Multilayer film containing amorphous nylon copolymer

Abstract: Novel orientable single and multilayer thermoplastic flexible films utilizing blends comprising an amorphous nylon copolymer such as nylon 6I/6T and a nylon copolyamide having a melting point of at least about 145°C having improved processability, shrinkage and optical properties.

Description: Background of the Invention The present invention relates to multilayer films and casings containing nylon resin blends for use in packaging. In particular, the invention relates to multilayer films and casings made thereof which are suitable for packaging food products such as fresh meat, processed meat, cheese and sausages. Nylon is the generic name for a family of polyamide polymers characterized by the presence of the amide group-CONH. The utility of nylon compositions and products are well known with everyday examples including usage in packaging, brushes, and tires, as synthetic films, fibers, plastics and molding resins. Thermoplastic flexible films are used in a wide variety of applications including bags (e.g. for merchandise, leaves, garbage) wrappings for industrial packaging, in electrical and electronic uses, as communications media substrates, adhesive coated products such as tapes and labels, medical packaging, and food packaging. In the food industry, thermoplastic flexible films are used to keep food fresh prior to consumption. Greater use of centralized processing of foods in conjunction with increased handling and longer delivery times associated with long distance transportation have increased the demand for packaging films having superior properties. In the poultry and meat segments of the food industry thermoplastic flexible films are utilized to maintain freshness. Meat is frequently cold fresh, frozen or cooked; therefore films advantageously provide protection at various temperatures. Food items such as primal and subprimal cuts of beef, ground beef and processed meals are known to use coaxtruded or laminated films which utilize such compositions as nylon, polyester, copolymer of vinylidene chloride (PVDC), ethylene-vinyl acetate copolymer (EVA) and ionomers. It is also generally known that selection of films for packaging food products includes consideration of such criteria as barrier properties, cost, durability, puncture resistance, flex-crack resistance, FDA approval, machinability, optical properties such as gloss and haze, printability, sealability, shrinkabitity, shrink force, stiffness, and strength. In general, nylon films are made by processes which include casting or blown film and these films may be uni- or biaxially oriented. Specific types of nylon such as nylon 6, nylon 6,9. and nylon 12 have been made into films Known advantages of nylon films relative to other film materials In packaging applications include good oxygen and flavor barrier characteristics, durability at low temperatures and thermal stability. However, nylons in general are costly and are poor moisture barrier. It is known to use certain nylon films as core layers in oriented multilayer films. However, nylon selection is critical and processes very difficult. These multilayer films may include one or more additional layers of films made of various resins, for example, low density polyathylene (LDPE), ethylette-vinyl acetate copolymer (EVA), ionomer, PVDC. or copolymers of ethylene and methscrylale. Nylon containing films have also been used In vacuum packaging of fresh meat. Typical and generally known films suitable for packaging and information on film manufacture are described in the Encyclopedia of Polymer Science and Engineering 2nd Ed., Vol. 7. pp. 73-127, Vol. 10, pp. 684-695 (John Wiley & Sons, Inc., 1987). Also, amorphous nylons have been disclosed as useful in thermoplastic films including multilayer films and biaxially drawn films. U.S. Patent 4,688,195 and European Patent application No. 240,632 both disclose a process for preparation of a biaxially drawn polyamide film which utilizes what is termed "a substantially amorphous unoriented polyamide film". Also, U.S. Patent 4,668,571 (Moriarty, Jr.) discloses a multilayer stock material useful for producing flexible, thermoplastic bags in which an outer layer may comprise a polyamide resin. Among the examples of suitable polyamide resins is listed amorphous nylon. Additionally, European Patent application No. 236,098 (Fant et al) discloses a multilayer thermoplastic film having optional polyamide layers. Suitable polyamides are said to include a commercially available copolymer of nylon 6 and nylon 12 having a composition of about 80% nylon 6 and about 40% nylon 12 by weight sold under the trademark Grilon® CA-6 by Emser Indusbies. Another suitable nylon copolymer is disclosed as CR-9. having 20% to 30% nylon 6 and 70% to 80% nylon 12 by weight Also, more recently coextruded film packaging for processed meat was reportedly being used in Japan which utilizes an amorphous nylon sold under the brand name Novamid X21 by Mitsubishi Chemical Industries Ltd. of Tokyo (See "Coextrusion Developments Focus on Barrier Resins", Plastics Technology, Vol. 33, No. 13, pp. 5, 77-79, December, 1987 Bill Communications, inc., New York). EP-A 287 839, a counterpart of U.S. Patent 4,800,129,(Deak) discloses thermoformed multi-layer structures comprising a blend of amorphous polyamides having a Tg greater than 120 °C with one or more semicrystalline aliphatic polyamides. This document is prior art pursuant to Art. 54(3) EPC for all designated contracting states except Austria, so that different claims pursuant to Rule 87 I.R. EPC are necessary. Deak discloses blend of amorphous polyamide with aliphatic polyamide wherein the amount of amorphous polyamide ranges from 60 to 80 % of the blend and preferably 70 to 85 %. EP-A 273 337 discloses a three layer plastic film comprising: a) a core layer of between about 60 and 90 wt.% hydrolyzed ethylene vinyl acetate copolymer containing between about 28 and 40 wt% ethylene and blended with between about 10 and 40 wt.% amide polymer having a melting point below about 420 °F, said core layer providing an oxygen transmission rate through the film below about 90 cc/m 2 /mil thickness/24 hrs/Atm;b) a first outer layer directly adhered to one side of said core layer comprising a blend of ethylene vinyl acetate containing between about 7 and 15 wt.% vinyl acetate, and between about 5 and 20 wt.% of an ethylene vinyl acetate-anhydride functionality compound; and c) a second outer layer directly adhered to the other side of said core layer and comprising ethylene vinyl acetate containing between about 7 and 15 wt.% vinyl acetate, and between about 5 and 20 wt.