesters, polyesteramides, polystyrenes, polymethyl methacrylates, polyphenylene ethers, liquid crystal polymers (LCPs), polyetheretherketones (PEEKs), cyclic olefin (co)polymers (COPs), or combinations thereof. The resins can be homopolymers, copolymers, or mixtures thereof, and can be branched or unbranched.

[0013] Examples of suitable polyamides (PA) include branched polyamides such as PA6, PA46, PA66, PA6 / 66, PA11, and PA12; semi-aromatic polyamides such as MXD6, PA6I / 6T, PA66 / 6T, and PA4T; fully aromatic polyamides; and aliphatic polyamides, which may be copolymers and blends of the listed polyamides. Examples of suitable polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyethylene naphthanoate (PEN), and polybutylene naphthanoate (PBN). Preferred polyesters are polyethylene terephthalate and polybutylene terephthalate. Polyphenylene ethers are typically used in combination with polyamides or polystyrene. Examples of suitable LCPs are commercially available as Vectra® E845i LDS, E840i LDS, and TECACOMP LCP LDS black 4107. An example of a suitable PEEK is commercialized as TECACOMP PEEK LDS. An example of a suitable COP is commercialized as ZEONEX RS420-LDS Cyclo Olefin Polymer.

[0014] The thermoplastic resin may further comprise a rubbery polymer. Examples of rubbery polymers are described in WO2009024496A, which is incorporated herein by reference. The rubbery polymer is or comprises an elastomeric (i.e., rubbery) polymer that preferably has a Tg of less than about 10°C, more specifically less than about -10°C, or even more specifically between about -20°C and -80°C.

[0015] In some embodiments, compositions according to the present invention contain less than 2.5 wt.% of rubbery polymer. The present invention has the advantage that it can prevent polymer degradation even in compositions that contain little or no rubbery polymer.

[0016] In a preferred embodiment, the thermoplastic resin is a polycarbonate-based resin. The polycarbonate-based resin can be a polycarbonate or a blend of a polycarbonate and a rubbery polymer such as acrylonitrile butadiene styrene rubber (ABS). The polycarbonate can be a homopolymer, a copolymer, or a mixture thereof, and can be branched or unbranched. Suitable polycarbonate-based resins are described, for example, in U.S. Patent Application Publication No. 2009 / 0292048, which is incorporated herein by reference.

[0017] The polycarbonates containing aromatic carbonate chain units have the formula (I): -R1-O-CO-O-(I) wherein the R group is an aromatic, aliphatic, or alicyclic group. Advantageously, R is an aromatic organic group, and in another embodiment, the composition has a structural unit of formula (II): -A1-Y1-A2-(II) wherein each of A1 and A2 is a monocyclic divalent aryl group, and Y1 is a bridging group having zero, one, or two atoms separating A1 from A2. In an exemplary embodiment, one atom separates A1 from A2. Specific examples of this type of group are -O-, -S-, -S(O)-, -S(O2)-, -C(O)-, methylene, cyclohexyl-methylene, 2-[2,2,1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, adamantylidene, and the like. In another embodiment, zero atoms separate A1 from A2, and a specific example is bisphenol. The bridging group Y1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.

[0018] Suitable aromatic polycarbonate resins include polycarbonates produced from at least a dihydric phenol and a carbonate precursor, for example, by the commonly known interfacial polymerization process or melt polymerization method. Suitable applicable dihydric phenols are compounds having one or more aromatic rings containing two hydroxy groups, each 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-hydroxyphenyl sulfone, Bis-4-hydroxyphenyl sulfide.

[0019] The carbonate precursor may be a carbonyl halide, halogen formate, or carbonate ester. Examples of carbonyl halide include carbonyl chloride and carbonyl bromide. Examples of suitable halogen formates include bishalogen formates of dihydric phenols such as hydroquinone or glycols such as ethylene glycol. Examples of suitable carbonate esters include diphenyl carbonate, di(chlorophenyl)carbonate, di(bromophenyl)carbonate, di(alkylphenyl)carbonate, phenyltolylcarbonate, and the like, and mixtures thereof. Although other carbonate precursors can be used, it is preferred to use a carbonyl halide, particularly carbonyl chloride, also known as phosgene.

[0020] The aromatic polycarbonate resin in the composition according to the present invention can be prepared using a catalyst, an acid acceptor, and a compound for controlling molecular weight.

[0021] 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.

[0022] Examples of organic acid acceptors are pyridine, triethylamine, dimethylaniline, etc. Examples of inorganic acid acceptors are hydroxides, carbonates, bicarbonates and phosphates of alkali or alkaline earth metals.

[0023] Examples of compounds for controlling molecular weight are monohydric phenols such as phenol, p-alkylphenols and para-bromophenol, and secondary amines.

[0024] rubbery polymer Examples of rubbery polymers that can be blended with resins such as polycarbonates are described in WO 2009024496 A, which is incorporated herein by reference. The rubbery polymer is preferably an elastomeric (i.e., rubbery) polymer having a Tg of less than about 10°C, more specifically less than about -10°C, or even more specifically between about -20°C and -80°C.

[0025] Preferably, the amount of rubbery polymer in the thermoplastic resin a) is 0 to 60% by weight, for example 1 to 50% by weight, 5 to 40% by weight, or 10 to 30% by weight of the amount of the thermoplastic resin a).

[0026] Examples of elastomeric polymers include polyisoprene, polybutadiene, styrene-butadiene random copolymers and block copolymers, hydrogenated versions of the aforementioned block copolymers, butadiene-based rubbers such as acrylonitrile-butadiene copolymers and butadiene-isoprene copolymers, acrylate-based rubbers such as ethylene-methacrylate and ethylene-butyl acrylate, acrylic elastomeric polymers such as acrylate ester-butadiene copolymers, e.g., butyl acrylate-butadiene copolymers, e.g., polydimethylsiloxane, polymethylphenylsiloxane, and dimethylsiloxane. Examples of suitable elastomeric polymers include siloxane-based rubbers such as polyorganosiloxanes, such as butyl-diphenylsiloxane copolymers, and other elastomeric polymers such as ethylene-propylene random and block copolymers, copolymers of ethylene and α-olefins, copolymers of ethylene and aliphatic vinyls, such as ethylene-vinyl acetate, and ethylene-propylene non-conjugated diene terpolymers, such as ethylene-propylene-hexadiene copolymers, butylene-isoprene copolymers, and chlorinated polyethylene, which may be used individually or in combination of two or more.

[0027] Particularly preferred elastic polymers include ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), AAS resin (acrylonitrile-acrylic elastomer-styrene copolymer), and MBS (methyl methacrylate-butadiene-styrene copolymer). Particularly preferred graft copolymers are acrylonitrile butadiene styrene rubber (ABS), methyl methacrylate butadiene styrene rubber (MBS), or a mixture of these copolymers, because of the high compatibility between the polycarbonate matrix and such copolymers, which allows these copolymers to be uniformly dispersed in the polycarbonate matrix. This reduces any degradation of the thermoplastic resin, which can be caused by certain types of component b). From an economical point of view, acrylonitrile butadiene styrene (ABS) is even more preferred. Any commercially available ABS can be used. Particularly preferred acrylonitrile butadiene styrene (ABS) is acrylonitrile butadiene styrene having a rubber content of 10 to 50 parts by weight, preferably 10 to 40 parts by weight, and even more preferably 10 to 30 parts by weight.

[0028] In a particularly preferred embodiment, the thermoplastic resin a) is a blend of 45-75 wt. % polycarbonate, 5-40 wt. % ABS, and 0-10 wt. % MBS, the amounts being relative to the thermoplastic resin a).

