Polymer compositions and ovenable trays, tray blanks and sheets formed therefrom

Abstract: A crystallisable polymer composition comprises from about 70 - 95% PET, from about 4% to about 29% of a core/shell polymer, from about 1 to about 5% of an aromatic polyester crystallisation rate acceleration, and optionally upto 14.5% of an aromatic polycarbonate. The compositions may be used to form sheets, tray blanks and, particularly, ovenable trays.

Description: This invention is concerned with the production of amorphous sheet which is a crystallizable polymer composition, more particularly a poly(ethylene terephthalate) polymer composition. The present invention is especially, though not exclusively, concerned with a process for making sheet which is suitable for forming ovenable plastic trays. Aluminium had previously dominated the materials for making trays in which frozen foods may be both stored and cooked in an oven. The advent of microwave ovens has created a need for non-metallic trays which may be safely heated in both conventional and microwave ovens. Such trays should retain reasonable strength and dimensional stability over a range of temperatures from about -13°C to about 230°C; they must resist embrittlement at the lower temperatures, distortion and yellowing at the higher temperatures, and should resist torsion and flexion sufficiently to allow removal of a hot tray and contents from an oven without sagging and spilling the contents. Materials such as paper and various polymers, including polyesters such as poly(ethylene terephthalate), have been used with varying degrees of success. US-A-3,960,807, has used modified poly(ethylene terephthalate) to make ovenable trays. This modified poly(ethylene terephthalate) contains a "crack-stopping" agent, which is taught for example as a non-conjugated polyolefinic material, polyamides, polycarbonates, polysulfones, certain polyesters and natural and synthetic rubbers, and a mucleating agent, which he teaches is taught as a finely divided, inorganic material or an organic material. US-A-4,463,121, teaches that the inorganic nucleating agent of US-A-3960807 may be omitted while retaining adequate crystallization times. US-A-4463121 further teaches optional use of a heat stabilizer, which is disclosed as substituted phenols, bisphenols and substituted bisphenols, aromatic amines, organic phosphates. DE-A-2440174 discloses that poly(butylene terephthalate) will increase the temperature range within which poly(ethylene terephthalate) crystallises as it cools from the molten state. However, there is no teaching of the effect upon PET impact modifier/polycarbonate compositions nor of the effect during heating from a partially quenched glossy state. US-A-4,180,494 discloses compositions containing poly(ethylene terephthalate), polycarbonate and core/shell polymer. However, these compositions do not contain poly(butylene terephthalate). The polyester resins are formed into trays by first extruding a sheet of the polyester, then stamping out a tray blank and thermoforming the blank in a tray mold. For this operation to be successful, the extruded sheet should be largely amorphous so that the tray may be readily thermoformed at temperatures up to about 200°C, but the tray composition, after thermoforming, must crystallize to form a rigid structure that will not deform at temperatures well above 200°C. Such a crystallization must be rapid, because requirements for holding the formed tray for any significant period of time at high temperatures, as in the hot tray mold or in a heater chamber, reduces the number of trays that can be produced in a given time. The crystallization must not, however, be too rapid; the composition must allow time for quenching the extruded sheet prior to crystallization; it must also allow time for re-heating to thermoforming temperatures and for the thermoforming step itself. An object of the present invention is to provide sheet made from a polymer composition which provides the requisite strength and dimensional stability over the range of about -18°C to about 230°C, and which further provides the necessary rapid but not instantaneous crystallization time, for suitability to the preparation of ovenable trays. The present invention provides a process for making amorphous sheet