# US 10,370,534 B2 · High heat polycarbonate compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,534 B2 - Document ID: US10370534B2 - Status: Granted - Kind: B2 - Application number: 15/302,502 - Filed: 2015-04-15 - Published: 2017-01-26 - Granted: 2019-08-06 - Earliest claimed: 2014-04-15 - Assignees: Sabic Global Technologies B.V. - Applicants: Sabic Global Technologies B.V. - Inventors: Sarah E. Grieshaber; Tony Farrell; Daniel Francis Lowery; Mark Adrianus Johannes van der Mee; Roland Sebastian Assink; Robert Dirk van de Grampel - Web page: https://patentgrep.com/patent/US10370534B2 ## CPC - C08L 69/00: Compositions of polycarbonates; Compositions of derivatives of polycarbonates - B32B 15/09: comprising polyesters - C23C 18/1641: {Organic substrates, e.g. resin, plastic} - C08L 2201/08: Stabilised against heat, light or radiation or oxydation - C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure - C08L 2205/03: containing three or more polymers in a blend - C08L 2205/035: containing four or more polymers in a blend - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) ## Abstract Polycarbonate blend compositions are disclosed. The compositions include at least one polycarbonate useful for high heat applications. The compositions can include one or more additional polymers. The compositions can include one or more additives. The compositions can be used to prepare articles of manufacture, and in particular, automotive bezels. ## Claims ### Claim 1 A metallized article comprising a metallized surface and a thermoplastic composition comprising: (a) a first polycarbonate that includes structural units derived from at least one of: wherein Ra and Rb at each occurrence are each independently halogen, C1-C12 alkyl, C1-C12 alkenyl, C3-C8 cycloalkyl, or C1-C12 alkoxy; p and q at each occurrence are each independently 0 to 4; R13 at each occurrence is independently a halogen or a C1-C6 alkyl group; c at each occurrence is independently 0 to 4; R14 at each occurrence is independently a C1-C6 alkyl, phenyl, or phenyl substituted with up to five halogens or C1-C6 alkyl groups; Rg at each occurrence is independently C1-C12 alkyl or halogen, or two Rg groups together with the carbon atoms to which they are attached form a four-, five-, or six-membered cycloalkyl group; t is 0 to 10; and x:y is 1:99 to 99:1, the first polycarbonate having a Mw of 16,000 g/mol [±1,000 g/mol] to 20,000 g/mol [±1,000 g/mol], as determined by GPC using polycarbonate standards; (b) 15 to 60 wt % of a second polycarbonate that is a Bisphenol A (BPA) polycarbonate having a Mw of greater than 19,800 g/mol to 40,000 g/mol [±1,000 g/mol], as determined by GPC using BPA polycarbonate standards; (c) optionally 15 wt % to 45 wt % of a third polycarbonate that is a BPA polycarbonate having a Mw of 17,000 g/mol [±1,000 g/mol] to 40,000 g/mol [±1,000 g/mol], as determined by GPC using BPA polycarbonate standards; provided the third polycarbonate is different from the second polycarbonate; and (d) 0.5 wt % to 10 wt % of a first polyester of formula wherein T at each occurrence is independently selected from a divalent aliphatic radical, a divalent alicyclic radical, a divalent aromatic radical, and a polyoxyalkylene radical; D at each occurrence is independently selected from a divalent aliphatic radical, a divalent alicyclic radical, and a divalent aromatic radical; and m is an integer selected from 25 to 1000; provided that the combined wt % value of all components does not exceed 100 wt %; wherein the composition has a heat deflection temperature of at least 155° C., measured at 0.45 MPa in accordance with ASTM D 648 or ISO 75; wherein the composition has a melt viscosity of less than 395 Pa s, measured in accordance with ISO 11443 at 300° C. at a shear rate of 1500 s1; wherein a molded sample of the composition has at least 60% ductility in a multi-axial impact test at 23° C., measured in accordance with ASTM D3763 or ISO 6603; and wherein the article achieves a GT0 metal adhesion