[0029] In some embodiments, the rubber is a graft copolymer containing an elastic component containing Si. This has the advantage of improving the flame retardancy of the composition. The graft copolymer is formed by graft copolymerizing the elastic component containing Si with a monomer component copolymerizable therewith. The elastic component generally has a glass transition temperature of at most 0°C, preferably at most -20°C, more preferably at most -30°C.

[0030] The graft copolymer is preferably a core / shell type graft copolymer in which the core is an elastic component containing Si. The elastic component containing Si is preferably polyorganosiloxane.

[0031] The graft copolymer is preferably a polyorganosiloxane-containing graft copolymer, which is preferably prepared by polymerizing 5 to 60 parts by weight of vinyl monomer (I) in the presence of 40 to 95 parts by weight of polyorganosiloxane particles (II) (the sum of (I) and (II) being 100 parts by weight), as described, for example, in U.S. Patent Application Publication No. 2005 / 0143520. Examples of the vinyl monomer (I) include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, and p-butylstyrene, cyanide vinyl monomers such as acrylonitrile and methacrylonitrile, methacrylic acid ester 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 (aI) may optionally include a polyfunctional monomer having at least two polymerizable unsaturated bonds in one molecule. Examples of polyfunctional monomers include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. The vinyl monomer (I) can be used alone or in combination. The polyorganosiloxane particles (II) are preferably prepared by emulsion polymerization of the constituent components. The graft copolymerization can be performed by conventional seeded emulsion polymerization, which can be achieved by radical polymerization of the vinyl monomer (I) in the latex of the polyorganosiloxane particles (II).

[0032] These graft copolymers containing polyorganosiloxanes are commercially available, for example, as Kane Ace MR01 and Kane Ace MR02 from Kaneka Company.

[0033] Other suitable graft copolymers containing an Si-containing elastomeric component include Mitsubishi Rayon's Metablen S-2001, Metablen S-2200, and Metablen SX-005.

[0034] In a particularly preferred embodiment, the thermoplastic resin a) is a blend of 80 to 99 wt. % polycarbonate and 1 to 20 wt. % graft copolymer with an elastomeric component containing Si, the amounts being relative to the thermoplastic resin a).

[0035] In some embodiments, the thermoplastic resin a) is or comprises a polysiloxane-polycarbonate copolymer. Examples of polysiloxane-polycarbonate copolymers are described, for example, in U.S. Pat. No. 5,380,795 and WO 09,040,772. This also has the advantage of improving the flame retardancy of the composition.

[0036] Thus, in some preferred embodiments, component a) is a blend consisting of 45 to 75% by weight of polycarbonate and 5 to 40% by weight of ABS, said amounts being relative to the thermoplastic resin a), a blend consisting of 45 to 75% by weight of polycarbonate, 5 to 40% by weight of ABS and 1 to 10% by weight of MBS, said amounts being relative to the thermoplastic resin a), A blend consisting of 80 to 99% by weight of polycarbonate and 1 to 20% by weight of a graft copolymer containing an elastomeric component containing Si, In this case, the graft copolymer is a core / shell type graft copolymer in which the core is a polyorganosiloxane, and the amount thereof is relative to the thermoplastic resin a).

[0037] The amount of a) in the composition of the present invention is 20 to 90% by weight, for example at least 30% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, and / or at most 85% by weight, at most 80% by weight, at most 75% by weight, at most 70% by weight, at most 67% by weight, or at most 65% by weight, relative to the total weight of the composition.

[0038] The thermoplastic resin a), particularly a polycarbonate-based resin or polycarbonate, may have a melt flow rate of, for example, 5 to 25 dg / min, e.g., 8 to 20 dg / min, at 300°C according to ISO 1133-1:2011. In some cases, the thermoplastic resin a) comprises or consists of different polycarbonates having different melt flow rates, e.g., virgin polycarbonate and post-consumer recycled (PCR) polycarbonate. The MFR of PCR polycarbonate is largely limited by the products in which it is used, such as beverage bottles (e.g., water bottles), CDs, and automotive lighting. For example, PCR polycarbonate obtained from beverage bottles tends to have a relatively low MFR, e.g., 5 to 10 dg / min, at 300°C according to ISO 1133-1:2011.

[0039] b) Laser Direct Structuring Additives The LDS additive includes b1) a conductive metal oxide as described below, and / or b2) copper calcium titanate.

[0040] A particularly preferred embodiment of the present invention comprises: a) 20 to 90% by weight of a thermoplastic resin; b) a laser direct structuring additive; and c) optionally ceramic filler particles without laser direct structuring additive functionality; d) 0.1 to 5.0 wt % of an acid-modified polymer; a thermoplastic composition comprising In this case, b) is b1) a conductive metal oxide containing zinc and aluminum, preferably aluminum-doped zinc oxide, and / or b2) Contains copper calcium titanate.

[0041] b1) Conductive metal oxide The conductive metal oxide in the LDS additive has a resistivity of 5×10 Ω cm or less, preferably 8×10 Ω cm or less, more preferably 7×10 Ω cm or less, and even more preferably 5×10 Ω cm or less. There is no particular lower limit, but it can be, for example, 1×10 Ω cm or more, more specifically 1×10 Ω cm or more.

[0042] As used herein, the resistivity of a conductive oxide typically refers to powder resistivity. The resistivity of a conductive metal oxide can be measured, for example, using a multimeter to measure a compact of the conductive metal oxide prepared by pressing a fine powder of the conductive metal oxide. More specifically, the resistivity of a conductive metal oxide can be measured using a multimeter to measure a compact of the conductive metal oxide prepared by pressing 10 g of the fine powder of the conductive metal oxide at 100 kg / cm². The fine powder can be pressed by filling 10 g of the fine powder of the conductive metal oxide into a cylinder with an inner diameter of 25 mm, the inside of which may be coated with polytetrafluoroethylene. The fine powder can be pressed so that the packing density of the compact is 20%. More specifically, the resistivity can be measured using a Yokogawa Electric Corporation tester, model 3223, by filling 10 g of the fine powder of the conductive oxide into a cylinder with an inner diameter of 25 mm, the inside of which is coated with Teflon®, and pressing it at 100 kg / cm² (packing density of 20%).

[0043] The conductive metal oxide contains at least a metal from Group n of the periodic table and a metal from Group n+1 of the periodic table, where n is an integer from 3 to 13. The conductive metal oxide contains at least a metal from Group 3 and a metal from Group 4, a metal from Group 4 and a metal from Group 5, a metal from Group 5 and a metal from Group 6, a metal from Group 6 and a metal from Group 7, a metal from Group 7 and a metal from Group 8, a metal from Group 8 and a metal from Group 9, a metal from Group 9 and a metal from Group 10, a metal from Group 10 and a metal from Group 11, a metal from Group 11 and a metal from Group 12, a metal from Group 12 and a metal from Group 13, or a metal from Group 13 and a metal from Group 14.

[0044] Suitable metals from Group n or n+1 of the periodic table include, for example, Group 4 (such as titanium and zirconium), Group 5 (such as vanadium and niobium), Group 6 (such as chromium and molybdenum), Group 7 (such as manganese), Group 8 (such as iron and ruthenium), Group 9 (such as cobalt, rhodium and iridium), Group 10 (such as nickel, palladium and platinum), Group 11 (such as copper, silver and gold), Group 12 (such as zinc and cadmium), and Group 13 (such as aluminum, gallium and indium).

