WO2015051508A1 - Glass-filled polycarbonate-poly(ethylene terephthalate) composition and associated article - Google Patents

Glass-filled polycarbonate-poly(ethylene terephthalate) composition and associated article Download PDF

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WO2015051508A1
WO2015051508A1 PCT/CN2013/084896 CN2013084896W WO2015051508A1 WO 2015051508 A1 WO2015051508 A1 WO 2015051508A1 CN 2013084896 W CN2013084896 W CN 2013084896W WO 2015051508 A1 WO2015051508 A1 WO 2015051508A1
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weight percent
composition
polycarbonate
poly
weight
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PCT/CN2013/084896
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French (fr)
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Lin Chen
Hongtao Shi
Dake Dakota SHEN
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Sabic Innovative Plastics Ip B.V.
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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • Polycarbonate is an engineering plastic widely used in various applications due to its good heat resistance, impact resistance, and transparency.
  • the self-charring capability of polycarbonate during combustion makes it especially suitable for consumer electronics and electrical applications where halogen-free flame retardants are prohibited.
  • glass fiber reinforcement is added to polycarbonate.
  • the use of glass fiber increases rigidity, but also reduces melt flow and impact strength.
  • Melt flow can be improved by blending a polyester, such as poly (ethylene terephthalate), with polycarbonate, but the crystallinity of the polyester limits its content in the blend, as too much polyester causes post-molding warpage in molded parts. Also, acceptable contents of polyester do not compensate for the impact strength loss associated with glass fiber reinforcement.
  • glass-filled polycarbonate compositions exhibiting improved impact strength while maintaining high levels of rigidity, melt flow, and flame retardancy.
  • One embodiment is a composition
  • a composition comprising: 40 to 50 weight percent of a polycarbonate; 8 to 20 weight percent of a poly (ethylene terephthalate); 5 to 15 weight percent of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate; and 15 to 35 weight percent of glass fibers having a substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
  • Another embodiment is an article comprising the composition.
  • compositions comprising specific amounts of a polycarbonate, a poly(ethylene terephthalate), glass fibers, and l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate.
  • a composition comprising 40 to 50 weight percent of a polycarbonate; 8 to 20 weight percent of a poly(ethylene terephthalate); 5 to 15 weight percent of l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate; and 15 to 35 weight percent of glass fibers having a
  • composition substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
  • the composition comprises a polycarbonate.
  • Polycarbonate as used herein means a polymer or copolymer having repeating structural carbonate units of the formula
  • each R 1 can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of the formula
  • n, p, and q are each independently 0, 1, 2, 3, or 4; R a is independently at each occurrence halogen, or unsubstituted or substituted C 1-10 hydrocarbyl; and X a is a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a C 1-18 hydrocarbylene, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise one or more heteroatoms selected from halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • hydrocarbyl refers to a residue that contains only carbon and hydrogen unless it is specifically identified as "substituted hydrocarbyl".
  • the hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
  • substituted means including at least one substituent such as a halogen (i.e., F, CI, Br, I), hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, sulfide, disulfide, nitro, C 1-18 alkyl, C 1-18 alkoxyl, C 6-18 aryl, C 6-18 aryloxyl, C 7 _ 18 alkylaryl, or C 7-18 alkylaryloxyl. So, when the hydrocarbyl residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen.
  • a halogen i.e., F, CI, Br, I
  • dihydroxy compounds include the following: bisphenol compounds such as 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4- hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-l-naphthylmethane, l,2-bis(4- hydroxyphenyl)ethane, l,l-bis(4-hydroxyphenyl)-l-phenylethane, 2-(4-hydroxyphenyl)-2-(3- hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1,1 -bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane
  • 1.6- bis(4-hydroxyphenyl)-l,6-hexanedione ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol”), 3,3-bis(4- hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,
  • resorcinol substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5, 6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl
  • hydroquinone 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone,
  • dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl) propane (“bisphenol A” or "BPA”), 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3'- bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, "PPPBP”, or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one), l,l-bis(4-hydroxy-3- methylphenyl)cyclohexane (DMBPC), l,l-bis(4-hydroxy-3-methylphenyl)-3,3,5- trimethylcyclohexane (isophorone bisphenol), and combinations thereof.
  • BPA 2,2-bis(4-hydroxyphenyl) propane
  • PPPBP 3,3-bis(4-hydroxyphenyl) phthalimidine
  • 2-phenyl-3,3'- bis(4-hydroxyphenyl) phthalimidine
  • At least 90 percent of the total number of R 1 groups in the polycarbonate have the formula
  • the polycarbonate comprises or consists of bisphenol A polycarbonate resin.
  • the composition can comprise a first polycarbonate having a weight average molecular weight of 18,000 to 25,000 atomic mass units and a second polycarbonate having a weight average molecular weight of 27,000 to 35,000 atomic mass units.
  • the composition comprises the polycarbonate in an amount of 40 to 50 weight percent, based on the total weight of the composition. Within this range, the polycarbonate amount can be 43 to 49 weight percent.
  • the composition comprises poly(ethylene terephthalate), CAS Registry No. 25038-59-9.
  • the poly(ethylene terephthalate) has an intrinsic viscosity of 0.6 to 1.2 deciliter per gram, specifically 0.7 to 1.0 deciliter per gram, as measured by Ubbelohde viscometer at 25 °C in a 1 : 1 weight/weight mixture of phenol and 1,1,2,2-tetrachloroethane.