wherein a polymer composition which comprises, in general terms, from about 70 to 95% poly(ethylene terephthalate), from 4 to 29% of a core/shell polymer, from 1 to 5% of an aromatic polyester crystallization-rate accelerator, and up to 14.5% of an aromatic polycarbonate is made and formed into sheet 0.5 to 1.5mm thick. The weight ratio of core/shell polymer to aromatic polycarbonate, where present, is from 5:1 to 1:1. The poly(ethylene terephthalate) useful in the present invention is that having a relatively high molecular weight; such polyesters have marginally adequate toughness, but low crystallization rates accompanying the high molecular weight. A suitable molecular weight for poly(ethylene terephthalate) useful in the present invention is that indicated by an intrinsic viscosity of from 0.70 to 1.10, preferably from 0.72 to 0.95, deciliters/gram (dl/g) measured at 30°C for a solution of the polymer in 60/40 phenol/tetrachloroethane. All intrinsic viscosities given herein are measured at these conditions unless otherwise noted, and all percentages and ratios are by weight unless otherwise noted. The core/shell polymers useful in the present invention include those described in US-A-4,180,494 and US-A-,264,487. The preferred core/shell polymers are those of US-A-4,264,487. The core/shell polymers comprise (1) from 25 to 95% of a first, elastomeric phase polymerized from a monomer system comprising (a) from 75 to 99.8% of a monomer or monomer mixture which yields a rubbery polymer on polymerization, (b) from 0.1 to 5% crosslinking monomer and (c) 0 up to 5% graftlinking monomer, and (2) from 5 to 75% of an outer, vinyl rigid thermoplastic phase. The first phase is preferably graftlinked to the outer, rigid phase, either with a separate graftlinking monomer or, in the case of a conjugated diene first-phase polymer, with residual unsaturated groups in the first-phase polymer. If graftlinker is present, it is preferably present at from about 0.1 to 5%. The core/shell polymer may optionally comprise one or more additional intermediate phases; for example, an intermediate phase polymerized from 75 to 100% by weight styrene may be used. The first elastomeric phase has a high glass-transition temperature (T g ) below 0°C. The monomer or monomer mixture which yields a rubbery polymer on polymerization is preferably an alkyl acrylate, the alkyl group having from 1 to 6 carbon atoms, preferably butyl acrylate, or butadiene or other conjugated diene, as for example isoprene, and including cyclic dienes such as cyclopentadiene, or ethylene, or propylene or similar monomers producing rubbery polymers. These monomers may be mixed together in any proportions, and they may incorporate minor amounts (less than 50% by weight) of copolymerizable vinylic monomers which form rubbery or non-rubbery polymers on polymerization. A preferred copolymerizable vinylic monomer is styrene. A preferred monomer mixture comprises butadiene and styrene. It is a requirement of the crosslinking monomer that it be polyethylenically unsaturated monomer copolymerizable with the other core monomers, the reactivity of its unsaturated groups being such that essentially all of them react during the initial polymerization. The following are to be regarded as preferred crosslinking monomers: butylene diacrylate or dimethacrylate, divinyl benzene and trimethylolpropane trimethacrylate or triacrylate. It is a requirement of the graftlinking monomer that it be polyethylenically unsaturated monomer copolymerizable with the other core monomers and having sufficiently low reactivity of one or more of the unsaturated groups to allow significant residual unsaturation to remain in the core polymer subsequent to its polymerization. The following are to be regarded as preferred graftlinking monomers: allyl methacrylate and diallyl maleate, allyl methacrylate is most preferred. The outer, rigid thermoplastic phase is polymerized from a monomer system comprising from 50 to 100% by weight of alkyl methacrylate, the alkyl group having 1 to 4 carbon atoms. The core/shell polymers may be prepared using conventional emulsion polymerization techniques. The aromatic polycarbonate useful in the present invention is preferably a polycarbonate of a di(monohydroxyphenol)-substituted aliphatic hydrocarbon, wherein