Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
  • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
  • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/0011—Working of insulating substrates or insulating layers
  • H05K3/0014—Shaping of the substrate, e.g. by moulding
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0104—Properties and characteristics in general
  • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49117—Conductor or circuit manufacturing
  • Y10T29/49119—Brush

Definitions

• the present invention relates to an impact resistant, flame retardant thermoplastic composition and an article made from the composition.
• the invention also relates to use of the composition for a laser direct structuring process.
• EP2336247 discloses a polycarbonate resin composition comprising at least a polycarbonate resin (A), a metal organic sulfonate (B), a fluoropolymer (C), a
• polyalkylsilsesquioxane particle having an average particle diameter of 0.6 to 5 micrometres (D), and a graft copolymer having a butadiene content of 50 percent or more (E).
• EP2336247 mentions that the composition has an extremely high flame resistance and is also excellent in the impact resistance and the external appearance.
• US7985788 discloses a flame retardant resin composition comprising a polyalkylene furan dicarboxylate, an aromatic polycarbonate, a phosphazene compound, a fluorine- containing compound and a silicone/acrylic core-shell rubber. US7985788 states that the composition is excellent in both impact resistance and flame retardancy.
• W01 1 10365 discloses an ignition resistant carbonate polymer composition consisting of: (i) an aromatic polycarbonate or an aromatic polyester carbonate, (ii) a non-silicon- containing graft (co)polymer produced by mass polymerization, (iii) a silicon-containing graft (co)polymer having a core-shell morphology, (iv) an oligomeric aromatic
• phosphorous compound (v) a polytetrafluoroethylene polymer, a fluorothermoplast, or mixture thereof, and (vi) one or more of a thermoplastic vinyl (co)polymer, an impact modifier different from (iii), a filler, a reinforcing material, a stabilizer, a pigment, a dye, a mold release, a lubricant, or an anti-static agent.
• W01 1 10365 states that the composition has excellent ignition resistance, in particular short burn time, and good mechanical properties and elevated heat resistance.
• WO09024496 discloses a polymer composition containing a) 30-97 mass percent of aromatic polycarbonate, b) 0.5-20 mass percent of a metal compound capable of being activated by electromagnetic radiation and thereby forming elemental metal nuclei, and c) 2.5-50 mass percent of at least one rubber-like polymer, wherein the sum of a)-c) is 100 percent.
• the rubber may be siloxane based rubbers.
• a polymer composition was provided which can be used for a laser direct structuring process and in which the degradation of the aromatic polycarbonate is reduced.
• thermoplastic composition which shows a good flame retardancy and a good impact strength.
• thermoplastic composition which shows a good flame retardancy and a good impact strength.
• thermoplastic composition comprises :
• thermoplastic composition comprises components a) and c), b) and c) or a), b) and c). It has surprisingly been found that the combination of the Si containing component and the metal (oxy)hydroxide, i.e., the combination of the components a2) and c) or b) and c) results in a good flame retardancy and a good impact strength.
• Improvement of the impact strength of a thermoplastic composition generally results in a large decrease in the flame retardancy.
• Use of a Si component as an impact modifier results in a less decrease in the flame retardancy compared to the addition of other types of impact modifier such as the ones containing butadiene. Nevertheless, the composition with an improved impact strength by use of a Si component still leads to a decrease in the flame retardancy compared to a composition without a rubber.
• a high flame retardancy was obtained by the addition of the metal (oxy)hydroxide having BET surface area of at least 10 to a composition comprising a Si containing component as the impact modifier.
• the size of the metal (oxy)hydroxide was found to be an essential factor in achieving the improvement in the flame retardancy.
• a good weathering/UV performance is also observed with the composition of the present invention.
• the ratio of the total of a) and b) is preferably 75 to 99 wt% of with respect to the total composition.
• the ratio of a) with respect to the total of a) and b) may be 0-100 wt%, 1 -99 wt%, 5-95 wt%, 10-90 wt%, 25-75 wt% or 40-60 wt%.
• the ratio of the total of a1 ) and b) is preferably 75 to 99 wt% of with respect to the total composition.
• the ratio of a1 ) with respect to the total of a1 ) and b) may be 0-100 wt%, 1 - 99 wt%, 5-95 wt%, 10-90 wt%, 25-75 wt% or 40-60 wt%.
• a moulded part of the composition has a UL94 V2 rating, preferably V1 rating, more preferably V0 rating, at a thickness of 1 .6 mm. More preferably, a moulded sample of the composition has a V2 rating, preferably V1 rating, more preferably V0 rating at a thickness of 0.8 mm.
• UL94V is a method for evaluating the flame resistance from an afterflame time and drip property.
• the flame retardancy can be evaluated with a test piece having a prescribed size for the UL test kept in a temperature-controlled room.
• composition according to the present invention has a good hydrolytic stability.