[0045] Suitable metals from Group n of the periodic table further include the metals from Group 3 (scandium, yttrium).

[0046] Suitable metals from Group n+1 of the periodic table further include the metals from Group 14 (germanium, tin, etc.).

[0047] Preferably, n is an integer of 10 to 13, more preferably 12 or 13, and most preferably 12.

[0048] Preferably, the conductive metal oxide comprises a Group 12 metal and a Group 13 metal.

[0049] Preferably, the amount of the Group n metal relative to the total of the Group n metal and the Group n+1 metal in the conductive metal oxide is 15 mol% or less, more preferably 12 mol% or less, and particularly preferably 10 mol% or less. Alternatively, the amount of the Group n+1 metal relative to the total of the Group n metal and the Group n+1 metal in the conductive metal oxide is 15 mol% or less, more preferably 12 mol% or less, and particularly preferably 10 mol% or less. There is no particular lower limit, but it must be 0.0001 mol% or more. Particularly preferably, the conductive metal oxide is an oxide of a Group n metal doped with a Group n+1 metal. High plating properties can be obtained.

[0050] Furthermore, it is preferable that 98% by weight or more of the metal components contained in the conductive metal oxide are metals of Group n and Group n+1 of the periodic table.

[0051] Particularly preferably, the conductive metal oxide comprises zinc and aluminum, and most preferably, the conductive metal oxide is aluminum-doped zinc oxide.

[0052] In some preferred embodiments, b) comprises or is particles of b1), and the amount of particles of b1) relative to the amount of b) can be, for example, 10 to 100% by weight, preferably at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99.0% by weight, at least 99.5% by weight, at least 99.9% by weight, or 100% by weight.

[0053] b2) Copper calcium titanate The LDS additive may include b2) copper calcium titanate.

[0054] In some preferred embodiments, b) comprises or is particles of b2), and the amount of particles of b2) relative to the amount of b) can be, for example, 10 to 100% by weight, preferably at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98%, at least 99.0%, at least 99.5%, at least 99.9%, or 100% by weight.

[0055] b) Further ingredients In some preferred embodiments, b) comprises or is a particle consisting of a core and a shell surrounding the core, in which case the shell is made from b1) and / or b2). The core is preferably made from a material having a high dielectric constant. The weight ratio between the core and the shell can be any value, for example, 1:2 to 100:1, as long as b1) and / or b2) function as an LDS additive. The amount of particles consisting of a core and a shell surrounding the core, in which the shell is made from b1) and / or b2), relative to the amount of b) can be, for example, 10 to 100% by weight, for example, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99.0% by weight, at least 99.5% by weight, at least 99.9% by weight, or 100% by weight.

[0056] In some preferred embodiments, b) consists of particles of b1) and / or b2), or particles consisting of a core and a shell surrounding the core, where the shell is made from b1) and / or b2). b) can also consist of particles of b1) and / or b2), and can also consist of particles consisting of a core and a shell surrounding the core, where the shell is made from b1) and / or b2).

[0057] Thus, in these preferred embodiments, the composition does not contain any material other than b1) and / or b2) that functions as a laser direct structuring additive. For example, the composition can contain less than 0.1 wt. % or less than 0.05 wt. % of a heavy metal mixed oxide spinel, such as a copper chromium oxide spinel, a copper salt, such as copper hydroxide phosphate, copper phosphate, copper sulfate, or copper thiocyanate, or a combination comprising at least one of the aforementioned LDS additives. For example, the composition can contain less than 0.1 wt. % or less than 0.05 wt. % of an LDS additive that is not a particle of b1) and / or b2), or a particle consisting of a core and a shell surrounding the core, based on the total composition, where the shell is made from b1) and / or b2).

[0058] The terms "laser direct structuring additive" and "material having laser direct structuring additive functionality" are understood to mean a material capable of forming a plating layer on an article produced by the following steps: 1) molding a test specimen by adding 10 parts by weight of a candidate LDS additive to 100 parts by weight of a thermoplastic resin, e.g., polycarbonate; 2) irradiating the test specimen with a laser; and 3) electrolessly plating the irradiated test specimen. For example, step 2) can be irradiating the test specimen with a YAG laser having a wavelength of 1064 nm at a power output of 13 W, a frequency of 20 kHz, and a scan speed of 2 m / s. For example, step 3) can be electrolessly plating the irradiated test specimen using a MID Copper 100XB Strike plating bath (manufactured by MacDermid Performance Solutions).

[0059] When b) consists of particles consisting of a core and a shell surrounding the core, the shell being made from b1) and / or b2), the core is preferably selected so as to contribute to achieving the desired high frequency performance of the composition according to the invention.

[0060] Preferably, the core is made from a ceramic material, preferably selected from metal oxides, metal silicates, metal borides, metal carbides and metal nitrides.

[0061] Suitable examples of metal oxides include magnesium oxide, titanium oxide (e.g., TiO), zinc oxide, copper oxide, cerium oxide, niobium oxide, tantalum oxide, yttrium oxide, zirconium oxide, aluminum oxide (e.g., alumina and / or fumed alumina), CaTiO3, MgZrSrTiO6, MgTiO3, MgAl2O4, BaZrO3, BaSnO3, BaNb2O6, BaTa2O6, WO3, MnO2, SrZrO3, SnTiO4, ZrTiO4, CaZrO3, CaSnO3, CaWO4, MgTa2O6, MgZrO3, La2O3, CaZrO3, MgSnO3, MgNb2O6, SrNb2O6, MgTa2O6, Ta2O3, barium titanate (BaTiO3), strontium titanate These include lead zirconate titanate (SrTiO3), barium strontium titanate, strontium-doped lanthanum manganate, lanthanum aluminum oxide (LaAlO3), cadmium copper titanate (CdCu3Ti4O12), Ca1-xLaxMnO3, (Li, Ti) doped NiO, lanthanum strontium copper oxide (LSCO), yttrium barium copper oxide (YBa2Cu3O7), lead zirconate titanate, and lanthanum modified lead zirconate titanate.

[0062] Examples of silicates are Na2SiO3, LiAlSiO4, Li4SiO4, BaTiSiO9, Al2SiO7, ZrSiO4, KAlSiO3, NaAlSiO8, CaAl2SiO8, CaMgSiO6, and Zn2SiO4. It should be noted that mica and talc are not preferred for the core because they do not contribute to achieving the desired high frequency performance.

[0063] Examples of borides are lanthanum boride (LaB6), cerium boride (CeB6), strontium boride (SrB6), aluminum boride, calcium boride (CaB6), titanium boride (TiB2), zirconium boride (ZrB2), vanadium boride (VB2), tantalum boride (TaB2), chromium borides (CrB and CrB2), molybdenum boride (MoB2, Mo2B5 and MoB), and tungsten boride (W2B5).

[0064] Examples of carbides are silicon carbide, tungsten carbide, tantalum carbide, iron carbide and titanium carbide.

[0065] Examples of nitrides include silicon nitride, boron nitride, titanium nitride, aluminum nitride, and molybdenum nitride.

[0066] Preferably, the core is made from a ceramic material selected from metal oxides, metal borides, metal carbides, and metal nitrides.

[0067] Preferably, the core is made from a metal oxide, more preferably titanium dioxide and / or barium titanate, most preferably titanium dioxide.