the hydrocarbon preferably has 2 to 4 carbon atoms. For example, it is possible to use an aromatic polycarbonate derived by the ester exchange process or phosgene process from 2,2-(4,4'-dihydroxy diphenol) propane, this aromatic polycarbonate being known as bisphenol A. Other polycarbonates may similarly be made frrom 4,4'-dihydroxy diphenol alkane, 4,4'-dihydroxy diphenol sulfone, or 4,4'dihydroxy diphenol ether, or mixtures thereof. The polycarbonate preferably has a molecular weight of from 15,000 to 100,000, and more preferably from 20,000 to 50,000. The aromatic polyester crystallization-rate accelerator is poly(alkyl terephthalate), the alkyl group containing 4 to 6 carbon atoms, more preferably poly(butylene terephthalate). The preferred poly(butylene terephthalate) has a molecular weight indicated by an intrinsic viscosity of from 0.9 to 1.2 deciliters per gram. The amount of the polyester crystallization rate modifier is from 1 to 5% by weight of the polymer composition. This range is critical in that too little crystallization-rate accelerator will allow the extruded polymer composition sheet to crystallize too slowly for a practical thermoforming operation, but excessive crystallization-rate accelerator will tend to crystallize the polymer before the quenching or thermoforming steps can be completed. To form the composition used in the present invention, the core/shell polymer, polyester crystallization-rate accelerator and optional aromatic polycarbonate are blended in any order with the polyester matrix polymer, preferably using conventional melt-blending techniques. The preferred melt-blending temperature is 260°C, which is the melting temperature of the poly(ethylene terephthalate) matrix polymer, but preferably below 285°C to reduce degradation of any of the polymer components. Blending energy and time should be sufficient to assure thorough mixing of the components. The sheet of the present invention is particularly suitable for forming ovenable trays. The ovenable trays may be prepared by forming the thin, amorphous sheet, typically from 0.5 to 1.5 mm thick, from the composition of the present invention, by extrusion or rolling, at a melt temperature above 260°C and immediately quenching the sheet to a temperature below 75°C to fix the sheet in the amorphous state, and cutting from this sheet a tray blank approximately the size of the finished tray. This blank may be reheated, preferably to 160-170°C and formed into the tray shape in a thermoforming mold. It is allowed to remain in the mold for a few seconds, typically from 5 to 10 seconds, to allow the amorphous polymer composition to crystallize, and is then removed from the mold. The formed and crystallized tray is suitable for low temperature storage as well as heating of foods. The following examples are intended to exemplify the invention. All percentages are by weight unless otherwise specified and all reagents are of good, commerical grade, except as otherwise specified. Example 1 This example illustrates preparation of poly(ethylene terephthalate), hereinafter designated PET, and preparation of tray samples from unmodified PET. The PET used in this and subsequent examples have an intrinsic viscosity, measured at 30°C in 60/40 phenol/tetra-chloroethane solution, of 0.80 deciliters per gram (dl/g). Such a PET may be made by transesterifying dimethyl terephthalate and ethylene glycol at atmospheric pressure at 160°C to 250°C using a suitable catalyst, such as cobalt acetate. After a stoichiometric amount of methanol is distilled from the reaction mixture, phosphoric acid is added as a stabilizer, and a polycondensation catalyst such as antimony trioxide is added. While agitating, the temperature of the mixture is increased to 280°C and the reaction vessel is evacuated. When the intrinsic viscosity of the polymer reaches 0.62 dl/g, the polymer is removed from the reactor in strands, and is cooled and cut into pellets. The pellets are crystallized by heating them to 125°C for 15 minutes, and the crystallized pellets are further polymerized by heating them at 200°C in a stream of nitrogen gas until the intrinsic viscosity of the resin reaches 0.80 dl/g. The pellets are then cooled and stored. Such pellets, having an intrinsic viscosity of 0.80 dl/g were dried to