• the composition according to the present invention has a ratio between a second melt flow index (MFI) and a first melt flow index (MFI) of at most 3, preferably at most 2.5, more preferably 2.0, wherein the second melt flow index is a melt flow index (MFI) as measured according ISO 1 133 at a melt temperature of 300 ' ⁇ and with a load of 1 .2 kg after a hydrolytic exposure test in which the composition is placed in an autoclave at a temperature of 120°C, 100% Relative Humidity and 2 bar pressure for 50 hours and the composition is dried for 4 hours at 120 ⁇ in a vacuum-N2 oven and the first melt flow index is a melt flow index (MFI) as measured according ISO 1 133 at a melt temperature of 300 ' ⁇ and with a load of 1 .2 kg before the hydrolytic exposure test.
• MFI melt flow index
• MFI melt flow index
• the composition according to the invention has a high impact strength, for example expressed in Izod Notched impact strength.
• the Izod Notched impact strength at -20 Q C (measured at a sample thickness of 3.2 mm according to ISO 180/4A) of a molded part of the thermoplastic composition has a value higher than 25 kJ/m 2 .
• the Izod Notched impact strength at room temperature (measured at a sample thickness of 3.2 mm according to ISO 180/4A) of a molded part of the thermoplastic composition has a value higher than 40 kJ/m 2 .
• the thermoplastic composition comprises a1 ) a thermoplastic resin and a2) a Si containing rubber.
• the thermoplastic resin is used as the major component of the composition and the Si containing rubber is added as an impact modifier of the thermoplastic resin.
• the thermoplastic composition may or may not further comprise b) polysiloxane-polycarbonate copolymer.
• the inventor has found that the addition of the Si containing rubber to the thermoplastic resin reduces the hydrolytic stability of the composition, but addition of component c) minimizes this hydrolytic degradation caused by addition of the Si containing rubber.
• the concentration of a1 ) thermoplastic resin in the composition of the present invention is preferably between 50 wt% and 98 wt%, more preferably between 70 wt% and 97 wt%, with respect to the weight of the total composition.
• thermoplastic resins that may be present in the composition according to the invention include, but are not limited to polycarbonate, in particular aromatic
• polycarbonate polyamide, polyester, polyesteramide, polystyrene, polymethyl
• the resins may be homopolymers, copolymers or mixtures thereof, and may be branched or non-branched. It is to be understood that the a2) thermoplastic resin does not include a polysiloxane- polycarbonate.
• suitable polyamides (PA) are aliphatic polyamides, that may eventually be branched polyamides, such as PA6, PA46, PA66, PA6/66, PA 1 1 , PA12, semi aromatic polyamides as MXD6, PA6I/6T, PA66/6T, PA4T fully aromatic polyamides and
• polyesters examples include polyethylene terephtalate (PET), polybutylene terephtalate (PBT), polypropylene terephtalate (PPT), polyethylene naphtanoate (PEN), polybutylene naphtanoate (PBN).
• Preferred polyesters are polyethylene terephtalate and polybutylene terephtalate.
• the thermoplastic resin comprises a polycarbonate-based resin.
• the polycarbonate-based resin may be selected from a polycarbonate or a resin blend that includes a polycarbonate.
• the polycarbonates may be homopolymers, copolymers and mixtures thereof, and may be branched or non-branched. Suitable polycarbonate-based resins are described e.g. in US2009/0292048, which is incorporated herein by reference.
• Polycarbonates including aromatic carbonate chain units include compositions having structural units of the formula (I):
• R is an aromatic organic radical and, in an alternative embodiment, a radical of the formula (II): -A -Y -A 2 - (II)
• each of A 1 and A 2 is a monocyclic divalent aryl radical and Y is a bridging radical having zero, one, or two atoms which separate A 1 from A 2 .
• one atom separates A 1 from A 2 .
• radicals of this type are -0-, -S-, - S(O)-, -S(02)-, -C(O)-, methylene, cyclohexyl-methylene, 2-[2,2,1 ]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, adamantylidene, or the like.
• zero atoms separate A 1 from A 2 , with an illustrative example being bisphenol.
• the bridging radical Y can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene or isopropylidene.
• Suitable aromatic polycarbonates include polycarbonates made from at least a divalent phenol and a carbonate precursor, for example by means of the commonly known interfacial polymerization process or the melt polymersiation method.
• Suitable divalent phenols that may be applied are compounds having one or more aromatic rings that contain two hydroxy groups, each of which is directly linked to a carbon atom forming part of an aromatic ring. Examples of such compounds are:
• the carbonate precursor may be a carbonyl halogenide, a halogen formate or carbonate ester.
• carbonyl halogenides are carbonyl chloride and carbonyl bromide.
• suitable halogen formates are bis-halogen formates of divalent phenols such as hydroquinone or of glycols such as ethylene glycol.
• carbonate esters examples include diphenyl carbonate, di(chlorophenyl)carbonate, di(bromophenyl)carbonate, di(alkylphenyl)carbonate, phenyltolylcarbonate and the like and mixtures thereof. Although other carbonate precursors may also be used, it is preferred to use the carbonyl halogenides and in particular carbonylchloride, also known as phosgene.
• the aromatic polycarbonates in the composition according to the invention may be prepared using a catalyst, an acid acceptor and a compound for controlling the molecular mass.