  • Poly(ethylene terephthalate) is
  • the composition comprises the poly(ethylene terephthalate) in an amount of 8 to 20 weight percent, based on the total weight of the composition. Within this range, the poly (ethylene terephthalate) amount can be 10 to 16 weight percent.
  • the composition comprises the flame retardant l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, CAS Registry No. 139189-30-3.
  • l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate instead of bisphenol A bis(diphenyl phosphate) provides the composition with a substantial and unexpected increase in impact strength.
  • Methods for synthesizing 1,3-phenylene- tetrakis(2,6-dimethylphenyl)diphosphate are known, and it is commercially available from suppliers including Daihachi Co. Ltd. and Go Yen Chemical Industrial Co. Ltd.
  • the composition comprises the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate in an amount of 5 to 15 weight percent, based on the total weight of the composition. Within this range, the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate amount can be 8 to 12 weight percent.
  • the composition comprises glass fibers.
  • Suitable glass fibers include those based on E, A, C, ECR, R, S, D, and NE glasses, as well as quartz.
  • the glass fibers have a substantially circular cross-section and are therefore distinguished from glass fibers have other cross-sectional shapes, such as those described in Japanese Patent Application Publication No. JP2012057023 A of Tai et al.
  • the glass fibers have a diameter of 2 to 30 micrometers, specifically 5 to 25 micrometers, more specifically 8 to 16 micrometers.
  • the length of the glass fibers before compounding is 2 to 7 millimeters, specifically 3 to 5 millimeters.
  • the glass fibers can, optionally, include an adhesion promoter to improve their compatibility with the polycarbonate and poly (ethylene terephthalate) resins.
  • Adhesion promoters include chromium complexes, silanes, titanates, zirco-aluminates, propylene maleic anhydride copolymers, reactive cellulose esters and the like.
  • Suitable glass fiber is commercially available from suppliers including, for example, Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.
  • the composition comprises the glass fibers in an amount of 15 to 35 weight percent, based on the total weight of the composition. Within this range, the glass fiber amount can be 25 to 35 weight percent.
  • the composition can, optionally, further comprise one or more additives, including impact modifiers, flow modifiers, fillers other than the glass fibers (provided that the below-described limit on scale-like fillers is respected), antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, UV absorbing additives, plasticizers, lubricants, mold release agents, antistatic agents, anti-fog agents, antimicrobial agents, colorants (including dyes and pigments), surface effect additives, radiation stabilizers, flame retardants other than the l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate, anti-drip agents (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), and combinations thereof.
  • additives including impact modifiers, flow modifiers, fillers other than the glass fibers (provided that the below-described limit on scale-like fillers is respected), antioxidants, heat stabilizer
  • the additives when present, are used in a total amount of less than or equal to 5 weight percent, based on the total weight of the composition. Within this limit, the additives can be used in a total amount of less than or equal to 2 weight percent, specifically less than or equal to 1.5 weight percent.
  • black colorants including black pigments and dye combinations yielding black
  • the black colorants can be used in an amount of about 0.2 to 1 weight percent, specifically about 0.3 to about 0.8 weight percent, based on the total weight of the composition.
  • composition comprises 0 to 1 weight percent of scale-like fillers.
  • Scale-like fillers include mica, glass flakes, talc, and graphite. In some embodiments, the composition excludes scale-like fillers. The use of scale-like fillers can cause undesirable reductions in stiffness and ductility.
  • the composition can, optionally, exclude impact modifiers.
  • the exclusion of impact modifiers is facilitated by the surprising improvement in impact strength associated with the use of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate.
  • Impact modifiers include, for example, natural rubber, fluoroelastomers, ethylene-propylene rubber (EPR), ethylene-butene rubber, ethylene -propylene-diene monomer rubber (EPDM), acrylate rubbers, hydrogenated nitrile rubber (HNBR) silicone elastomers, styrene-butadiene-styrene block copolymers (SBS), styrene-butadiene rubber (SBR), styrene-(ethylene-butene)-styrene block copolymers (SEBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene- diene-styrene (AES), styrene-isoprene-styrene block copolymers (SIS), styrene-(ethylene- propylene)-styrene block copolymers (SEPS), methyl me
  • composition in a specific embodiment, it comprises 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly(ethylene terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers.
  • the polycarbonate comprises repeat units having the formula
  • the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram; the glass fibers have a diameter of 8 to 16 micrometers; the composition comprises 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly (ethylene
  • the composition excludes scale-like fillers.
  • composition is useful for molding articles, including television bezels and notebook computer covers. Suitable methods of forming such articles include single layer and multilayer sheet extrusion, injection molding, blow molding, film extrusion, profile extrusion, pultrusion, compression molding, thermoforming, pressure forming, hydroforming, vacuum forming, and the like. Combinations of the foregoing article fabrication methods can be used.
  • the invention includes at least the following embodiments.
  • Embodiment 1 A composition comprising: 40 to 50 weight percent of a polycarbonate; 8 to 20 weight percent of a poly (ethylene terephthalate); 5 to 15 weight percent of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate; and 15 to 35 weight percent of glass fibers having a substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
  • Embodiment 2 The composition of embodiment 1, wherein the
  • polycarbonate comprises repeat units having the formula
  • Embodiment 3 The composition of embodiment 2, wherein R 1 is the residue of a dihydroxy compound having the formula
  • n, p, and q are each independently 0, 1, 2, 3, or 4;
  • R a is independently at each occurrence halogen, or unsubstituted or substituted C 1-10 hydrocarbyl;
  • X is a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or C 1-18 hydrocarbylene, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise one or more heteroatoms selected from halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • Embodiment 4 The composition of embodiment 2, wherein at least 90 percent of the total number of R 1 roups have the formula
  • Embodiment 5 The composition of any of embodiments 1-4, comprising a first polycarbonate having a weight average molecular weight of 18,000 to 25,000 atomic mass units and a second polycarbonate having a weight average molecular weight of 27,000 to 35,000 atomic mass units.