less than 0.005% moisture, melted at 275°C, and extruded into strands using a two-stage mixing screw. The strands were then cut into pellets. This step was added as a control, so that unmodified PET experienced the same processing history as the modified PET of subsequent excamples. The pellets were subsequently extruded into a 0.75 mm (0.030 mil) sheet using a conventional sheet die. The sheet was cooled rapidly as it left the die, so that it was largely amorphous. Strips were cut from the sheet and immersed in a silicone oil bath at a 160°C for 15, 20 or 25 seconds, as indicated in Table I, and then immediately quenched in 0°-4°C water. Samples cut from these conditioned strips were tested by differential scanning calorimetry at a temperature increase rate of 20°C per minute; the differential temperature versus time was recorded as the samples first crystallized and then melted. The areas under the differential temperature curves for the exotherm and endotherm were determined and the heats of crystallization and melting were calculated in calories per gram from the sample weight, calibration constant of the calorimeter, and the differential temperature curve areas. The difference between the endothermic and exothermic heats of melting and crystallization, divided by the theoretical heat of fusion of completely crystallized PET (27 calories/gram) yielded the percentage of crystallinity of each sample. Table I shows the results of this example. Example 2 This example illustrates the addition of a crystallization-rate accelerator to the PET matrix resin. Three parts of poly(butylene terephthalate) having an intrinsic viscosity of 1.1 dl/g (Valox * 310, from General Electric Corp.) were mixed with 97 parts of PET resin having an intrinsic viscosity of 0.80 dl/g; this mixture of pellets was thoroughly dried, melted and extruded at 275°C in an extruder equipped with a two-stage screw to form strands of the polymer blend. The strands were cut into pellets which were thoroughly dried, melted and extruded into 0.75-mm sheet as described in Example 1. The crystallinity of this sheet was determined as described in Example 1, and the results are listed in Table I. Example 3 This example illustrates an ovenable tray composition of the present invention. For this example 87 parts of the PET of Example 1, three parts of the poly(butylene terephthalate) of Example 2, 2.5 parts of bisphenol-A-based polycarbonate resin (Merlon * N-50 from Mobay Chemical Corp.), and 7.5 parts of a core/shell polymer having 80 parts core polymer of 99 parts butyl acrylate, 0.5 parts butylene glycol diacrylate and 0.5 parts allyl methacrylate and 20 parts shell polymer of methyl methacrylate were mixed and thoroughly dried. The mixture was melted and extruded at 275°C from a two-stage mixing screw extruder into strands. The strands were cut into pellets, dried and extruded into a 0.75-mm sheet; the degree of crystallization of the sheet was determined according to the procedure described in Example 1 and the results are shown in Table I. Example 4 This Example illustrates the ovenable tray composition with the poly(butylene terephthalate) omitted. The sheet was prepared according to the procedure of Example 3, the three-parts of poly(butylene terephthalate) in the blend being replaced by an equal amount of additional PET. The results of testing are shown in Table I. Example 4a This Example illustrates the ovenable tray composition with the polycarbonate omitted. The sheet was prepared according to the procedure of Example 3, the 2.5 parts of Merlon N-50 (R) polycarbonate being replaced by an equal mount of PET. Two separate samples were prepared and tested. The results of testing are shown in Table I. Example 5 This Example repeats the procedure of Example 4 using a different ratio of components. The procedure of Example 3 was repeated; the amounts of the components were 77 parts PET, 3 parts poly(butylene terephthalate) and 15 parts core/shell polymer and 5 parts polycarbonate. The results of testing are shown in Table I; they demonstrate that the crystallization rate of the composition decreases as the concentration of components that increase impact strength increases. Example 6 This example illustrates preparation of simulated ovenable trays from the compositions prepared