• catalysts examples include tertiary amines such as triethylamine, tripropylamine and ⁇ , ⁇ -dimethylaniline, quaternary ammonium compounds such as tetraethylammoniumbromide and quaternary phosphonium compounds such as methyltriphenylfosfoniumbromide.
• organic acid acceptors are pyridine, triethylamine, dimethylaniline and so forth.
• inorganic acid acceptors are hydroxides, carbonates, bicarbonates and phosphates of an alkali metal or earth alkali metal.
• compounds for controlling the molecular mass are monovalent phenols such as phenol, p-alkylphenols and para-bromophenol and secondary amines.
• Component a2) is preferably a graft copolymer comprising an elastomeric component containing Si.
• the graft copolymer is formed by graft-copolymerizing an elastomeric component containing Si with a monomer component copolymerizable therewith.
• the elastomeric component generally has a glass transition temperature of at most 0 °C, preferably at most -20 °C, more preferably-30 °C.
• graft copolymer for use in the invention, core/shell type graft copolymers are preferable wherein the core is the elastomeric component containing Si.
• the elastomeric component containing Si is preferably polyorganosiloxane.
• Component a2) is preferably a polyorganosiloxane containing graft copolymer preferably prepared by polymerizing 5 to 60 parts by weight of a vinyl monomer (I) in the presence of 40 to 95 parts by weight of polyorganosiloxanes particles (I I) (the sum of (I) and (II) is 100 parts by weight), as for example described in US2005/0143520.
• vinyl monomers (I) include, for example, aromatic vinyl monomers such as styrene, alpha - methylstyrene, p-methylstyrene, and p-butylstyrene; vinylcyanide monomers such as acrylonitrile and methacrylonitrile; (meth)acrylic 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
• the vinyl monomer (a-l) may include a multifunctional monomer having at least two polymerizable unsaturated bonds per molecule, if necessary.
• the multifunctional monomers include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, ethylene glycol dimethacrylate, 1 ,3-butylene glycol dimethacrylate, and divinylbenzene.
• the vinyl monomer (I) may be used alone or in combination.
• the polyorganosiloxane particles (II) are preferably prepared by emulsion polymerization of the constituent components. A normal seeded emulsion polymerization can be applied to the graft copolymerization and can be achieved by radical-polymerizing the vinyl monomer (I) in latex of the
• polyorganosiloxane particles (II) These graft copolymers comprising polyorganosiloxane are commercially available, e.g. as Kane Ace MR01 and Kane Ace MR02 from Kaneka Company.
• component a2 Other materials suitable as component a2) include Metablen S-2001 , Metablen S-2200 and Metablen SX05 from Mitsubishi Rayon.
• the thermoplastic composition comprises 1 -20 wt% of Si-containing rubber, preferably 2-15 wt%, more preferably 3-10 wt%.
• the thermoplastic composition according to the present invention is substantially free of other types of rubber, especially rubbers comprising butadiene.
• the thermoplastic composition may comprise a polysiloxane-polycarbonate copolymer as the major component of the composition.
• the polysiloxane- polycarbonate copolymer has an improved impact strength by the presence of the polysiloxane block in the copolymer. Examples of the polysiloxane- polycarbonate copolymer are described e.g. in US5380795 and WO09040772, which are incorporated herein as follows:
• polysiloxane blocks of the copolymer comprise repeating siloxane units (also referred to as “diorganosiloxane units”) of formula (1 ):
• R can independently be a C Ci 3 alkyl group, C Ci 3 alkoxy group, C2-C13 alkenyl group, C 2 -Ci 3 alkenyloxy group, C 3 -C 6 cycloalkyl group, C 3 -C 6 cycloalkoxy group, C 6 -Ci4 aryl group, C 6 -Ci 0 aryloxy group, C 7 -Ci 3 arylalkyl group, C 7 -Ci 3 arylalkoxy group, C 7 -Ci 3 alkylaryl group, or C 7 -Ci 3 alkylaryloxy group.
• the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Combinations of the foregoing R groups can be used in the same copolymer.
• the value of E in formula (1 ) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, the desired properties of the composition, and like considerations. Generally, E can have an average value of 2 to 1 ,000, specifically 2 to 500, and more specifically 5 to 100. In one embodiment, E has an average value of 10 to 75, and in still another embodiment, E has an average value of 20 to 60.
• the composition comprising the polysiloxane-polycarbonate copolymer can comprise a low amount of the thermoplastic resin and a high amount of the Si-containing rubber.
• E is of a higher value, e.g., greater than 40
• the composition comprising the polysiloxane-polycarbonate copolymer comprises a high amount of the thermoplastic resin and a low amount of the Si-containing rubber.
• a combination of a first and a second (or more) polysiloxane-polycarbonate copolymer can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.
• polydiorganosiloxane blocks are provided by repeating structural units of formula 2):
• each R can independently be the same or different, and is as defined above; and each Ar can independently be the same or different, and is a substituted or unsubstituted C 6 -C 3 o arylene radical, wherein the bonds are directly connected to an aromatic moiety.