  • Embodiment 6 The composition of any of embodiments 1-5, wherein the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram as measured by Ubbelohde viscometer at 25 °C in a 1 : 1 weight/weight mixture of phenol and 1 , 1 ,2,2-tetrachloroethane.
  • Embodiment 7 The composition of any of embodiments 1-6, wherein the glass fibers have a diameter of 8 to 16 micrometers.
  • Embodiment 8 The composition of any of embodiments 1-7, comprising 25 to 35 weight percent of the glass fibers.
  • Embodiment 9 The composition of any of embodiments 1-8, excluding scalelike fillers.
  • Embodiment 10 The composition of any of embodiments 1-9, excluding impact modifiers.
  • Embodiment 11 The composition of any of embodiments 1-10, comprising 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly(ethylene terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers.
  • Embodiment 12 The composition of embodiment 1, wherein the
  • polycarbonate comprises repeat units having the formula
  • the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram; wherein the glass fibers have a diameter of 8 to 16 micrometers; wherein the composition comprises 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly(ethylene terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers; and wherein the composition excludes scale-like fillers.
  • Embodiment 13 An article comprising a composition comprising: 40 to 50 weight percent of a polycarbonate; 8 to 20 weight percent of a poly(ethylene terephthalate); 5 to 15 weight percent of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate; and 15 to 35 weight percent of glass fibers having a substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
  • Embodiment 14 The article of embodiment 13, wherein the article is a television bezel.
  • Embodiment 15 The article of embodiment 13 or 14, wherein the
  • polycarbonate comprises repeat units having the formula
  • the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram; wherein the glass fibers have a diameter of 8 to 16 micrometers; wherein the composition comprises 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly(ethylene terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers; and wherein the composition excludes scale-like fillers.
  • PCI Bisphenol A polycarbonate resin (CAS Reg. No. 25971-63-5) having a weight average molecular weight of about 22,000 atomic mass units; obtained as LEX ANTM ML5221 Resin from SABIC Innovative Plastics.
  • PC2 Bisphenol A polycarbonate resin (CAS Reg. No. 25971-63-5) having a weight average molecular weight of about 30,000 atomic mass units; obtained as LEX ANTM ML5721 Resin from SABIC Innovative Plastics.
  • PET Polyethylene terephthalate resin (CAS Reg. No. 25038-59-9)
  • DMPPD Tetrakis(2,6-dimethylphenyl) m-phenylene diphosphate
  • BPADP Bisphenol A bis(diphenyl phosphate) (CAS Reg. No. 5945-33-5), obtained as CR741 from Daihachi Co. Ltd.
  • Additives A mixture of monozinc phosphate, mold release agent, antidripping agent, hindered phenol antioxidant, phosphite antioxidant, carbon black pigment, and auxiliary colorants.
  • compositions were prepared as follows. All components except glass fiber were dry-blended, then added to the feed throat of a Toshiba SE37 twin-screw extruder having a 37 millimeter screw diameter and operating at 200 rotations per minute. Glass fibers were added downstream.
  • the extruder temperature profile from feed throat to die was 100 °C / 200 °C / 250 °C / 250 °C / 260 °C / 260 °C / 260 °C / 265 °C / 265 °C / 260 °C.
  • the extruded was pelletized and dried for six hours at 120° C before molding.
  • Test articles were prepared in accordance with ASTM standards using a FANUC S2000i 150 ton injection molding machine operating with a barrel temperature of 260 °C and a mold temperature of 80 °C.
  • MFR Melt flow rate
  • Flexural modulus (Flex. Mod.) values (express in units of megapascals), were determined at 23 °C according to ASTM D790-07 using test bars having dimensions 127 x 12.7 x 3.2 millimeters and a test rate of 1.3 millimeters per minute.
  • Notched Izod impact strength (Nil) values (expressed in units of joules/meter), were determined at 23 °C according to ASTM D 256-10 using test bars having dimensions 63.5 x 12.7 x 3.2 millimeters.
  • Heat deflection temperature (HDT) values (expressed in °C), were determined according to ASTM D 648-07 using test bars having dimensions 127 x 12.7 x 3.2 millimeters, and a loading fiber stress of 1.82 megapascals.
  • first afterflame time, tl was noted.
  • the flame was then reapplied and removed, and the time required for the bar to self-extinguish (second afterflame time, t2) and the post-flame glowing time (afterglow time, t3) were noted.
  • the afterflame times tl and t2 for each individual specimen must have been less than or equal to 10 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 50 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + t3) must have been less than or equal to 30 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops.
  • the afterflame times tl and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 250 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops.
  • the afterflame times tl and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 250 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; but the cotton indicator can have been ignited by flaming particles or drops. Compositions not achieving a rating of V-2 were considered to have failed.