[0068] Preferably, the amount of b1), b2), or the sum of b1) and b2) is at least 0.1 wt.% and at most 80 wt.% of the total composition. Preferably, the amount of b1), b2), or the sum of b1) and b2) is at least 1.0 wt.%, at least 3.0 wt.%, at least 5.0 wt.%, at least 10 wt.%, at least 15 wt.%, at least 16 wt.%, at least 17 wt.%, at least 18 wt.%, at least 19 wt.%, at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 31 wt.%, at least 32 wt.%, at least 33 wt.%, at least 34 wt.%, or at least 35 wt.% of the total composition. Preferably, the amount of b1), b2), or the sum of b1) and b2) is at most 75 wt.%, at most 70 wt.%, at most 65 wt.%, or at most 60 wt.% of the total composition. The higher the amount of b1), b2), or the sum of b1) and b2), the better the high frequency performance.

[0069] Preferably, the amount of b) is at least 0.1 wt.% and at most 80 wt.% of the total composition. Preferably, the amount of b) is at least 1.0 wt.%, at least 3.0 wt.%, at least 5.0 wt.%, at least 10 wt.%, at least 15 wt.%, at least 16 wt.%, at least 17 wt.%, at least 18 wt.%, at least 19 wt.%, at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 31 wt.%, at least 32 wt.%, at least 33 wt.%, at least 34 wt.%, or at least 35 wt.% of the total composition. Preferably, the amount of b) is at most 75 wt.%, at most 70 wt.%, at most 65 wt.%, or at most 60 wt.% of the total composition.

[0070] Preferably, the LDS additive has a particle size d90, as determined by light scattering techniques, of at most 8 μm, more preferably at most 5 μm, more preferably at most 4 μm, more preferably at most 2 μm.

[0071] Preferably, the LDS additive has a particle size d50, determined by light scattering techniques, of at most 5 μm, more preferably at most 4 μm, more preferably at most 2 μm.

[0072] It has been found that LDS additives with smaller size impart good mechanical strength to compositions according to the invention.

[0073] Particle size can be determined, for example, by light scattering techniques using a Malvern Mastersize particle size analyzer, which can be done, for example, in accordance with ISO 13320-1:2009.

[0074] In some embodiments, b) may further comprise a material with laser direct structuring additive functionality, which is preferably a metal compound selected from the group consisting of: copper-containing spinels such as copper chromium oxide spinel, copper molybdenum oxide spinel, and copper chromium manganese oxide spinel; Copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate, and copper thiocyanate; organometallic complexes such as palladium / palladium-containing heavy metal complexes; tin-containing oxides such as antimony tin oxide (antimony-doped tin oxide), bismuth tin oxide (bismuth-doped tin oxide), aluminum tin oxide (aluminum-doped tin oxide), and molybdenum tin oxide (molybdenum-doped tin oxide); ZnxNi1-xFe2O4 (wherein x is greater than 0.60 and less than 0.85), and combinations thereof.

[0075] When present, the amount of further material with laser direct structuring additive functionality is typically 0.1 to 10 wt. %, for example 1.0 to 5.0 wt. %, based on the total composition.

[0076] In some embodiments, the composition according to the present invention is substantially free of additional materials having laser direct structuring additive functionality other than b1) or b2). For example, the composition may contain less than 0.1 wt. %, less than 0.05 wt. %, or less than 0.01 wt. % of a metal compound selected from the group consisting of: copper-containing spinels such as copper chromium oxide spinel, copper molybdenum oxide spinel, and copper chromium manganese oxide spinel; copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate, and copper thiocyanate; organometallic complexes such as palladium / palladium-containing heavy metal complexes; tin-containing oxides such as antimony tin oxide (antimony-doped tin oxide), bismuth tin oxide (bismuth-doped tin oxide), aluminum tin oxide (aluminum-doped tin oxide), and molybdenum tin oxide (molybdenum-doped tin oxide); ZnxNi1-xFe2O4 (where x is greater than 0.60 and less than 0.85); and combinations thereof.

[0077] c) Ceramic filler particles without laser direct structuring additive function The composition according to the invention may further comprise component c) which is particles of a ceramic material that does not have an LDS additive function.

[0078] Preferably, the amount of c) relative to the total composition is at most 75% by weight, for example at most 60% by weight, at most 50% by weight, or at most 40% by weight. Preferably, the amount of c) relative to the total composition is at most 30% by weight. When the amount of c) is at most 30% by weight, desired flame retardancy can be obtained.

[0079] Additionally, the amount of c) may be at most 20 wt.%, less than 10 wt.%, or at most 9 wt.%, based on the total composition. The amount of c) may be 0 wt.%, based on the total composition. It is advantageous to be able to obtain desirable properties without using substantial amounts of ceramic filler particles.

[0080] However, because c) is more cost-effective than b) for achieving desirable dielectric properties, it may be advantageous for the composition according to the present invention to include some amount of c). Furthermore, c) can improve the mechanical properties of the composition, such as impact strength, more efficiently than b). Preferably, the amount of c) relative to the total composition is at least 0.1 wt%, at least 1.0 wt%, or at least 3.0 wt%. In some embodiments, the amount of c) relative to the total composition is at least 0.1 wt% and less than 10 wt%. In some embodiments, the amount of c) relative to the total composition is at least 10 wt% and at most 27 wt%.

[0081] In this specification, the term "particle of material" is understood as a particulate component of the material, regardless of its shape (sphere, whisker, fiber, etc.). This term is used to distinguish it from the core of the core-shell particle described with respect to component b).

[0082] Preferably, the ceramic material is selected from metal oxides, metal silicates, metal borides, metal carbides and metal nitrides.

[0083] Preferably, the ceramic material is selected from metal oxides, metal borides, metal carbides and metal nitrides.

[0084] Preferably, the ceramic material is a metal oxide, more preferably one or more selected from the group consisting of titanium dioxide, barium titanate, and barium strontium titanate.

[0085] In some preferred embodiments, at least 80% by weight of the ceramic filler particles present in the composition without laser direct structuring additive functionality are titanium dioxide. This results in a composition with a low loss tangent at high frequencies. Preferably, the amount of titanium dioxide relative to the ceramic filler particles present in the composition without laser direct structuring additive functionality is at least 90%, at least 95%, at least 99%, or 100% by weight.

[0086] In some preferred embodiments, at least 80 wt.% of the ceramic filler particles present in the compositions according to the invention that do not have laser direct structuring additive functionality are barium titanate. Preferably, the amount of barium titanate relative to the ceramic filler particles present in the compositions according to the invention that do not have laser direct structuring additive functionality is at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, or 100 wt.%.

[0087] In some preferred embodiments, at least 80% by weight of the ceramic filler particles present in the composition of the present invention that do not have laser direct structuring additive functionality are barium strontium titanate. This results in a composition with very high flame retardancy. Preferably, the amount of barium strontium titanate relative to the ceramic filler particles present in the composition of the present invention that do not have laser direct structuring additive functionality is at least 90% by weight, at least 95% by weight, at least 99% by weight, or 100% by weight.

[0088] Preferably, the total amount of b1), b2) and c) relative to the total composition is at least 35% by weight, more preferably at least 40% by weight, which increases the dielectric constant. Preferably, the total amount of b1), b2) and c) relative to the total composition is at most 70% by weight or at most 65% by weight.

[0089] Preferably, the total amount of b) and c) relative to the total composition is at least 35% by weight, more preferably at least 40% by weight. Preferably, the total amount of b) and c) relative to the total composition is at most 70% by weight or at most 65% by weight.

[0090] Preferably, the weight ratio of the total amount of b1) and b2) in the composition to the amount of c) in the composition is at least 1.0, preferably at least 1.2, at least 1.5, at least 1.8, at least 2.0, at least 2.5, at least 3.0, at least 3.5, or at least 4.0.