• Useful Ar groups in formula (2) can be derived from a C 6 -C 3 o dihydroxyarylene compound, for example a dihydroxyarylene compound. Combinations comprising at least one of the foregoing dihydroxyarylene compounds can also be used.
• dihydroxyarylene compounds are 1 ,1 -bis(4- hydroxyphenyl) methane, 1 ,1 -bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4- hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, 1 ,1 -bis(4- hydroxyphenyl) propane, 1 ,1 -bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l- methylphenyl) propane, 1 ,1 -bis(4-hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulphide), and 1 ,1 -bis(4-hydroxy-t-butylphenyl) propane.
• Units of formula (2) can be derived from the corresponding dihydroxy compound of formula 3):
• polydiorganosiloxane blocks comprise units of formula (4):
• R and E are as described above, and each occurrence of R is independently a divalent Ci-C 30 alkylene, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound.
• the polydiorganosiloxane blocks are provided by repeating structural units of formula (5):
• Each R 5 in formula (5) is independently a divalent C 2 -C 8 aliphatic group.
• Each M in formula (5) can be the same or different, and can be a halogen, cyano, nitro, C C 8 alkylthio, C C 8 alkyl, C 2 -C 8 alkoxy, C 2 -C 8 alkenyl, C 2 -C 8 alkenyloxy group, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkoxy, C 6 -Ci 0 aryl, C 6 -Ci 0 aryloxy, C 7 - Ci 2 arylalkyl, C 7 -Ci 2 arylalkoxy, C 7 -Ci 2 alkylaryl, or C 7 -Ci 2 alkylaryloxy, wherein each n is independently 0, 1 , 2, 3, or 4.
• 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;
• R 5 is a dimethylene, trimethylene or tetramethylene group; and
• R is a Ci_s alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
• R is methyl, or a mixture of methyl and trifluoropropyl, or a mixture of methyl and phenyl.
• M is methoxy, n is one, R 5 is a divalent C C 3 aliphatic group, and R is methyl.
• Units of formula (5) can be derived from the corresponding dihydroxy polydiorganosiloxane (6):
• Such dihydroxy polysiloxanes can be made by effecting a platinum catalyzed addition between a siloxane hydride of formula (7 :
• R and E are as previously defined, and an aliphatically unsaturated monohydric phenol.
• Useful aliphatically unsaturated monohydric phenols included, for example, eugenol, 2-allylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2- bromophenol, A- allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4- propylphenol, 2-allyl-4,6- dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6- methoxy-4-methylphenol and 2- allyl-4,6-dimethylphenol. Mixtures comprising at least one of the foregoing can also be used.
• the polysiloxane block is a poly(dimethyl siloxane) (PDMS) block.
• the polysiloxane-polycarbonate can comprise 85 to 99 weight percent of carbonate units and 1 to 15 weight percent siloxane units. Within this range, the polysiloxane- polycarbonate copolymer can comprise 88, 90, 92, 94, 96, or 98 weight percent of carbonate units and correspondingly 2, 4, 6, 8, 10, or 12 weight percent of siloxane units. In a specific embodiment, the polysiloxane-polycarbonate comprises 85 to 98 weight percent of carbonate units and 2 to 15 weight percent siloxane units. In another specific embodiment, the polysiloxane-polycarbonate comprises 90 to 98 weight percent of carbonate units and 2 to 10 weight percent siloxane units.
• the polysiloxane-polycarbonate can comprise polysiloxane units, and carbonate units derived from bisphenol A.
• Polysiloxane-polycarbonates can have a weight average molecular weight of 2,000 to 100,000, specifically 5,000 to 50,000 as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with polycarbonate standards.
• the polysiloxane-polycarbonate can have a melt volume flow rate, measured at 300 degrees centigrade under a load of 1 .2 kg, of 1 to 50 cubic centimeters per 10 minutes (cc/10 min), specifically 2 to 30 cc/10 min. Mixtures of polysiloxane-polycarbonates of different flow properties can be used to achieve the overall desired flow property.
• exemplary polysiloxane-polycarbonates are marketed under the trade name LEXAN (R) EXL polycarbonates, available from Sabic Innovative Plastics.
• the thermoplastic composition comprises siloxane units of formula (1 ) in an amount of less than or equal to 2 weight percent, specifically 0.1 to 2 weight percent, more specifically 0.1 to 1 .5 weight percent, and still more specifically 0.1 to 1 .0 weight percent, based on the total weight of the thermoplastic composition.
• the weight ratio of the component (b) with respect to the total of the components (a1 ) and (b) may e.g. be at least 50% and may be 100%.
• the composition may comprise (a1 ) 0-50 wt% of the thermoplastic resin, (a2) 1 -20 wt% of the Si-containing rubber and (b) 50-99 wt% of the polysiloxane- polycarbonate copolymer.
• the weight ratio of the component (b) with respect to the total of the components (a1 ) and (b) may preferably be e.g. less than 50%.
• the composition may comprise (a1 ) 50-98 wt% of the thermoplastic resin, (a2) 1 -20 wt% of the Si-containing rubber and (b) 1 -49 wt% of the polysiloxane- polycarbonate copolymer.