  • Example 1 uses tetrakis(2,6- dimethylphenyl) m-phenylene diphosphate (DMPPD), and Comparative Example 1 uses Bisphenol A bis(diphenyl phosphate) (BPADP). The property results for the two
  • Example 1 with DMPPD has a substantially higher notched Izod impact strength.

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Abstract

A composition includes specific amounts of a polycarbonate, poly(ethylene terephthalate), glass fibers, and the flame retardant 1,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate. Relative to a composition with the related phosphate ester flame retardant bisphenol A bis(diphenyl phosphate), the inventive composition provides improved impact strength while maintaining stiffness, melt flow, heat resistance, and flame retardancy. The composition is useful for fabricating articles including television bezels and notebook computer covers.

Description

GLASS-FILLED POLYCARBONATE-POLY(ETHYLENE TEREPHTHALATE) COMPOSITION AND ASSOCIATED ARTICLE
BACKGROUND OF THE INVENTION
[0001] Polycarbonate is an engineering plastic widely used in various applications due to its good heat resistance, impact resistance, and transparency. The self-charring capability of polycarbonate during combustion makes it especially suitable for consumer electronics and electrical applications where halogen-free flame retardants are prohibited. In some specific applications where rigidity is required, such as notebook computer covers and television bezels, glass fiber reinforcement is added to polycarbonate. The use of glass fiber increases rigidity, but also reduces melt flow and impact strength. Melt flow can be improved by blending a polyester, such as poly (ethylene terephthalate), with polycarbonate, but the crystallinity of the polyester limits its content in the blend, as too much polyester causes post-molding warpage in molded parts. Also, acceptable contents of polyester do not compensate for the impact strength loss associated with glass fiber reinforcement. There remains a need for glass-filled polycarbonate compositions exhibiting improved impact strength while maintaining high levels of rigidity, melt flow, and flame retardancy.
BRIEF SUMMARY OF EMBODIMENTS OF THE INVENTION
[0002] One embodiment is a composition comprising: 40 to 50 weight percent of a polycarbonate; 8 to 20 weight percent of a poly (ethylene terephthalate); 5 to 15 weight percent of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate; and 15 to 35 weight percent of glass fibers having a substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
[0003] Another embodiment is an article comprising the composition.
[0004] These and other embodiments are described in detail below.
DETAILED DESCRIPTION OF THE INVENTION
[0005] The present inventors have determined that an improved balance of rigidity, impact strength, melt flow, and flame retardancy is provided by a composition comprising specific amounts of a polycarbonate, a poly(ethylene terephthalate), glass fibers, and l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate. Thus, one embodiment is a composition comprising 40 to 50 weight percent of a polycarbonate; 8 to 20 weight percent of a poly(ethylene terephthalate); 5 to 15 weight percent of l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate; and 15 to 35 weight percent of glass fibers having a
substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
[0006] The composition comprises a polycarbonate. "Polycarbonate" as used herein means a polymer or copolymer having repeating structural carbonate units of the formula
Figure imgf000003_0001
wherein at least 60 percent of the total number of R1 groups are aromatic. Specifically, each R1 can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of the formula
Figure imgf000003_0002
wherein n, p, and q are each independently 0, 1, 2, 3, or 4; Ra is independently at each occurrence halogen, or unsubstituted or substituted C1-10 hydrocarbyl; and Xa is a single bond, -0-, -S-, -S(O)-, -S(0)2-, -C(O)-, or a C1-18 hydrocarbylene, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise one or more heteroatoms selected from halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. As used herein, the term
"hydrocarbyl", whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen unless it is specifically identified as "substituted hydrocarbyl". The hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. As used herein, "substituted" means including at least one substituent such as a halogen (i.e., F, CI, Br, I), hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, sulfide, disulfide, nitro, C1-18 alkyl, C1-18 alkoxyl, C6-18 aryl, C6-18 aryloxyl, C7_ 18 alkylaryl, or C7-18 alkylaryloxyl. So, when the hydrocarbyl residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen.
[0007] Some illustrative examples of specific dihydroxy compounds include the following: bisphenol compounds such as 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4- hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-l-naphthylmethane, l,2-bis(4- hydroxyphenyl)ethane, l,l-bis(4-hydroxyphenyl)-l-phenylethane, 2-(4-hydroxyphenyl)-2-(3- hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1,1 -bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis (4-hydroxyphenyl)isobutene, 1 , 1 -bis (4- hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4- hydroxyphenyl)adamantane, alpha,alpha'-bis(4-hydroxyphenyl)toluene,
bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3- ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3- isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2- bis(4-hydroxyphenyl)hexafluoropropane, l,l-dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1 , 1 -dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1 , 1 -dichloro-2,2-bis(5-phenoxy-4- hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,
1.6- bis(4-hydroxyphenyl)-l,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4- hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,
2.7- dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,
3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole; resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5, 6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl
hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone,
2,3,5, 6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, and 2,3,5,6-tetrabromo hydroquinone.
[0008] Specific dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl) propane ("bisphenol A" or "BPA"), 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3'- bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, "PPPBP", or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one), l,l-bis(4-hydroxy-3- methylphenyl)cyclohexane (DMBPC), l,l-bis(4-hydroxy-3-methylphenyl)-3,3,5- trimethylcyclohexane (isophorone bisphenol), and combinations thereof.
[0009] In some embodiments, at least 90 percent of the total number of R1 groups in the polycarbonate have the formula
Figure imgf000005_0001
In some embodiments, the polycarbonate comprises or consists of bisphenol A polycarbonate resin.