rating when measured in accordance with ASTM 3359/ISO 2409. ### Claim 2 (depends on 1) The metallized article of claim 1, wherein the article has one or more of the following properties: a minimum haze onset temperature of 150° C.; and exhibits 0% corrosion when stored for 240 hours at 98% relative humidity at 40° C., in accordance with DIN 50017. ### Claim 3 (depends on 1) The metallized article of claim 1, wherein the first polycarbonate comprises at least 18 mol % structural units derived from BPA, and has a Tg of at least 170° C. ### Claim 4 (depends on 1) The metallized article of claim 1, wherein the first polycarbonate comprises 31 mol % to 35 mol % structural units derived from PPPBP. ### Claim 5 (depends on 1) The metallized article of claim 1, wherein the first polycarbonate has a Mw of greater than 17,000 g/mol [±1,000 g/mol] and less than 20,000 g/mol [±1,000 g/mol], as determined by GPC using polycarbonate standards. ### Claim 6 (depends on 5) The metallized article of claim 5, wherein the article has one or more of the following properties: a minimum haze onset temperature of 150° C.; and exhibits 0% corrosion when stored for 240 hours at 98% relative humidity at 40° C., in accordance with DIN 50017. ### Claim 7 (depends on 5) The metallized article of claim 5, wherein the first polycarbonate comprises at least 18 mol % structural units derived from BPA, and has a Tg of at least 170° C. ### Claim 8 (depends on 5) The metallized article of claim 5, wherein the first polycarbonate comprises 31 mol % to 35 mol % structural units derived from PPPBP. ### Claim 9 (depends on 1) The metallized article of claim 1, wherein the first polycarbonate is selected from: a para-cumylphenol end-capped polycarbonate comprising structural units derived from PPPBP and BPA, having a Mw of 20,000 g/mol [±1,000 g/mol] as determined by GPC using BPA polycarbonate standards; a para-cumylphenol end-capped polycarbonate comprising structural units derived from PPPBP and BPA, having a Mw of 18,500 g/mol [±1,000 g/mol] as determined by GPC using BPA polycarbonate standards; and a para-cumylphenol end-capped polycarbonate comprising structural units derived from PPPBP and BPA, having a Mw of 17,000 g/mol [±1,000 g/mol] as determined by GPC using BPA polycarbonate standards. ### Claim 10 (depends on 1) The metallized article of claim 1, wherein the second polycarbonate and the third polycarbonate are each independently selected from: a Bisphenol A (BPA) polycarbonate having a Mw of greater than 19,800 g/mol to 22,000 g/mol [±1,000 g/mol], as determined by GPC using BPA polycarbonate standards; and a BPA polycarbonate having a Mw of 29,000 g/mol [±1,000 g/mol] to 30,000 g/mol [±1,000 g/mol], as determined by GPC using BPA polycarbonate standards. ### Claim 11 (depends on 1) The metallized article of claim 1, wherein the second polycarbonate and the third polycarbonate are each independently selected from: a linear BPA polycarbonate having a Mw of 21,700 g/mol [±1,000 g/mol], as determined by GPC using BPA polycarbonate standards; a phenol end-capped linear BPA polycarbonate having a Mw of 21,800 g/mol as determined by GPC using BPA polycarbonate standards; a PCP end-capped linear BPA polycarbonate having a Mw of 21,900 g/mol [±1,000 g/mol] as determined by GPC using BPA polycarbonate standards; a PCP end-capped linear BPA polycarbonate having a Mw of 29,900 g/mol [±1,000 g/mol] as determined by GPC using BPA polycarbonate standards; and a phenol end-capped linear BPA polycarbonate having a Mw of 30,000 g/mol [±1,000 g/mol] as determined by GPC using BPA polycarbonate standards. ### Claim 12 (depends on 1) The metallized article of claim 1, wherein the composition comprises 40 wt % to 85 wt % of the first polycarbonate; 15 wt % to 60 wt % of the second polycarbonate; 15 wt % to 45 wt % of the third polycarbonate; and 0.5 wt % to 10 wt % of the first polyester; provided that the combined wt % value of all components does not exceed 100 wt %. ### Claim 13 (depends on 