• metal (oxy)hydroxide is herein understood to mean both a metal hydroxide and a metal oxyhydroxide.
• the metal (oxy)hydroxide is a compound represented by the general formula M a (OH) b or M a O(OH) b , wherein M is selected from the group consisting of Li, Na, K, Mg, Ca, Al, Zn and Fe and a is 1 or 2 and b is 1 , 2 or 3.
• M is Mg or Al.
• M is Al since the metal (oxy)hydroxides based on Al have high temperature stability.
• the metal (oxy)hydroxide is a metal oxyhydroxide represented by the general formula M a O(OH) b , wherein a is 1 or 2 and b is 1 , 2 or 3.
• a is 1 and b is 2.
• the metal (oxy)hydroxide examples include AIO(OH), AI(OH) 3 , Mg(OH) 2 , Mg 2 0(OH) 2 .
• the metal oxyhydroxide is AIO(OH), preferably ⁇ - ⁇ ( ⁇ ).
• the metal (oxy)hydroxide preferably has a BET surface area of at least 12, more preferably at least 15.
• the thermoplastic composition comprises 1 -20 wt% of the metal (oxy)hydroxide, preferably 2-15 wt%, more preferably 3-10 wt%.
• thermoplastic composition of the present invention comprise a graft copolymer having a core/shell structure wherein the core comprises polyorganosiloxane as component a2) and AIO(OH) as component c).
• thermoplastic composition of the present invention may further comprise a flame retardant.
• the flame retardancy is further improved. Any known flame retardant may be used. Suitable examples of the flame retardant are certain alkali or earth alkali sulfonates (e.g. potassium perfluoro butane sulfonate), sulphonamide salts, perfluoroborates, halogenated compounds, especially bromated aromatic compounds, and phosphorus- bearing organic compounds, especially phosphate esters such as triphenyl phosphate and organic compounds containing phosphorus-nitrogen bonds.
• alkali or earth alkali sulfonates e.g. potassium perfluoro butane sulfonate
• sulphonamide salts e.g. potassium perfluoro butane sulfonate
• perfluoroborates e.g. halogenated compounds, especially bromated aromatic compounds
• phosphorus- bearing organic compounds especially phosphate esters such as triphenyl
• Suitable phosphorus-bearing compounds are described in for example DE 19828535 A1 (Komponente E), in EP 0640655 A2 ( Komponente D) and in EP 0363608 A1 (component C).
• a phosphorous-based flame retardant such as resorcinol diphenylphosphate (RDP), bisphenol-A diphenylphosphate (BDP), triphenyl phosphate or mixtures thereof.
• RDP resorcinol diphenylphosphate
• BDP bisphenol-A diphenylphosphate
• triphenyl phosphate or mixtures thereof.
• Phosphorous-based flame retardants are preferred, since the flame retardancy are significantly improved in combination with the metal hydroxide.
• the thermoplastic composition comprises 0-15 wt% of the d) flame retardant. Further suitable ranges of the amount of the flame retardant is 0.1 -10 wt% or 1 -5 wt%.
• Component e Coloring / LDS enabling additive
• the composition further comprises e) an additive selected from copper containing spinels such as copper chromium oxide spinel, copper molybdenum oxide spinel and copper chromium manganese oxide spinel; and tin containing oxides such as tin antimony oxide, tin bismuth oxide, tin aluminum oxide and tin molybdenum oxide.
• copper containing spinels such as copper chromium oxide spinel, copper molybdenum oxide spinel and copper chromium manganese oxide spinel
• tin containing oxides such as tin antimony oxide, tin bismuth oxide, tin aluminum oxide and tin molybdenum oxide.
• LDS laser direct structuring
• laser direct structuring additive or "LDS additive” is known and used e.g. in e.g. EP2291290B1 , US200506471 1 , WO20051031 13 and WO2009024496.
• a thermoplastic composition comprising a thermoplastic resin and a laser direct structuring additive is provided and the thermoplastic composition is irradiated at areas on which conductive tracks are to be formed with laser radiation. Subsequently the irradiated areas are selectively metalized to form conductive tracks. No metallization occurs on the areas that are not irradiated with laser radiation. The metallization can be done e.g.
• the laser direct structuring additive may be capable of being activated by laser radiation and thereby form elemental metal particles. It is believed that these metal particles act as nuclei for copper deposition in a standard electroless copper plating process and form the basis for the formation of conductive tracks. It is also possible that the radiation is not directly absorbed by the laser direct structuring additive, but is absorbed by other substances which then transfer the absorbed energy to the laser direct structuring additive and thus bring about the liberation of elemental metal.
• the laser radiation may be UV light (wavelength from 100 to 400 nm), visible light (wavelength from 400 to 800 nm), or infrared light (wavelength from 800 to 25 000 nm).
• Other preferred forms of radiation are X-rays, gamma rays, and particle beams (electron beams, a-particle beams, and ⁇ -particle beams).
• the laser radiation is preferably infrared light radiation, more preferably with a wavelength of 1064 nm.