[0010] More than one polycarbonate can be used. For example, the composition can comprise a first polycarbonate having a weight average molecular weight of 18,000 to 25,000 atomic mass units and a second polycarbonate having a weight average molecular weight of 27,000 to 35,000 atomic mass units.
[0011] Methods of forming polycarbonates are known, and many are commercially available from suppliers including SABIC Innovative Plastics, Bayer MaterialScience, and Mitsubishi Chemical Corp.
[0012] The composition comprises the polycarbonate in an amount of 40 to 50 weight percent, based on the total weight of the composition. Within this range, the polycarbonate amount can be 43 to 49 weight percent.
[0013] In addition to the polycarbonate, the composition comprises poly(ethylene terephthalate), CAS Registry No. 25038-59-9. In some embodiments, the poly(ethylene terephthalate) has an intrinsic viscosity of 0.6 to 1.2 deciliter per gram, specifically 0.7 to 1.0 deciliter per gram, as measured by Ubbelohde viscometer at 25 °C in a 1 : 1 weight/weight mixture of phenol and 1,1,2,2-tetrachloroethane. Poly(ethylene terephthalate) is
commercially available from suppliers including DuPont, DAK Americas LLC, and Foshan Shunde Shunyan Plastic Co., Ltd.
[0014] The composition comprises the poly(ethylene terephthalate) in an amount of 8 to 20 weight percent, based on the total weight of the composition. Within this range, the poly (ethylene terephthalate) amount can be 10 to 16 weight percent.
[0015] In addition to the polycarbonate and the poly(ethylene terephthalate), the composition comprises the flame retardant l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, CAS Registry No. 139189-30-3. As demonstrated in the working examples below, using l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate instead of bisphenol A bis(diphenyl phosphate) provides the composition with a substantial and unexpected increase in impact strength. Methods for synthesizing 1,3-phenylene- tetrakis(2,6-dimethylphenyl)diphosphate are known, and it is commercially available from suppliers including Daihachi Co. Ltd. and Go Yen Chemical Industrial Co. Ltd.
[0016] The composition comprises the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate in an amount of 5 to 15 weight percent, based on the total weight of the composition. Within this range, the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate amount can be 8 to 12 weight percent.
[0017] In addition to the polycarbonate, the poly(ethylene terephthalate), and the l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate, the composition comprises glass fibers. Suitable glass fibers include those based on E, A, C, ECR, R, S, D, and NE glasses, as well as quartz. The glass fibers have a substantially circular cross-section and are therefore distinguished from glass fibers have other cross-sectional shapes, such as those described in Japanese Patent Application Publication No. JP2012057023 A of Tai et al. In some embodiments, the glass fibers have a diameter of 2 to 30 micrometers, specifically 5 to 25 micrometers, more specifically 8 to 16 micrometers. In some embodiments, the length of the glass fibers before compounding is 2 to 7 millimeters, specifically 3 to 5 millimeters. The glass fibers can, optionally, include an adhesion promoter to improve their compatibility with the polycarbonate and poly (ethylene terephthalate) resins. Adhesion promoters include chromium complexes, silanes, titanates, zirco-aluminates, propylene maleic anhydride copolymers, reactive cellulose esters and the like. Suitable glass fiber is commercially available from suppliers including, for example, Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.
[0018] The composition comprises the glass fibers in an amount of 15 to 35 weight percent, based on the total weight of the composition. Within this range, the glass fiber amount can be 25 to 35 weight percent.
[0019] The composition can, optionally, further comprise one or more additives, including impact modifiers, flow modifiers, fillers other than the glass fibers (provided that the below-described limit on scale-like fillers is respected), antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, UV absorbing additives, plasticizers, lubricants, mold release agents, antistatic agents, anti-fog agents, antimicrobial agents, colorants (including dyes and pigments), surface effect additives, radiation stabilizers, flame retardants other than the l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate, anti-drip agents (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), and combinations thereof. In general, the additives, when present, are used in a total amount of less than or equal to 5 weight percent, based on the total weight of the composition. Within this limit, the additives can be used in a total amount of less than or equal to 2 weight percent, specifically less than or equal to 1.5 weight percent. When using the composition to form television bezels, black colorants (including black pigments and dye combinations yielding black) are particularly useful. When present, the black colorants can be used in an amount of about 0.2 to 1 weight percent, specifically about 0.3 to about 0.8 weight percent, based on the total weight of the composition.
[0020] The composition comprises 0 to 1 weight percent of scale-like fillers.
Scale-like fillers include mica, glass flakes, talc, and graphite. In some embodiments, the composition excludes scale-like fillers. The use of scale-like fillers can cause undesirable reductions in stiffness and ductility.
[0021] The composition can, optionally, exclude impact modifiers. The exclusion of impact modifiers is facilitated by the surprising improvement in impact strength associated with the use of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate. Impact modifiers include, for example, natural rubber, fluoroelastomers, ethylene-propylene rubber (EPR), ethylene-butene rubber, ethylene -propylene-diene monomer rubber (EPDM), acrylate rubbers, hydrogenated nitrile rubber (HNBR) silicone elastomers, styrene-butadiene-styrene block copolymers (SBS), styrene-butadiene rubber (SBR), styrene-(ethylene-butene)-styrene block copolymers (SEBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene- diene-styrene (AES), styrene-isoprene-styrene block copolymers (SIS), styrene-(ethylene- propylene)-styrene block copolymers (SEPS), methyl methacrylate-butadiene-styrene block copolymers (MBS), and high rubber graft (HRG).