[0091] Preferably, the weight ratio of the amount of b) in the composition to the amount of c) in the composition is at least 1.0, preferably at least 1.2, at least 1.5, at least 1.8, at least 2.0, at least 2.5, at least 3.0, at least 3.5, or at least 4.0.

[0092] Sum of a), b) and c) Preferably, the total amount of components a), b) and c) is from 90 to 99.9% by weight of the total composition, for example from 95 to 99% by weight.

[0093] d) Acid-modified polymer The acid-modified polymer may be a polymer obtained by modifying a polymer with a compound having a functional group such as an unsaturated carboxylic acid.

[0094] Preferably, the acid-modified polymer is an acid-modified olefin polymer or an acid-modified styrene polymer, more preferably an acid-modified olefin polymer.

[0095] The olefin polymer is preferably polyethylene or polypropylene.

[0096] The olefin polymer preferably has a weight average molecular weight of 1,000 to 5,000.

[0097] 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 acid monoamide.

[0098] Most preferably, the acid-modified olefin polymer is maleic anhydride-modified polyethylene.

[0099] Suitable examples include commercially available Mitsui Hi-WAX 1105A from Mitsui Chemicals, Inc., with an Mv of 1500, a density of 940 kg / m3, and an acid number of 60 KOH mg / g.

[0100] The amount of d) is 0.1 to 5.0% by weight, preferably 0.3 to 3.0% by weight, more preferably 0.5 to 1.5% by weight, based on the total composition.

[0101] The sum of a), b), c) and d) Preferably, the total amount of components a), b), c) and d) is 90 to 100% by weight of the total composition, for example 90 to 99.9%, 92 to 99.0% or 95 to 98% by weight of the total composition. Preferably, the total amount of components a), b), c) and d) is at least 96%, at least 97%, at least 98% or at least 99% by weight of the total composition.

[0102] e) Flame retardants Preferably, the thermoplastic composition according to the present invention further comprises e) a flame retardant.

[0103] Preferably, the amount of component e) relative to the total composition is 0 to 15 wt.%, for example at least 0.01 wt.%, at least 0.05 wt.%, or at least 0.1 wt.%, and / or at most 10 wt.%, at most 5 wt.%, or at most 1.0 wt.%.

[0104] The flame retardant may be an inorganic flame retardant or an organic flame retardant.

[0105] Examples of inorganic flame retardants include sulfonates such as potassium perfluorobutanesulfonate (limale salt) and potassium diphenylsulfonesulfonate, salts formed by reacting an alkali metal or alkaline earth metal (preferably lithium, sodium, potassium, magnesium, calcium, or barium salts) with an inorganic acid complex, such as an oxoanion such as alkali metal and alkaline earth metal carbonates such as Na2CO3, K2CO3, MgCO3, CaCO3, BaCO3, and BaCO3, or fluoroanion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, and / or Na3AlF6. Inorganic flame retardants are advantageous for maintaining the Vicat temperature.

[0106] Examples of organic flame retardants include organic phosphates and / or organic compounds containing a phosphorus-nitrogen bond.

[0107] One type of exemplary organic phosphate is an aromatic phosphate of 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 can be linked together to provide a cyclic group, such as diphenylpentaerythritol diphosphate, which is described by Axelrod in U.S. Pat. No. 4,154,775. Other suitable aromatic phosphates can be, 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, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5′-trimethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate, etc. Particular aromatic phosphates are those in which each G is aromatic, such as, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, etc.

[0108] Di- or polyfunctional aromatic phosphorus-containing compounds are also useful, such as compounds of the formula: [ka] (wherein each G1 is independently a hydrocarbon having 1 to 30 carbon atoms, each G2 is independently a hydrocarbon or hydrocarbonoxy having 1 to 30 carbon atoms, each X is independently bromine or chlorine, m is 0 to 4, and n is 1 to 30.) Examples of suitable di- or polyfunctional aromatic phosphorus-containing compounds include resorcinol tetraphenyl diphosphate (RDP), bis(diphenyl)phosphate of hydroquinone, and bis(diphenyl)phosphate of bisphenol-A (including their oligomeric and polymeric counterparts, respectively). Methods for preparing the aforementioned di- or polyfunctional aromatic compounds are described in GB 2,043,083.

[0109] Further examples of organic flame retardants are phosphazene compounds, in particular [ka] (wherein t is an integer from 3 to 25, R5 and R6 may be the same or different, each of which is an aryl group or an alkylaryl group, and [ka] (wherein u is an integer of 3 to 10,000; R9 represents at least one selected from a -N=P(OR)3 group, a -N=P(OR8)3 group, a -N=P(O)OR7 group, and a -N=P(O)OR8 group; R10 represents at least one selected from a -P(OR7)4 group, a -P(OR8)4 group, a -P(O)(OR7)2 group, and a -P(O)(OR8)2 group; R7 and R8 may be the same or different, and each represents an aryl group or an alkylaryl group).

[0110] Examples of such phosphazene compounds represented by the above two formulas include phenoxyphosphazene, (poly)tolyloxyphosphazene (e.g., o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o,m-tolyloxyphosphazene, o,p-tolyloxyphosphazene, m,p-tolyloxyphosphazene, and o,m,p-tolyloxyphosphazene), and cyclic and / or linear C1-6 alkyl C6-20 aryloxyphosphazenes such as (poly)xylyloxyphosphazene, and (poly)phenoxytolyloxyphosphazene (e.g., phenoxy-o-tolyloxyphosphazene, phenoxy-m-tolyloxyphosphazene, phenoxy-p-tolyloxyphosphazene, phenoxy-o,m-tolyloxyphosphazene, and / or linear C6-20 arylC1-10 alkylC6-20 aryloxyphosphazenes such as phenoxy-o,p-tolyloxyphosphazene, phenoxy-m,p-tolyloxyphosphazene, and phenoxy-o,m,p-tolyloxyphosphazene), (poly)phenoxyxylyloxyphosphazene, and (poly)phenoxytolyloxyxylyloxyphosphazene, in which case preferred examples include cyclic and / or linear phenoxyphosphazene, cyclic and / or linear C1-3 alkylC6-20 aryloxyphosphazenes, and C6-20 aryloxyC1-3 alkylC6-20 aryloxyphosphazenes (for example, cyclic and / or linear tolyloxyphosphazene, and cyclic and / or linear phenoxytolylphenoxyphosphazene).

[0111] Examples of such phosphazene compounds include cyclic phenoxyphosphazene from Otsuka Chemical Co. Ltd., trade name SPB-100, and cyclic phenoxyphosphazene from Fushimi Pharmaceutical Co. Ltd., trade name Rabitle FP-110.

[0112] Such phosphazene compounds are described in detail in US Patent Application Publication No. 2012 / 0301766,

[0133] -

[0142] , which is incorporated by reference.

[0113] The thermoplastic compositions of the present invention may be essentially free of chlorine and bromine, particularly chlorine and bromine flame retardants, which may be defined as having a bromine and / or chlorine content of less than 100 ppm, less than 75 ppm, or less than 50 ppm, based on the total composition.

[0114] Preferably, molded parts of the composition have at least a UL94 V2 rating (ie, a V2, V1, or V0 rating) at a thickness of 3.0 mm (±10%).

[0115] Preferably, molded parts of the composition have at least a UL94 V2 rating (ie, a V2, V1 or V0 rating) at a thickness of 1.5 mm (±10%).