• the additive may be copper containing spinels such as copper chromium oxide spinel, copper manganese oxide spinel and copper molybdenum oxide spinel. Copper containing spinels may function as a black pigment. Copper containing spinels may further function as a laser direct structuring (LDS) additive. Therefore, a composition is obtained having a good impact strength and a good flame retardancy and which can be used for an LDS process.
• copper containing spinels such as copper chromium oxide spinel, copper manganese oxide spinel and copper molybdenum oxide spinel.
• Copper containing spinels may function as a black pigment. Copper containing spinels may further function as a laser direct structuring (LDS) additive. Therefore, a composition is obtained having a good impact strength and a good flame retardancy and which can be used for an LDS process.
• LDS laser direct structuring
• the present invention provides a thermoplastic composition
• a thermoplastic composition comprising a) a1 ) a thermoplastic resin and a2) a Si containing rubber, c) a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010 and e) copper containing spinel.
• the present invention further provides a thermoplastic composition comprising b) a polysiloxane-polycarbonate copolymer, c) a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010 and e) copper containing spinel.
• the additive may be tin containing oxide such as tin antimony oxide, tin bismuth oxide, tin aluminum oxide and tin molybdenum oxide.
• Tin containing oxides have varying colors from almost white to light grey and may function as a pigment for giving the corresponding color such as light grey.
• Tin containing oxide may further function as a laser direct structuring (LDS) additive.
• LDS laser direct structuring
• the present invention provides a thermoplastic composition
• a thermoplastic composition comprising a) a1 ) a thermoplastic resin and a2) a Si containing rubber, c) a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010 and e) tin containing oxide.
• the present invention further provides a thermoplastic composition comprising b) a polysiloxane-polycarbonate copolymer, c) a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010 and e) tin containing oxide.
• the additive e) has a small size for giving a good mechanical strength to the composition according to the present invention.
• the additive e) has a particle size D90 of at most 10 ⁇ , more preferably at most 8 ⁇ .
• the metal oxide has a particle size D90 of at most 6 ⁇ , more preferably at most 4 ⁇ , more preferably at most 2.5 ⁇ .
• the additive e) has a particle size D50 of at most 6 ⁇ , more preferably at most 5 ⁇ . Even more preferably, the additive e) has a particle size D50 of at most 3 ⁇ , more preferably at most 1 ⁇ .
• the particle size may e.g. be determined by light scattering technology using a Microtrac full range analyzer (FRA) or a Malvern Mastersize particle size analyzer.
• FFA Microtrac full range analyzer
• Malvern Mastersize particle size analyzer Malvern Mastersize particle size analyzer
• the concentration of the component e) present in the composition of the present invention is preferably between 0 wt% and 25 wt%, more preferably between 1 and 20 wt%, even more preferably between 3 wt% and 15 wt%, and particularly preferably from 5 wt% up to 10 wt%, with respect to the weight of the total composition.
• the composition further comprises a white pigment selected from Ti0 2 , ZnO and BaS0 4 .
• a white or a light colored thermoplastic composition can be thereby obtained.
• the white pigment is advantageous in that the pigments or dyes of other colors may be added to give a desired color to the composition, as long as their amounts do not interfere with the desired properties of the composition.
• Other pigments and dyes for giving the thermoplastic composition desired colours are known to the skilled person and are commercially available.
• Known pigments include metal oxides available from companies such as Ferro, The Shepherd Color Company, Heubach, Rockwood Pigments, Tomatec and Broll-Buntpigmente.
• thermoplastic composition comprising a) a1 ) a thermoplastic resin and a2) a Si containing rubber, c) a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010 and f) Ti02.
• the present invention further provides a thermoplastic composition
• a thermoplastic composition comprising b) a polysiloxane-polycarbonate copolymer, c) a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010 and f) Ti02.
• the present invention further provides a thermoplastic composition comprising a) a1 ) a thermoplastic resin and a2) a Si containing rubber, c) a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010, e) an additive selected from copper containing spinels and tin containing oxides and f) Ti02.
• the present invention further provides a thermoplastic composition
• a thermoplastic composition comprising b) a polysiloxane-polycarbonate copolymer, c) a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010, e) an additive selected from copper containing spinels and tin containing oxides and f) Ti02.
• the concentration of component f) present in the composition of the present invention is preferably between 0 wt% and 25 wt%, more preferably between 0.1 and 20 wt%, even more preferably between 0.5 wt% and 10 wt%, and particularly preferably from 1 wt% up to 5 wt%, with respect to the weight of the total composition.
• thermoplastic composition according to the invention may further comprise from 0 up to 25 wt% of one or more other additives, relative to the total weight of the composition.
• additives such as stabilizers against thermal or thermo- oxidative degradation, stabilizers against hydrolytic degradation, stabilizers against degradation from light, in particular UV light, and/or photo-oxidative degradation, anti-drip agents such as for example PTFE, processing aids such as release agents and lubricants, colourants such as pigments and dyes.
• Suitable examples of such additives and their customary amounts are stated in the aforementioned Kunststoff Handbuch, 3/1 .