according to the preceding examples. Samples 7.6 cm square were cut from the 0.75-mm-thick extruded sheets of polymer prepared in Examples 1 through 5. The samples were placed between two polished steel caul plates and heated in a 125°C oven for one hour to crystallize the polymer. The cooled sample from Example 1 was tested by differential scanning calorimetry as described in Example 1, and was found to have a crystallinity of 33%. Each of the samples was tested for impact strength at -18°C using a Dynatup tester. In this test a 13.6-Kg weight with a 1.27-cm-diameter impact head is dropped on the sample at 3 meters per second. An area of the sample 3.18 cm in diameter, located directly under the impact head, is unsupported. The breaking strength of the sample is measured in Joules. For this test the samples and the impact site of the tester were cooled to -18°C. Results of this test are shown in Table I. Sample from Crystallinity after Time at 160°C Impact Strength Example No. 0 sec 15 sec 20 sec 25 sec Joules 1 4.4% 5.6% 6.3% 17.0% 0.11 2 7.8 25.2 28.9 29.6 0.09 3 8.1 18.9 24.1 28.9 1.40 4 6.7 11.9 20.4 24.1 2.43 4a - - - - I.7, 0.90 5 4.8 8.8 18.9 18.5 4.86 Example 7 This example illustrates additional testing of the simulated ovenable trays of the preceding example. Dimensional stability of the sheets prepared in Example 3 and crystallized according to Example 6 was measured by cutting a 7.6-cm x 2-cm strip from the sheet and precisely measuring a 5-cm interval on the strip. The strip was heated to 200°C and held at that temperature for one hour; it showed no evidence of warping or bending. It was removed from the oven, cooled and remeasured; the 5-cm interval remained unchanged. This example shows that the components promoting impact strength do not adversely affect dimensional stability of the tray composition under conditions that simulate actual use. Example 8 This Example represents an unmodified PET such as may be made according to Example 1. This PET is Goodyear * clear tough 1006B resin from Goodyear Tire & Rubber Co., and has an intrinsic viscosity, measured according to the parameters given in Example 1, of 1.04 dl/g. The resin was extruded into strands under the following conditions: 2.5-cm Killion single-screw extruder, L/D=24/l, with two-stage, high-work, vacuum-vented screw with water on the feed throat Screw speed 60 rpm at 5.0-6.0 amperes Die pressure 700-2800 KPa Rear set temperature 260°C Middle set temperature 260°C Front set temperature 274°C Nozzle set temperature 274°C The strands were cut into pellets which were dried and extruded into sheet at the following conditions: 2.5 cm Killion single-screw extruder, L/D=24/l, with single-stage screw No vacuum, with water on the feed throat Screw speed 60 rpm at 4.8-5.5 ampere Die pressure 4100-8300 KPa Rear set temperature 288°C Middle set temperature 288°C Front set temperature 274°C Die set temperature 260°C Roller temperature Full cooling Samples were cut, crystallized by annealing for 1 hour at 125°C, and tested for impact strength as described in Example 6. The results of the tests are shown in Table II. Example 9 This example illustrates a polyester resin containing only the crystallization-rate accelerator. The procedure of Example 8 was repeated except that 3% by weight, based on the total resin weight, of the poly(butylene terephthalate) of Example 2 was mixed with the PET prior to the strand extrusion step. The results of testing are shown in Table II. Example 10 This example illustrates the polyester matrix resin with the crystallization-rate accelerator and the aromatic polycarbonate. The procedure of Example 9 was repeated, except that 2.5% by weight, based on the total resin weight, of the aromatic polycarbonate of Example 3 was mixed with the PET and poly (butylene terephthalate) prior to the strand extrusion step. The results of testing are shown in Table II. Example 11 This example illustrates the modified polyester resins of the present invention. The procedure of Example 10 was repeated, except that 7.5% by weight (based on the total resin weight) of the core/shell polymer of Example 3 was mixed with the PET, poly(butylene terephthalate) and aromatic polycarbonate prior to the strand extrusion step. The results of testing are shown in Table II. Example 12 This