[0022] In a specific embodiment of the composition, it comprises 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly(ethylene terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers.
[0023] In another specific embodiment of the composition, the polycarbonate comprises repeat units having the formula
Figure imgf000007_0001
wherein at least 90 percent of the total number of R groups have the formula
Figure imgf000008_0001
the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram; the glass fibers have a diameter of 8 to 16 micrometers; the composition comprises 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly (ethylene
terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers; and the composition excludes scale-like fillers.
[0024] The composition is useful for molding articles, including television bezels and notebook computer covers. Suitable methods of forming such articles include single layer and multilayer sheet extrusion, injection molding, blow molding, film extrusion, profile extrusion, pultrusion, compression molding, thermoforming, pressure forming, hydroforming, vacuum forming, and the like. Combinations of the foregoing article fabrication methods can be used.
[0025] All of the compositional variations described above apply as well to the article comprising the composition.
[0026] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Each range disclosed herein constitutes a disclosure of any point or sub-range lying within the disclosed range.
[0027] The invention includes at least the following embodiments.
[0028] Embodiment 1: A composition comprising: 40 to 50 weight percent of a polycarbonate; 8 to 20 weight percent of a poly (ethylene terephthalate); 5 to 15 weight percent of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate; and 15 to 35 weight percent of glass fibers having a substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
[0029] Embodiment 2: The composition of embodiment 1, wherein the
polycarbonate comprises repeat units having the formula
Figure imgf000008_0002
wherein at least 60 percent of the total number of R groups are aromatic.
[0030] Embodiment 3: The composition of embodiment 2, wherein R1 is the residue of a dihydroxy compound having the formula
Figure imgf000009_0001
wherein n, p, and q are each independently 0, 1, 2, 3, or 4; Ra is independently at each occurrence halogen, or unsubstituted or substituted C1-10 hydrocarbyl; and X is a single bond, -0-, -S-, -S(O)-, -S(0)2-, -C(O)-, or C1-18 hydrocarbylene, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise one or more heteroatoms selected from halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
[0031] Embodiment 4: The composition of embodiment 2, wherein at least 90 percent of the total number of R1 roups have the formula
Figure imgf000009_0002
[0032] Embodiment 5: The composition of any of embodiments 1-4, comprising a first polycarbonate having a weight average molecular weight of 18,000 to 25,000 atomic mass units and a second polycarbonate having a weight average molecular weight of 27,000 to 35,000 atomic mass units.
[0033] Embodiment 6: The composition of any of embodiments 1-5, wherein the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram as measured by Ubbelohde viscometer at 25 °C in a 1 : 1 weight/weight mixture of phenol and 1 , 1 ,2,2-tetrachloroethane.
[0034] Embodiment 7: The composition of any of embodiments 1-6, wherein the glass fibers have a diameter of 8 to 16 micrometers.
[0035] Embodiment 8: The composition of any of embodiments 1-7, comprising 25 to 35 weight percent of the glass fibers.
[0036] Embodiment 9: The composition of any of embodiments 1-8, excluding scalelike fillers.
[0037] Embodiment 10: The composition of any of embodiments 1-9, excluding impact modifiers.
[0038] Embodiment 11: The composition of any of embodiments 1-10, comprising 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly(ethylene terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers.
[0039] Embodiment 12: The composition of embodiment 1, wherein the
polycarbonate comprises repeat units having the formula
Figure imgf000010_0001
wherein at least 90 percent of the total number of R groups have the formula
Figure imgf000010_0002
wherein the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram; wherein the glass fibers have a diameter of 8 to 16 micrometers; wherein the composition comprises 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly(ethylene terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers; and wherein the composition excludes scale-like fillers.
[0040] Embodiment 13: An article comprising a composition comprising: 40 to 50 weight percent of a polycarbonate; 8 to 20 weight percent of a poly(ethylene terephthalate); 5 to 15 weight percent of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate; and 15 to 35 weight percent of glass fibers having a substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
[0041] Embodiment 14: The article of embodiment 13, wherein the article is a television bezel.
[0042] Embodiment 15: The article of embodiment 13 or 14, wherein the
polycarbonate comprises repeat units having the formula
Figure imgf000010_0003
wherein at least 90 percent of the total number of R groups have the formula
Figure imgf000011_0001
wherein the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram; wherein the glass fibers have a diameter of 8 to 16 micrometers; wherein the composition comprises 43 to 49 weight percent of the polycarbonate, 10 to 16 weight percent of the poly(ethylene terephthalate), 8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and 25 to 35 weight percent of the glass fibers; and wherein the composition excludes scale-like fillers.
[0043] The invention is further illustrated by the following non-limiting examples. EXAMPLE 1, COMPARATIVE EXAMPLE 1
[0044] Components used to prepare the compositions are summarized in Table 1.
Table 1
Component Description
PCI Bisphenol A polycarbonate resin (CAS Reg. No. 25971-63-5) having a weight average molecular weight of about 22,000 atomic mass units; obtained as LEX AN™ ML5221 Resin from SABIC Innovative Plastics.
PC2 Bisphenol A polycarbonate resin (CAS Reg. No. 25971-63-5) having a weight average molecular weight of about 30,000 atomic mass units; obtained as LEX AN™ ML5721 Resin from SABIC Innovative Plastics.