• the total of a)-f) is at least 90 wt%, at least 95 wt%, at least 98 wt% or at least 99 wt% of the total composition.
• the total of a)-f) may be 100 wt% of the total
• composition of the present invention comprises:
• the composition of the present invention comprises: a) a1 ) 0-49 wt% of a thermoplastic resin, a2) 0-20 wt% of a Si-containing rubber, b) 50-99 wt% of a polysiloxane-polycarbonate copolymer,
• the composition of the present invention comprises: a) a1 ) 1 -98 wt% of a thermoplastic resin, a2) 1 -20 wt% of a Si-containing rubber, b) 1 -97 wt% of a polysiloxane-polycarbonate copolymer,
• composition of the present invention comprises:
• the composition of the present invention comprises: a) a1 ) 0-48 wt% of a thermoplastic resin, a2) 0-20 wt% of a Si-containing rubber, b) 50-98 wt% of a polysiloxane-polycarbonate copolymer,
• the composition of the present invention comprises: a) a1 ) 1 -97 wt% of a thermoplastic resin, a2) 1 -20 wt% of a Si-containing rubber, b) 1 -96 wt% of a polysiloxane-polycarbonate copolymer,
• composition of the present invention comprises:
• a flame retardant 0-15 wt% of a flame retardant, e) 0-25 wt% of an additive selected from copper containing spinels and tin containing oxides and
• the composition of the present invention comprises: a) a1 ) 0-48 wt% of a thermoplastic resin, a2) 0-20 wt% of a Si-containing rubber, b) 50-98 wt% of a polysiloxane-polycarbonate copolymer,
• the composition of the present invention comprises: a) a1 ) 1 -97 wt% of a thermoplastic resin, a2) 1 -20 wt% of a Si-containing rubber, b) 1 -96 wt% of a polysiloxane-polycarbonate copolymer,
• composition of the present invention comprises:
• thermoplastic resin a) a1 ) 50-96 wt% of a thermoplastic resin, a2) 1 -20 wt% of a Si-containing rubber, c) 1 -20 wt% of a metal (oxy)hydroxide,
• the composition of the present invention comprises: a) a1 ) 0-47 wt% of a thermoplastic resin, a2) 0-20 wt% of a Si-containing rubber, b) 50-97 wt% of a polysiloxane-polycarbonate copolymer,
• a flame retardant 0-15 wt% of a flame retardant, e) 1 -25 wt% of an additive selected from copper containing spinels and tin containing oxides and
• the composition of the present invention comprises: a) a1 ) 1 -96 wt% of a thermoplastic resin, a2) 1 -20 wt% of a Si-containing rubber, b) 1 -95 wt% of a polysiloxane-polycarbonate copolymer,
• the components a)-f) and other additives as described above may be mixed by means of suitable mixing devices such as single-screw or twin-screw extruders, preferably a twin- screw extruder is used.
• suitable mixing devices such as single-screw or twin-screw extruders, preferably a twin- screw extruder is used.
• the invention therefore further relates to a process for producing a thermoplastic composition according to the present invention by melt mixing components a)-c) and other components.
• the invention further relates to moulded parts that contain the thermoplastic composition according to the present invention.
• the invention relates in particular to a moulded part produced by injection moulding of the composition according to the invention.
• the molded articles include parts of electric/electronic devices, OA devices and information terminal devices, machine parts, household electrical appliances, vehicle parts, building members, various vessels, leisure supplies/sundries, lighting devices, gauges, etc. Of those, in particular, the molded articles are favorably used for parts of electric/electronic devices, OA devices, information terminal devices, household electrical appliances, lighting devices, etc., and are particularly favorably used for parts of electric/electronic devices.
• Examples of the electric/electronic devices include personal computers, game machines, display devices such as televisions, printers, copiers, scanners, faxes, electronic notebooks and PDA, electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, battery packs, driving devices and reading devices of a recording medium, mouses, numeric keypads, CD players, MD players, portable radios/audio players, etc.
• the molded articles may be produced by any known methods. Examples thereof include an injection molding method, an ultrahigh-speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas-assisted molding, a molding method using an insulated mold, a molding method using a rapid heating mold, a foam molding (including a supercritical fluid, too), an insert molding, an IMC (in-mold coating) molding method, an extrusion molding method, a sheet molding method, a heat molding method, a rotation molding method, a laminate molding method, a press molding method, etc.
• a molding method using a hot runner system can also be employed.
• the invention further relates to an article, in particular a circuit carrier, that contains a moulded part produced from the composition according to the invention comprising a component which functions as an LDS additive as described above.
• a circuit carrier is used for producing an antenna.
• the invention further relates to a process for producing such a circuit carrier which process comprises the steps of providing a moulded part that contains the thermoplastic composition according to the present invention, irradiating areas of said part on which conductive tracks are to be formed with laser radiation, and subsequently metallizing the irradiated areas.
• the laser irradiation is used to simultaneously release metal nuclei and effect ablation of the part while forming an adhesion-promoting surface. This provides a simple means to achieve excellent adhesive strength of the deposited metallic conductor tracks.