1) The metallized article according to claim 1, wherein the composition is selected from the group consisting of (1), (2), and (3): (1) a composition comprising 65.00 wt % of the first polycarbonate; 29.61 wt % of the second polycarbonate; 5.00 wt % of the first polyester; 0.27 wt % of pentaerythritol tetrastearate; 0.08 wt % of phosphite stabilizer; and 0.04 wt % of hindered phenol; (2) a composition comprising 65.00 wt % of the first polycarbonate; 32.61 wt % of the second polycarbonate; 2.00 wt % of the first polyester; 0.27 wt % of pentaerythritol tetrastearate; 0.08 wt % of phosphite stabilizer; and 0.04 wt % of hindered phenol; and (3) a composition comprising 65.00 wt % of the first polycarbonate; 33.61 wt % of the second polycarbonate; 1.00 wt % of the first polyester; 0.27 wt % of pentaerythritol tetrastearate; 0.08 wt % of phosphite stabilizer; and 0.04 wt % of hindered phenol. ### Claim 14 (depends on 1) The metallized article of claim 1, wherein the composition has a heat deflection temperature of at least 160° C., measured at 0.45 MPa in accordance with ASTM D 648 or ISO 75; or wherein the composition has a melt viscosity of less than 275 Pa·s, measured in accordance with ISO 11443 at 316° C. at a shear rate of 1500 s−1. ### Claim 15 (depends on 1) The metallized article of claim 1, wherein a 3.0 mm plaque comprising the composition, metallized with a 100 nm to 150 nm thick aluminum layer using a physical vapor deposition process, and protected with a plasma-deposited siloxane hard-coat of 50 nm, has a minimum haze onset temperature of 150° C. ### Claim 16 (depends on 15) The metallized article of claim 15, wherein the plaque has a minimum haze onset temperature of 165° C.; wherein the plaque achieves a GT0 metal adhesion rating when measured in accordance with ASTM 3359/ISO 2409; or wherein the plaque exhibits 0% corrosion when stored for 240 hours at 98% relative humidity at 40° C., in accordance with DIN 50017. ### Claim 17 (depends on 1) The metallized article of claim 1, wherein a 1.5 mm plaque comprising the composition, metallized with a 100 nm to 150 nm thick aluminum layer using a physical vapor deposition process, and protected with a plasma-deposited siloxane hard-coat of 50 nm, has a minimum haze onset temperature of 150° C. ### Claim 18 (depends on 17) The metallized article of claim 17, wherein the plaque has a minimum haze onset temperature of 155° C.; wherein the plaque achieves a GT0 metal adhesion rating when measured in accordance with ASTM 3359/ISO 2409; wherein the plaque exhibits 0% corrosion when stored for 120 hours at 98% relative humidity at 40° C., in accordance with DIN 50017; or wherein the plaque exhibits 0% corrosion when stored for 240 hours at 98% relative humidity at 40° C., in accordance with DIN 50017. ### Claim 19 (depends on 1) The metallized article of claim 1, wherein a metallized part comprising the composition has an L* of 20 or less, when measured using a spectrophotometer in reflection mode with specular light excluded. ### Claim 20 (depends on 1) The metallized article of claim 1, selected from instrument panels, overhead consoles, interior trim, center consoles, panels, quarter panels, rocker panels, trim, fenders, doors, deck lids, trunk lids, hoods, bonnets, roofs, bumpers, fascia, grilles, minor housings, pillar appliques, cladding, body side moldings, wheel covers, hubcaps, door handles, spoilers, window frames, headlamp bezels, headlamps, tail lamps, tail lamp housings, tail lamp bezels, license plate enclosures, roof racks, circuit breakers, electrical and electronic housings, and running boards, or any combination thereof. ### Claim 21 (depends on 1) The metallized article of claim 1, wherein the metal layer has a thickness of 100 nanometers to 150 nanometers. ### Claim 22 (depends on 1) The metallized article of claim 1, wherein the metal layer comprises chrome, nickel, or aluminum. ### Claim 23 (depends on 1) The metallized article of claim 1, wherein the article is a molded article