PET Polyethylene terephthalate) resin (CAS Reg. No. 25038-59-9)
having an intrinsic viscosity of 0.80 to 0.86 deciliter per gram measured by Ubbelohde viscometer at 25 °C in a 1 : 1 weight/weight mixture of phenol and 1,1,2,2-tetrachloroethane; obtained as
BG-03-80 from Foshan Shunde Shunyan Plastic Co., Ltd.
DMPPD Tetrakis(2,6-dimethylphenyl) m-phenylene diphosphate (CAS Reg.
No. 139189-30-3); obtained as PX200 from Daihachi Co. Ltd.
BPADP Bisphenol A bis(diphenyl phosphate) (CAS Reg. No. 5945-33-5), obtained as CR741 from Daihachi Co. Ltd.
Glass fiber Surface-treated glass fiber having a diameter of about 13 micrometers and a pre-compounding length of about 4 millimeters; obtained as ECS303A from Chongqing Polycomp International Corp.
Additives A mixture of monozinc phosphate, mold release agent, antidripping agent, hindered phenol antioxidant, phosphite antioxidant, carbon black pigment, and auxiliary colorants.
[0045] Compositions were prepared as follows. All components except glass fiber were dry-blended, then added to the feed throat of a Toshiba SE37 twin-screw extruder having a 37 millimeter screw diameter and operating at 200 rotations per minute. Glass fibers were added downstream. The extruder temperature profile from feed throat to die was 100 °C / 200 °C / 250 °C / 250 °C / 260 °C / 260 °C / 260 °C / 265 °C / 265 °C / 260 °C. The extruded was pelletized and dried for six hours at 120° C before molding. Test articles were prepared in accordance with ASTM standards using a FANUC S2000i 150 ton injection molding machine operating with a barrel temperature of 260 °C and a mold temperature of 80 °C.
[0046] The following procedures were used for property testing. Melt flow rate (MFR) values (expressed in units of grams per 10 minutes) were determined according to ASTM D 1238-04 using Procedure B, 260 °C, and 2.16 kilogram load. Flexural modulus (Flex. Mod.) values (express in units of megapascals), were determined at 23 °C according to ASTM D790-07 using test bars having dimensions 127 x 12.7 x 3.2 millimeters and a test rate of 1.3 millimeters per minute. Notched Izod impact strength (Nil) values (expressed in units of joules/meter), were determined at 23 °C according to ASTM D 256-10 using test bars having dimensions 63.5 x 12.7 x 3.2 millimeters. Heat deflection temperature (HDT) values (expressed in °C), were determined according to ASTM D 648-07 using test bars having dimensions 127 x 12.7 x 3.2 millimeters, and a loading fiber stress of 1.82 megapascals.
[0047] Flame retardancy of injection molded flame bars was determined according to Underwriter's Laboratory Bulletin 94 "Tests for Flammability of Plastic Materials, UL 94", 20 mm Vertical Burning Flame Test. Before testing, flame bars with a thickness of 1.5 millimeters were conditioned at 23°C and 50% relative humidity for at least 48 hours. In the UL 94 20 mm Vertical Burning Flame Test, a set of five flame bars was tested. For each bar, a flame was applied to the bar then removed, and the time required for the bar to
self-extinguish (first afterflame time, tl) was noted. The flame was then reapplied and removed, and the time required for the bar to self-extinguish (second afterflame time, t2) and the post-flame glowing time (afterglow time, t3) were noted. To achieve a rating of V-0, the afterflame times tl and t2 for each individual specimen must have been less than or equal to 10 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 50 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + t3) must have been less than or equal to 30 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops. To achieve a rating of V-1, the afterflame times tl and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 250 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; and the cotton indicator cannot have been ignited by flaming particles or drops. To achieve a rating of V-2, the afterflame times tl and t2 for each individual specimen must have been less than or equal to 30 seconds; and the total afterflame time for all five specimens (tl plus t2 for all five specimens) must have been less than or equal to 250 seconds; and the second afterflame time plus the afterglow time for each individual specimen (t2 + t3) must have been less than or equal to 60 seconds; and no specimen can have flamed or glowed up to the holding clamp; but the cotton indicator can have been ignited by flaming particles or drops. Compositions not achieving a rating of V-2 were considered to have failed.
[0048] Compositions and results are summarized in Table 2, where component amounts are in weight percent based on the total weight of the composition. Example 1 and Comparative Example 2 differ only in the flame retardant type. Example 1 uses tetrakis(2,6- dimethylphenyl) m-phenylene diphosphate (DMPPD), and Comparative Example 1 uses Bisphenol A bis(diphenyl phosphate) (BPADP). The property results for the two
compositions are similar except that Example 1 with DMPPD has a substantially higher notched Izod impact strength.
Table 2
Example 1 Comparative Example 1
COMPOSITIONS
PCI 46.18 46.18
PC2 0.01 0.01
PET 12.43 12.43
DMPPD 9.95 0.00
BPADP 0.00 9.95 Glass Fiber 29.84 29.84
Additives 1.60 1.60
PROPERTIES
MFR (g/10 min) 40 42
Flex. Mod. (MPa) 8600 8900
Nil (J/m) 88 54
HDT (°C) 90 91
UL 94 Rating V-0 V-0

Claims

A composition comprising:
40 to 50 weight percent of a polycarbonate;
8 to 20 weight percent of a poly (ethylene terephthalate);
5 to 15 weight percent of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate; and
15 to 35 weight percent of glass fibers having a substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and
wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
The composition of claim 1, wherein the polycarbonate comprises repeat units having the formula
Figure imgf000015_0001
wherein at least 60 percent of the total number of R groups are aromatic.