example illustrates another emobidment of the present invention, using a different impact modifier. The procedure of Example 11 was repeated, except that the impact modifier was replaced with the same amount of a core/shell polymer having a core polymerized from 71 parts butadiene, 3 parts styrene, 4 parts methyl methacrylate and 1 part divinylbenzene, a second stage polymerized from 11 parts styrene, and an outer shell polymerized from 11 parts methyl methacrylate and 0.1 part 1,3-butylene glycol dimethacrylate. The results of testing are shown in Table II. Sample from Dynatup Dart Impact Strength, Joules Example No. Thickness, mm 23°C -18°C 8 0.76 0.7 0.1 9 0.76 0.4 0.1 10 0.76 1.6 0.1 11 0.76 9.8 2.8 12 0.76 12.6 6.4

Claims: A process for making amorphous sheet which comprises making a polymer composition comprising, (A) from 70 to 95% by weight of poly(ethylene terephthalate) resin having an intrinsic viscosity of from 0.7 to 1.1. dl/g, measured at 30°C for a solution of the polymer in 60 / 40 phenol/tetrachloroethane; (B) from 4 to 29% by weight of core/shell polymer having (1) from 25 to 95% by weight of a first, elastomeric phase, having a Tg below 0°C polymerized from a monomer system consisting of (a) up to 99.8% by weight of a monomer or monomer mixture which yields a rubbery polymer on polymerization, (b) from 0.1 to 5% by weight of polyunsaturated crosslinking monomer other than allyl methacrylate in which substantially all the unsaturated groups react in this phase, and (c) from 0 to 5% by weight of polyunsaturated, graftlinking monomer wherein, predominantly, the units retain residual unsaturation for subsequent reaction, and (2) from 5 to 75% by weight of an outer, thermoplastic phase, polymerized from a monomer system comprising from 50 to 100% by weight alkyl methacrylate wherein the alkyl group has from 1 to 4 carbon atoms; (C) from 1 to 5% by weight of poly(alkylene terephthalate) the alkylene group having from 4 to 6 carbon atoms, in order to accelerate the rate of crystallisation when the amorphous sheet is subsequently reheated to a thermoformable state; and (D) from 0 to 14.5% of an aromatic polycarbonate, the weight ratio of core/shell polymer to the aromatic polycarbonate, where present, being from 5:1 to 1:1; rolling or extruding it, into sheet of thickness 0.5 to 1.5 mm under melt conditions above 260°C and immediately quenching to a temperature below 75°C. A process as claimed in Claim 1 where the amount of graftlinking monomer is 0.1 to 5.0%. A process as claimed in Claim 1 or 2, wherein the crystallization-rate accelerator is poly(butylene terephthalate). A process as claimed in Claim 3 wherein the poly(butylene terephthalate) has an intrinsic viscosity of from 0.9 to 1.2 dl/g measured at 30°C for a solution of the polymer in 60 / 40 phenol/tetrachloroethane. A process as claimed in any one of the preceding claims, wherein the crosslinking monomer in the first elastomeric phase is butylene glycol dimethacrylate and/or divinyl benzene. A process as claimed in any one of the preceding claims, wherein the monomer/monomer mixture which yields a rubbery polymer on polymerization comprises (a) butyl acrylate and/or (b) butadiene, optionally together with styrene in an amount of less than 50% by weight. A process as claimed in any one of the preceding claims, wherein the graftlinking monomer in the first elastomeric phase is allyl methacrylate and/or diallyl maleate. A process as claimed in any one of the preceding claims wherein the polycarbonate (c) comprises a polycarbonate of a di(monohydroxyphenol)-substituted aliphatic hydrocarbon wherein the hydrocarbon has 2 to 4 carbon atoms. A process as claimed in any of the preceding claims wherein the intrinsic viscosity of the resin (A) is from 0.72 to 0.95 dl/g. A process as claimed in any of the preceding claims for making a tray blank. A process for making an ovenable tray from amorphous sheet made by a process as claimed in any one of the preceding claims comprising reheating and thermoforming it into the final tray shape while allowing the composition from which the sheet is formed to crystallise.

Inventors: CARSON WILLIAM GILMOUR, CARSON, WILLIAM GILMOUR
Applicants: ROHM & HAAS, ROHM AND HAAS COMPANY
Application year: 1987
Main classification: C08L67
IPC codes: C08L67