[0116] It has been observed that the LDS additive used in the present invention, unlike other types of LDS additives, can achieve the desired UL94 rating. Even more surprisingly, it has been found that the addition of the acid-modified polymer according to the present invention does not have a substantial adverse effect on flame retardancy. Thus, by adding an appropriate amount of flame retardant, the present invention can achieve the desired UL94 rating.

[0117] The sum of a), b), c), d) and e) Preferably, the total amount of components a), b), c), d), and e) is 90 to 100 wt.% of the total composition, for example, 90 to 99.9 wt.%, 92 to 99.0 wt.%, or 95 to 98 wt.% of the total composition. Preferably, the total amount of components a), b), c), d), and e) is at least 96 wt.%, at least 97 wt.%, at least 98 wt.%, or at least 99 wt.% of the total composition.

[0118] Ingredient f) Anti-drip agent The thermoplastic composition according to the present invention may further comprise f) an anti-drip agent.

[0119] Preferably, the amount of component f) is 0 to 2.0 wt. % or 0.05 to 2.0 wt. %, more preferably 0.1 to 1.5 wt. %, more preferably 0.2 to 1.0 wt. % of the total composition. The presence of component f) is optional, and thus, compositions 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 wt. %, less than 0.01 wt. %, or less than 0 wt. % of the total composition.

[0120] Suitable examples of anti-drip agents 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.

[0121] The anti-drip agent may be in the form of an (aqueous) dispersion of fluoropolymer, where the dispersion comprises a sufficient amount of fluoropolymer, for example at least 30% or at least 50% by weight of the dispersion of fluoropolymer.

[0122] The anti-drip agent can be in the form of a mixture of a fluoropolymer and an additional polymer, such as 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 the mixture. The additional 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 METABLENA-3800. The encapsulated fluoropolymer can be made by polymerizing a polymer in the presence of the fluoropolymer.

[0123] Preferably, the anti-drip agent is a mixture of a fluoropolymer and a further polymer, such as an encapsulated fluoropolymer, which can be handled better than an anti-drip agent in the form of a dispersion, since it is easier to feed into an extruder and does not require the removal of water from the composition.

[0124] The sum of a), b), c), d), e) and f) Preferably, the total amount of components a), b), c), d), e), and f) is 90 to 100% by weight of the total composition, for example, 90 to 99.9%, 92 to 99.0%, or 95 to 98% by weight of the total composition. Preferably, the total amount of components a), b), c), d), e), and f) is at least 96%, at least 97%, at least 98%, or at least 99% by weight of the total composition.

[0125] Other additives g) The thermoplastic composition according to the present invention may further comprise 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 or thermo-oxidative degradation, stabilizers against hydrolysis, stabilizers against degradation by light, especially ultraviolet light, and / or stabilizers against photo-oxidative degradation, as well as processing aids such as mold release agents and lubricants. Suitable examples of such additives and their conventional amounts are described in the aforementioned Kunststoff Handbuch, 3 / 1. The total amount of additives is typically 0 to 5% by weight, e.g., 0.1 to 3% by weight or 0.3 to 1% by weight.

[0126] The sum of a), b), c), d), e), f) and g) Preferably, the total amount of components a), b), c), d), e), f) and g) is 100% by weight of the total composition.

[0127] Glass filler h) The composition according to the present invention may or may not further comprise h) glass fillers, such as glass fibers, which are understood to be distinct from c) ceramic filler particles that do not have laser direct structuring additive functionality.

[0128] In some embodiments, the composition according to the present invention comprises less than 5 wt. % of glass fillers such as glass fibers, based on the total weight of the composition, preferably less than 4 wt. %, less than 3 wt. %, less than 2 wt. %, less than 1 wt. %, less than 0.5 wt. %, less than 0.1 wt. %, or 0 wt. %.

[0129] Preferably, the total amount of components a), b), c), d), e), f), g) and h) is 100% by weight of the total composition.

[0130] It will be understood that g) additives are different from e) flame retardants, f) anti-drip agents, and h) glass fillers, i.e., g) additives do not include e) flame retardants, f) anti-drip agents, and h) glass fillers.

[0131] The above components b) and d) and any optional components can be introduced into the thermoplastic resin a) by a suitable mixing device such as a single-screw or twin-screw extruder, preferably a twin-screw extruder. Preferably, thermoplastic resin pellets are introduced into the extruder together with at least components b) and d), extruded, then quenched in a water bath, and then pelletized. Thus, the present invention further relates to a process for producing the thermoplastic composition according to the present invention by melt-mixing components a), b), and d) and any optional components described above.

[0132] characteristics Preferably, the composition has a dielectric constant of at least 3.5 or at least 4.0 measured at 1 GHz, and / or at least 3.5 or at least 4.0 measured at 6 GHz. Such a DC can be achieved by selecting appropriate amounts of b1) and / or b2) and optional component c).

[0133] Preferably, compositions according to the present invention have a dielectric constant, measured at 1 GHz, of at least 3.5, more preferably at least 4.0, more preferably at least 4.2, more preferably at least 4.5, more preferably at least 4.7, more preferably at least 5.0.

[0134] Preferably, the compositions according to the present invention have a loss tangent (Df) measured at 1 GHz of 0.014 or less, more preferably 0.010 or less, more preferably 0.007 or less. A low Df minimizes energy loss (heat) and / or maximizes the energy irradiated.

[0135] Preferably, compositions according to the present invention have a dielectric constant, measured at 6 GHz, of 3.5 or greater, more preferably 4.0 or greater, more preferably at least 4.2, more preferably at least 4.5, more preferably at least 4.7, more preferably at least 5.0.

[0136] Preferably, the composition according to the invention has a loss tangent, measured at 6 GHz, of at most 0.014, more preferably at most 0.010, more preferably at most 0.007.

[0137] Preferably, compositions according to the present invention have a dielectric constant, measured at 40 GHz, of at least 3.5, more preferably at least 4.0, preferably at least 4.2, more preferably at least 4.5, more preferably at least 4.7, more preferably at least 5.0.

[0138] Preferably, the composition according to the invention has a loss tangent, measured at 40 GHz, of at most 0.014, preferably at most 0.010, more preferably at most 0.007.

[0139] Herein, the dielectric constant (DC) and loss tangent (sometimes referred to as dissipation factor (DF)) are measured in accordance with ASTM D-2520, Method B - Resonant Cavity Perturbation Technique. The nominal specimen size of the test specimen is 1.78 x 2.54 x 25.4 mm. Testing is conducted at ambient laboratory conditions (nominal 23°C and 51% RH).

[0140] Preferably, the thermoplastic resin has a melt flow rate measured in accordance with ISO 1133-1:2011 at 300°C and an MFR1 of 1.2 kg, and the composition according to the invention has a melt flow rate measured in accordance with ISO 1133-1:2011 at 300°C and an MFR2 of 1.2 kg, wherein MFR2 is at most 130% of MRF1.

[0141] Highly flame-retardant embodiment It has been found that the lower the amount of b) and c), the better the flame retardancy, and in this case the flame retardant e) can be (substantially) absent to obtain the desired flame retardancy.

[0142] Thus, in some embodiments, the amount of b1), b2) or the sum of b1) and b2) relative to the total composition is at least 0.1 wt.% and at most 20 wt.%, preferably at least 1.0 wt.%, at least 3.0 wt.%, or at least 5.0 wt.%, and / or at most 19 wt.%, at most 18 wt.%, at most 17 wt.%, at most 16 wt.%, at most 16 wt.%, or at most 15 wt.%.