3. The composition of claim 2, wherein R1 is the residue of a dihydroxy compound having the formula
Figure imgf000015_0002
wherein n, p, and q are each independently 0, 1, 2, 3, or 4; Ra is independently at each occurrence halogen, or unsubstituted or substituted C1-10 hydrocarbyl; and X is a single bond, -0-, -S-, -S(O)-, -S(0)2-, -C(O)-, or C1-18 hydrocarbylene, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise one or more heteroatoms selected from halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
4. The composition of claim 2, wherein at least 90 percent of the total number of R1 groups have the formula
Figure imgf000015_0003
5. The composition of claim 1, comprising a first polycarbonate having a weight average molecular weight of 18,000 to 25,000 atomic mass units and a second polycarbonate having a weight average molecular weight of 27,000 to 35,000 atomic mass units.
6. The composition of claim 1, wherein the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram as measured by Ubbelohde viscometer at 25 °C in a 1:1 weight/weight mixture of phenol and 1,1,2,2-tetrachloroethane.
7. The composition of claim 1, wherein the glass fibers have a diameter of 8 to 16 micrometers.
8. The composition of any of claims 1-7, comprising 25 to 35 weight percent of the glass fibers.
9. The composition of any of claims 1-7, excluding scale-like fillers.
10. The composition of any of claims 1-7, excluding impact modifiers.
11. The composition of any of claims 1-7, comprising
43 to 49 weight percent of the polycarbonate,
10 to 16 weight percent of the poly (ethylene terephthalate),
8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate, and
25 to 35 weight percent of the glass fibers.
12. The composition of claim 1,
wherein the polycarbonate comprises repeat units having the formula
Figure imgf000016_0001
wherein at least 90 percent of the total number of R groups have the formula
Figure imgf000016_0002
wherein the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram;
wherein the glass fibers have a diameter of 8 to 16 micrometers;
wherein the composition comprises
43 to 49 weight percent of the polycarbonate,
10 to 16 weight percent of the poly (ethylene terephthalate),
8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and
25 to 35 weight percent of the glass fibers; and wherein the composition excludes scale-like fillers.
13. An article comprising a composition comprising:
40 to 50 weight percent of a polycarbonate;
8 to 20 weight percent of a poly (ethylene terephthalate);
5 to 15 weight percent of l,3-phenylene-tetrakis(2,6-dimethylphenyl)diphosphate; and
15 to 35 weight percent of glass fibers having a substantially circular cross-section; wherein all weight percent values are based on the total weight of the composition; and
wherein the composition comprises 0 to 1 weight percent of scale-like fillers.
14. The article of claim 13, wherein the article is a television bezel.
15. The article of claim 13 or 14,
wherein the polycarbonate comprises repeat units having the formula
Figure imgf000017_0001
wherein at least 90 ercent of the total number of R groups have the formula
Figure imgf000017_0002
wherein the poly(ethylene terephthalate) has an intrinsic viscosity of 0.7 to 1.0 deciliter per gram;
wherein the glass fibers have a diameter of 8 to 16 micrometers;
wherein the composition comprises
43 to 49 weight percent of the polycarbonate,
10 to 16 weight percent of the poly (ethylene terephthalate),
8 to 12 weight percent of the l,3-phenylene-tetrakis(2,6- dimethylphenyl)diphosphate, and
25 to 35 weight percent of the glass fibers; and
wherein the composition excludes scale-like fillers.
PCT/CN2013/084896 2013-10-09 2013-10-09 Glass-filled polycarbonate-poly(ethylene terephthalate) composition and associated article WO2015051508A1 (en)

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JPH0333153A (en) * 1989-06-30 1991-02-13 Sumitomo Bakelite Co Ltd Thermoplastic resin composition
CN101104731A (en) * 2006-07-14 2008-01-16 上海普利特复合材料有限公司 Halogen-free anti-flaming polycarbonate/thermoplastic polyester resin composition
KR20080062975A (en) * 2006-12-30 2008-07-03 주식회사 삼양사 A composition having superior flame retarding property and an article prepared therefrom
US20090118402A1 (en) * 2006-04-14 2009-05-07 Cheil Industries Inc. Scratch-Resistant Flameproof Thermoplastic Resin Composition
CN103214808A (en) * 2012-01-18 2013-07-24 柯尼卡美能达商用科技株式会社 Copier or printer external part using halogen-free flame-retardant resin composition containing regenerated PC and regenerated PET

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0333153A (en) * 1989-06-30 1991-02-13 Sumitomo Bakelite Co Ltd Thermoplastic resin composition
US20090118402A1 (en) * 2006-04-14 2009-05-07 Cheil Industries Inc. Scratch-Resistant Flameproof Thermoplastic Resin Composition
CN101104731A (en) * 2006-07-14 2008-01-16 上海普利特复合材料有限公司 Halogen-free anti-flaming polycarbonate/thermoplastic polyester resin composition
KR20080062975A (en) * 2006-12-30 2008-07-03 주식회사 삼양사 A composition having superior flame retarding property and an article prepared therefrom
CN103214808A (en) * 2012-01-18 2013-07-24 柯尼卡美能达商用科技株式会社 Copier or printer external part using halogen-free flame-retardant resin composition containing regenerated PC and regenerated PET

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