• the wavelength of the laser is advantageously 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm or of even 10600 nm.
• the deposition of further metal onto the metal nuclei generated by laser radiation preferably takes place via plating processes.
• Said metallization is preferably performed by immersing the moulded part in at least one electroless plating bath to form electrically conductive pathways on the irradiated areas of the moulded part.
• electroless plating processes are a copper plating process, gold plating process, nickel plating process, silver plating, zinc plating and tin plating.
• thermoplastic composition for use in a laser direct structuring process.
• the invention further relates to use of a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010 in a thermoplastic composition comprising a thermoplastic resin and a Si-containing rubber for improving flame retardancy.
• the invention further relates to use of a metal (oxy)hydroxide in a thermoplastic composition comprising a thermoplastic resin and a Si-containing rubber for improving hydrolytic stability.
• the invention further relates to use of a metal (oxy)hydroxide with BET surface area of at least 10 as determined by DIN ISO 9277: 2010 in a thermoplastic composition comprising a thermoplastic resin and a Si-containing rubber for improving hydrolytic stability.
• the invention relates to all possible combinations of features described herein, preferred in particular are those combinations of features that are present in the claims. It is particularly noted that the invention relates to all possible combinations of the ranges of components described herein.
• compositions of Comparative Experiments CEx 1 -1 1 and of the Examples Ex 1 to Ex 5 were prepared from the components as given in Table 1 . Additionally, additives for processing and stabilization were added. These additives include Mold Release Agent (Loxiol P861/3.5, supplied by Cognis) and Heat Stabilizer (Irgafos 168, supplied by BASF).
• Table 2 gives the specific properties of the metal hydroxide materials used.
• the BET of the metal hydroxide particles were measured according to DIN ISO 9277: 2010.
• the metal hydroxide materials indicated as AIOOH 1 and AIOOH2 are similar materials except that AIOOH2 is provided with a surface coating, which did not influence the flame retardancy of the compositions of the examples.
• the metal hydroxide materials indicated as AIOOH3 and AIOOH4 are similar materials except that AIOOH4 is provided with a surface coating, which did not influence the flame retardancy of the compositions of the examples.
• the particle size distribution values (D10, D50 and D90) are values as obtained by the suppliers. According to supplier information a Malvern Mastersizer particle size analyser 2000 was used to measure the particle size distribution of materials AIOOH1 -4. Table 2
• Hydrolytic stability of the compounds was judged by measuring the Melt Flow Index (MFI) of the granulate material before and after a hydrolytic exposure test (HT) of the material in an autoclave operated at a temperature of 120 °C, 100% Relative Humidity and 2 bar pressure for 50 hours. MFI was measured according ISO 1 133 at a melt temperature of 300 ⁇ and with a load of 1 .2 kg. Before MFI testing the granulate was dried for 4 hours at 120 ⁇ in a vacuum-N2 oven.
• MFI Melt Flow Index
• HT hydrolytic exposure test
• CEx1 , CEx2, CEx3, Ex1 and Ex2 show the effect of AIOOH in a PC composition comprising a Si rubber, titanium dioxide and ATO.
• Comparison of CEx1 and CEx2 and CEx3 shows that the large sized AIOOH does not improve the flame retardancy of the composition, whereas comparison of CEx1 and Ex1 and Ex2 shows that the small sized AIOOH significantly improves the flame retardancy of the composition. It can also be seen that the difference in the AIOOH grade leads to substantially no difference in the flame retardancy.
• Comparison of CEx 1 and CEx 2, CEx 3, Ex 1 and Ex 2 shows that the hydrolytic stability of the composition without AIOOH is significantly improved by the addition of AIOOH. In CEx 1 , the MFI increased 9 times after the hydrolytic exposure test, whereas in the experiments with AIOOH, the increase in the MFI was at most 2.2.
• CEx4, CEx5, Ex 3 and Ex 4 show the effect of AIOOH in a PC composition comprising a Si rubber and titanium dioxide.
• Comparison of CEx4 and CEx5 shows that the large sized AIOOH does not improve the flame retardancy of the composition, whereas comparison of CEx4 and Ex3 and Ex4 shows that the small sized AIOOH significantly improves the flame retardancy of the composition. It can also be seen that the difference in the AIOOH grade leads to substantially no difference in the flame retardancy.
• Comparison of CEx 4 and CEx 5, Ex 3 and Ex 4 shows that the hydrolytic stability of the composition without AIOOH is significantly improved by the addition of AIOOH.
• CEx6, CEx7 and Ex5 show the effect of AIOOH in a PC composition comprising a Si rubber and ATO. Comparison of CEx6 and CEx7 shows that the large sized AIOOH does not improve the flame retardancy of the composition, whereas comparison of CEx6 and Ex5 shows that the small sized AIOOH significantly improves the flame retardancy of the composition.
• CEx8 and Ex6 show the effect of AIOOH in a PC composition comprising a Si rubber and CuCr 2 0 4 . Comparison of CEx8 and Ex 6 shows that the small sized AIOOH significantly improves the flame retardancy of the composition.

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