having a thickness of 1.5 millimeters to 3 millimeters. ### Claim 24 (depends on 1) The metallized article of claim 1, further comprising a siloxane hard-coat disposed on the metal layer. ### Claim 25 (depends on 24) The metallized article of claim 24, wherein the siloxane hard-coat has a thickness of 5 nanometers to 150 nanometers. ### Claim 26 (depends on 1) The metallized article of claim 1, wherein the thermoplastic composition further comprises 0.05 wt % to 5 wt % of tri(hydroxymethyl)aminomethan; glycerol monostearate; octadecanoic acid, 1,2,3-propanetriyl ester; or a combination comprising at least one of the foregoing. ### Claim 27 A metallized article comprising a metallized surface and a thermoplastic composition comprising: (a) 40 wt % to 85 wt % of a first polycarbonate that includes structural units derived from at least one of: wherein Ra and Rb at each occurrence are each independently halogen, C1-C12 alkyl, C1-C12 alkenyl, C3-C8 cycloalkyl, or C1-C12 alkoxy; p and q at each occurrence are each independently 0 to 4; R3 at each occurrence is independently a halogen or a C1-C6 alkyl group; c at each occurrence is independently 0 to 4; R14 at each occurrence is independently a C1-C6 alkyl, phenyl, or phenyl substituted with up to five halogens or C1-C6 alkyl groups; Rg at each occurrence is independently C1-C12 alkyl or halogen, or two Rg groups together with the carbon atoms to which they are attached form a four-, five-, or six-membered cycloalkyl group; t is 0 to 10; and x:y is 1:99 to 99:1, the first polycarbonate having a Mw of 16,000 g/mol [±1,000 g/mol] to 20,000 g/mol [±1,000 g/mol], as determined by GPC using polycarbonate standards; (b) 15 to 60 wt % of a second polycarbonate that is a Bisphenol A (BPA) polycarbonate having a Mw of greater than 19,800 g/mol to 40,000 g/mol [±1,000 g/mol], as determined by GPC using BPA polycarbonate standards; (c) optionally 15 wt % to 45 wt % of a third polycarbonate that is a BPA polycarbonate having a Mw of 17,000 g/mol [±1,000 g/mol] to 40,000 g/mol [±1,000 g/mol], as determined by GPC using BPA polycarbonate standards; provided the third polycarbonate is different from the second polycarbonate; and (d) 0.5 wt % to 10 wt % of a first polyester of formula wherein T at each occurrence is independently selected from a divalent aliphatic radical, a divalent alicyclic radical, a divalent aromatic radical, and a polyoxyalkylene radical; D at each occurrence is independently selected from a divalent aliphatic radical, a divalent alicyclic radical, and a divalent aromatic radical; and m is an integer selected from 25 to 1000; provided that the combined wt % value of all components does not exceed 100 wt %; wherein the composition has a heat deflection temperature of at least 155° C., measured at 0.45 MPa in accordance with ASTM D 648 or ISO 75; wherein the composition has a melt viscosity of less than 395 Pa s, measured in accordance with ISO 11443 at 300° C. at a shear rate of 1500 s1; wherein a molded sample of the composition has at least 60% ductility in a multi-axial impact test at 23° C., measured in accordance with ASTM D3763 or ISO 6603; and wherein the article achieves a GT0 metal adhesion rating when measured in accordance with ASTM 3359/ISO 2409. ### Claim 28 (depends on 4) The metallized article of claim 4, wherein the first polyester is selected from poly(ethylene terephthalate) (“PET”); poly(1,4-butylene terephthalate) (“PBT”); poly(ethylene naphthanoate) (“PEN”); poly(butylene naphthanoate) (“PBN”); poly(propylene terephthalate) (“PPT”); poly(1,4-cyclohexylenedimethylene) terephthalate (“PCT”); poly(1,4-cyclohexylenedimethylene 1,4-cyclohexandicarboxylate) (“PCCD”); poly(cyclohexylenedimethylene terephthalate) glycol (“PCTG”); poly(ethylene terephthalate) glycol (“PETG”); and poly(1,4-cyclohexylenedimethylene terephthalate-co-isophthalate) (“PCTA”). ### Claim 29 (depends on 27) The metallized article of claim 27, wherein the third polycarbonate is present in the thermoplastic composition.