[0143] In some embodiments, the amount of b) relative to the total composition is at least 0.1 wt.%, at most 20 wt.%, preferably at least 1.0 wt.%, at least 3.0 wt.%, or at least 5.0 wt.%, and / or at most 19 wt.%, at most 18 wt.%, at most 17 wt.%, at most 16 wt.%, at most 16 wt.%, or at most 15 wt.%.

[0144] In some embodiments, the amount of c) relative to the total composition is at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 10 wt%, less than 10 wt%, at most 9 wt%, at most 8 wt%, at most 5 wt%, at most 3 wt%, at most 1 wt%, or 0 wt%, relative to the total composition.

[0145] In some embodiments, the total amount of b1), b2) and c) relative to the total composition is less than 35 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 10 wt%, less than 10 wt%, at most 9 wt%, at most 8 wt%, at most 5 wt%, at most 3 wt%, at most 1 wt%, or 0 wt%, relative to the total composition.

[0146] In some embodiments, the total amount of b) and c) relative to the total composition is less than 35 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 10 wt%, less than 10 wt%, at most 9 wt%, at most 8 wt%, at most 5 wt%, at most 3 wt%, at most 1 wt%, or 0 wt%, relative to the total composition.

[0147] In these embodiments, preferably, molded parts of the composition have a UL94 V2, V1, or V0 rating at a thickness of 1.5 mm (±10%), and / or a UL94 V2, V1, or V0 rating at a thickness of 3.0 mm (±10%). The composition may or may not include a flame retardant. If the composition includes a flame retardant, the amount of flame retardant relative to the total composition may be, for example, at least 0.01 wt.% and / or at most 5 wt.%, at most 1.0 wt.%, at most 0.5 wt.%, at most 0.1 wt.%, at most 0.05 wt.%, or at most 0.01 wt.%.

[0148] Other Aspects The present invention further relates to a molded part comprising a thermoplastic composition according to the present invention. The present invention particularly relates to a molded part made by injection molding of a composition according to the present invention. The present invention also relates to an article, in particular a circuit carrier, comprising a molded part made from a composition according to the present invention and a conductive track provided thereon. In one embodiment, such a circuit carrier is used to make an antenna.

[0149] The present invention further relates to a process for producing such a circuit carrier, comprising the steps of providing a molded part containing a thermoplastic composition according to the present invention, irradiating the areas of said part where conductive tracks are to be formed with laser radiation, and then metallizing the irradiated areas. In a preferred embodiment, laser radiation is used to ablate the part while simultaneously releasing metal nuclei and forming an adhesion-promoting surface. This provides a simple means for achieving excellent adhesion strength of the deposited metal conductor tracks. The laser wavelength is advantageously 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm, or even 10,600 nm. Further metal deposition on the metal nuclei generated by laser radiation is preferably carried out by a plating process. The aforementioned metallization is preferably carried out by immersing the molded part in at least one electroless plating bath to form electrically conductive paths in the irradiated areas of the molded part. Non-limiting examples of electroless plating processes are copper plating, gold plating, nickel plating, silver plating, zinc plating, and tin plating. Preferably, the first plating is a copper plating. The conductive track can have one or more layers. The first layer can be, for example, a copper layer and can be 8 to 16 μm thick, more typically 8 to 12 μm thick. If present, the second layer can be, for example, a nickel layer and can be 2 to 4 μm thick. If present, the third layer can be, for example, a gold layer and can be 0.05 to 0.2 μm thick.

[0150] Irradiation of the molded part may be carried out under conditions including, for example, a power of 2 to 15 W, a frequency of 20 to 100 kHz, and / or a speed of 1 to 5 m / sec.

[0151] Irradiation of the molded part can be carried out, for example, with 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 25000 nm.

[0152] When irradiating the molded part with ultraviolet light having a wavelength of 100 to 400 nm, it may be preferable to subject the molded part having metallized regions to a heat treatment to improve peel resistance. Heat treatment can be performed by exposing the molded part to microwaves, for example, by placing the molded part in a microwave oven. Preferably, the molded part is irradiated with visible light having a wavelength of 400 to 800 nm or infrared light having a wavelength of 800 to 25,000 nm. These types of laser irradiation are advantageous in that the metal layer in the irradiated region has a relatively higher adhesive strength without the need for heat treatment after the plating process. Most preferably, the molded part is irradiated with infrared light having a wavelength of 800 to 25,000 nm, particularly 1,064 nm.

[0153] Preferably, the process for making the circuit carrier does not include a step of heat treatment after the step of metallizing the irradiated areas, which is advantageous in that it allows for an efficient process.

[0154] A further aspect of the present invention relates to a thermoplastic composition according to the present invention for use in a laser direct structuring process.

[0155] A further aspect of the present invention relates to the use of the thermoplastic composition according to the invention in a laser direct structuring process.

[0156] The present invention relates to the subject matter defined in the independent claims alone or in any possible combination of the features described herein. It should be noted that combinations of features present in the claims are particularly preferred. Thus, it is understood that all combinations of features related to the compositions according to the invention, all combinations of features related to the processes according to the invention, and all combinations of features related to the compositions according to the invention and the processes according to the invention are described herein. Thus, it is understood that combinations of features related to the molding step, the irradiation and metallization steps of the processes according to the invention, and features related to the compositions according to the invention are described herein. For example, the present specification discloses a process for producing a circuit carrier, which comprises the steps of providing a molded part comprising a thermoplastic composition according to the invention, irradiating with laser radiation the areas of the part where conductive tracks are to be formed, and then metallizing the irradiated areas, wherein the composition comprises component d), and the irradiation of the molded part is carried out with infrared light having a wavelength of 800 to 25,000 nm.

[0157] It should further be noted that the term "comprising" does not exclude the presence of other elements. However, it should be understood that a description of a product comprising certain components also discloses a product consisting of those components. Similarly, a description of a process comprising certain steps also discloses a process consisting of those steps. A product / composition consisting of those components may be advantageous in that it provides a simpler and more economical process for preparing the product / composition. Similarly, a description of a process comprising certain steps also discloses a process consisting of those steps. A process consisting of those steps may be advantageous in that it provides a simpler and more economical process.

[0158] When lower and upper limits for a parameter are listed, it is understood that the range formed by the combination of the lower and upper limits is also disclosed.

[0159] The present invention will now be illustrated by the following examples, but is not limited thereto. [Example]

[0160] experiment Comparative experiments (CEx) and example compositions (Ex) were prepared from the ingredients shown in Table 1.

[0161] All sample compositions were prepared according to the amounts shown in Tables 2 through 4. All amounts are in weight percent. In each experiment, the samples were extruded in a co-rotating twin-screw extruder at a temperature of 280°C. The extrudate was granulated, and the collected granules were dried at a temperature of 110°C for 4 hours and then injection molded into test parts using a melt temperature of approximately 290°C to 300°C.

[0162] High frequency properties—dielectric constant (DC) and dissipation factor (DF)—were measured at 6 GHz using the guidelines of ASTM D-2520, Method B—Resonant Cavity Perturbation Technique. The nominal specimen size of the test specimen was 1.78 x 2.54 x 25.4 mm. Testing was performed at ambient laboratory conditions (nominal 23°C and 51% RH).

[0163] Flammability performance was determined according to the UL94 V method after storing the samples for 48 hours at 23°C and 50% relative humidity. For each sample, five test bars were tested. In addition to the UL94 V rating (V-0, V-1, V-2, or NC (= no classification)), the total flame out time (FOT), which is the sum of the afterflame times of the first (t1) and second (t2) flame contacts of the five tested bars, is also recorded.

[0164] The degree of resin decomposition after compounding was determined by measuring the melt mass flow rate (MFR) of the resin before compounding and of the composition prepared by compounding the resin at 300°C / 1.2 kg according to ISO 1133. The presence of ceramic fillers in a composition generally leads to a lower MFR. Therefore, if no polymer decomposition occurred during compounding, the MFR of the composition would typically be lower than the MFR of the resin. Therefore, the increase in MFR after compounding is believed to be due to resin decomposition.

[0165] The degree of resin decomposition after compounding was further confirmed by measuring the Vicat temperature and Izod notched impact strength of the resin before compounding and of compositions prepared with the resin. Both the decrease in Vicat temperature and the decrease in impact strength are due to resin decomposition.

[0166] [Table 1]

[0167] [Table 2]

[0168] Table 2 shows the results using the most commonly used LDS additives, copper chromium oxide spinel and antimony-doped tin oxide.

[0169] In CEx1 and CEx2, where small amounts of LDS additive were used, the MFR of the compositions was lower than that of the resin, indicating that excessive degradation of the resin was not occurring. The same conclusion can be drawn from the values ​​of MV at high shear viscosity, Vicat temperature, and Izod notched impact strength.

[0170] CEx1 and CEx2 provide desirable dielectric properties, in particular a dielectric constant of at least 4.0 at 6 GHz.

[0171] However, CEx1 and CEx2 did not provide the desired flame retardancy.

[0172] It can be seen that excessive decomposition of the resin did not occur in CEx3, which used a large amount of CuCr. However, the dielectric constant was not very high, falling below 1.0 at 6 GHz. Desired flame retardancy was obtained.

[0173] It can be seen that excessive resin decomposition occurred in CEx4, which used a large amount of ATO. The MFR of the composition exceeded 200% of the MFR of the resin. Furthermore, while desirable dielectric properties were obtained, desirable flame retardancy was not.

[0174] Therefore, it can be concluded that the use of copper chromite or ATO does not provide the desired combination of properties.

[0175] [Table 3]

[0176] Table 3 shows the results using aluminum doped zinc oxide (AZO) according to the present invention.

[0177] In CEx5, where AZO is used without wax, desirable dielectric properties and desirable flame retardancy are achieved. However, it is evident that excessive decomposition of the resin has occurred. The MFR of the composition was too high to measure. Decomposition can also be confirmed by MV, Vicat temperature, and Izod notched impact strength.

[0178] In contrast, Ex1, in which AZO was used with wax, did not result in excessive resin decomposition and provided desirable dielectric properties and flame retardancy.

[0179] This is surprising considering CEx6, which uses ATO with wax instead of AZO and wax as in Ex1. CEx6 shows that the wax did not prevent excessive resin degradation caused by ATO. It also did not provide the desired flame retardancy. Therefore, it can be concluded that certain LDS additives in combination with waxes provide a desirable combination of properties.

[0180] Also, Ex2 and Ex3 show a desirable combination of properties. It can be seen that a higher DC can be obtained by using a larger amount of TiO2, but it can also be seen that the DC is still high even without using a large amount of TiO2. Comparing Ex2 and Ex3 shows that there is no significant difference depending on the type of ceramic filler (TiO2 or BST).

[0181] [Table 4]

[0182] A comparison of Ex4 and Ex5 shows that a lower amount of wax is more favorable for flame retardancy.

[0183] The comparison of Ex4 and Ex6 shows that a lower amount of TiO2 is more favorable for flame retardancy.

[0184] A comparison of Ex4 and Ex7 shows that a higher amount of PC relative to AZO is beneficial for impact strength.

[0185] The comparison of Ex4 and Ex6 shows that the higher the amount of TiO2, the more favorable the DC.

[0186] A comparison of Ex5 and Ex7 shows that the higher the amount of ATO, the more favorable it is for DC.

[0187] [Table 5]

[0188] A comparison of Ex4 and Ex8 shows that the addition of ATO reduces flame retardancy.

[0189] A comparison of Ex4 and Ex9 shows that the addition of smaller amounts of CuCr2O4 does not substantially change the properties.

[0190] [Table 6]

[0191] Table 6 shows the results using copper calcium titanate (CCTO) according to the present invention.

[0192] Similar to the experiments with AZO, wax-free CEx7 exhibits very high MFI and very low Izod impact strength due to polymer degradation.

[0193] Ex10, which contains a small amount of wax, exhibits excellent flame retardancy without significant decomposition (low MFI / high MV, high impact strength). Furthermore, Ex10 achieves a high DC.

[0194] Ex11, which uses a different type of flame retardant, shows a desirable combination of properties: the flame retardancy is even better than Ex10.

[0195] CEx8 shows that the addition of MZP has some effect on preventing polymer degradation, but the effect is very limited compared to the use of wax according to the present invention.

Claims

1. a) 20 to 90 wt. % of a thermoplastic resin; b) a laser direct structuring additive; and c) optionally ceramic filler particles without laser direct structuring additive functionality; d) 0.1 to 5.0 wt. % of maleic anhydride modified polyethylene; A thermoplastic composition comprising: b) is b1) A conductive metal oxide, wherein the conductive metal oxide has a surface area of ​​5×10 3 a conductive metal oxide having a resistivity of Ω cm or less and containing at least a metal from group n and group n+1 of the periodic table, where n is an integer between 3 and 13; and / or b2) Copper calcium titanate A thermoplastic composition comprising:

2. 10. The composition of claim 1, wherein a) is a polycarbonate or a blend of a polycarbonate and a rubbery polymer.

3. 3. The composition according to claim 1, wherein n is an integer from 10 to 13.

4. The composition according to any one of claims 1 to 3, wherein b) comprises particles of b1) and / or particles of b2).

5. The composition according to any one of claims 1 to 4, wherein the amount of b1), the amount of b2), or the total amount of b1) and b2) relative to the total composition is 0.1 to 80% by weight.

6. The composition of any one of claims 1 to 5, wherein a molded part of the composition has a UL94 V2, V1 or V0 rating at a thickness of 1.5mm (+ / - 10%).

7. The composition according to any one of claims 1 to 6, wherein the amount of c) relative to the total composition is less than 10% by weight.

8. 8. The composition of any one of claims 1 to 7, wherein the composition has a dielectric constant of at least 4.0, measured at 1 GHz, and / or the composition has a loss tangent, measured at 1 GHz, of 0.014 or less, and / or the composition has a dielectric constant, measured at 6 GHz, of 4.2 or greater, and / or the composition has a loss tangent, measured at 6 GHz, of 0.014 or less, and / or the composition has a dielectric constant, measured at 40 GHz, of 3.5 or greater, and / or the composition has a loss tangent, measured at 40 GHz, of 0.014 or less, wherein the dielectric constant and the loss tangent are measured in accordance with ASTM D-2520, Method B.

9. The composition according to any one of claims 1 to 8, wherein the total amount of b1), b2) and c) relative to the total composition is at least 35% by weight.

10. The composition of any one of claims 1 to 9, wherein the composition comprises less than 2.5% by weight of the rubbery polymer based on the total composition.

11. A molded part comprising the composition according to any one of claims 1 to 10.

12. 12. A process for making a circuit carrier, comprising the steps of providing a molded part according to claim 11, irradiating with laser radiation the areas of said part where conductive tracks are to be formed, and then metallizing the irradiated areas.

13. A circuit carrier obtainable by the process according to claim 12.

14. An antenna comprising the circuit carrier of claim 13.

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