% of an ethylene vinyl acetate-anhydride functionality compound; d) said film having been irradiated at a level of between about 1 and 5 MR. JP-A 62/131 060 discloses a heat-shrinkable polyamide film which is a biaxially oriented polyamide film comprising a blend of (A) a polyamide prepared by polymerizing 100-85 wt.% of a polyamide-forming component composed of an aliphatic diamine and isophthalic acid and/or terephtharic acid and 0-15 wt.% of a polyamide-forming component composed of a lactam or aliphatic diamine and an aliphatic dicarboxylic acid, and (B) a polyamide prepared by polymerizing 70-99 wt.% of an aliphatic polyamide-forming component and 30-1 wt% of a polyamide-forming component composed of at least one aliphatic diamine and at least one aromatic dicarboxylic acid, said film having hot-water shrinkage rate of 25 % or more at 75 °C. EP-A 0 070 001 discloses a thermoplastic molding resin comprising a particular amorphous thermosplastic polyamide copolymer contined with a semicrystalline thermoplastic polyamide, wherein such resin is to have a wide variety of applications depending on the relative amounts of the compounds of the resin. As specific applications, page 8, lines 15 to 21 names articles having good solvent resistance, good dimensional stability and good relation of physical properties mater most and wet condition, e.g. for producing shaped bodies (e.g. automobile feaders, bumpers and the like). Oriented nylon films are also well known in the packaging industry for their toughness, puncture resistance, and oxygen barrier properties. In particular, biaxial orientation is known to generally improve film strength. The oxygen barrier properties of oriented nylon films generally provide greater resistance to oxygen permeability as the level of absorbed moisture decreases. As the moisture content increases, the oxygen barrier properties of most oriented nylons deteriorate. When nylon films are to be used or stored under humid or other moist conditions, it becomes desirable to protect the nylon film e.g. by placement between layers having relatively low permeability to moisture, in order to keep the nylon dry. However, orientation of coextruded multilayer blown films having nylon as a protected core layer is difficult due to processing constraints. Often nylon is the outer layer in coextruded processing because of the necessity for rapid quenching to achieve suitable processing in a multilayer structure. Of course, lamination processes may be and are presently utilized to attach a moisture protective layer to nylon, but this is disadvantageously expensive. In many packaging applications, it is also desirable that at least one of the layers have good heat seal properties. Resins which have both good heat sealability and are substantially impermeable to moisture include various polyethylenes, ethylene copolymers and ionomers. Oriented nylon films are currently used alone and in combination with these heat sealable and moisture resistant layers. Disadvantageously, it has proved difficult to find film layers (other than PVDC) which have good barrier properties to both moisture vapor and oxygen. Therefore, multilayer films are commonly employed to utilize the most beneficial properties of various film layers. The Encyclopedia of Polymer Science and Engineering, 2nd Edition., Vol. 7, pp. 77-79 (John Wiley & Sons, Inc., 1987) discloses that "nylon is frequently the core portion of the film being coextruded or coated with sealant resins, such as LDPE, EVA, ionomers, or copolymers of ethylene and methacrylate". The nylon layer acts as an oxygen and flavor barrier for such applications as processed meat and cheese packaging, boil-in-bags, and bags for baked goods. In a typical known process for producing multilayer films containing oriented nylon, the nylon film is oriented by heating to a softened state below the melting point and stretching the softened material. Many conventional nylon resins crystallize very rapidly and have melting points well in excess of adjacent polyethylene layers. Due to these temperature differences and because nylon and polyethylene tend to have different stretching characteristics, the nylon layer is typically oriented separately and in advance of its combination with the adjacent polyethylene layers. The combination of the oriented nylon with the adjacent layers is then accomplished using a conventional but relatively expensive and complex lamination process. This requires an adhesive such as polyurethane type adhesive applied with a coater-laminator. Another problem with current multilayer oriented nylon stuctures is that while a material such as polyethylene generally protects the nylon from moisture, some moisture gradually aseps in from either the packaged food article or the atmosphere and is absorbed by the nylon. This causes an increase in oxygen permeability which shortens the shalf the of oxygen sensitive foods. Due to recent growth in the market for barrier films, there currently exists an industry wide search for films with improved barrier properties such as low oxygen permeability and low water permeabillity. For economic reasons, there is also a demand for an oriented nylon multilayer film which can be produced by a coextrusion process. Production of multilayer films by coextrusion is generally more ecanomical than use of lamination methods. The present invention provides multilayer films comprising a nylon resin blend, which ameliorate many problems associatetl with known films. It is not necessary that each and every problem listed above be overcorne by all embodiments of the invention. It is sufficient that the invention may be advantageously employed when compared to the prior art. SUMMARY OF THE INVENTION According to the present invention, there is provided a novel thermoplastic flexible coextruded biaxially oriented heat shrinkable multilayer film as defined in Claim 1. Further embodiments are the subject-matter of dependent Claims 2 to 9. Thus, provided is a thermoplastic flexible coextrued biaxially oriented heat shrinkable multilayer film comprising a first outer layer, a second outer layer, and at least one intermediate layer between said first outer layer and said second outer layer, said intermediate layer comprising a nylon blend containing (a) 10 to 70 weight percent of an amorphous nylon copolymer having no measurable melting point or no heat of fusion (less than 2.1 J/g (0.5 cal/g)) as measured by differential scanning calorimetry (DSC) using ASTM 3417-83, said amorphous nylon copolymer comprising hexamethyleneisophthalamide/hexamethyleneterephthalamide copolymer provided that said amorphous copolymer is not present in an amount of from 60 to 90 weight percent of said blend; and (b) 10 to 90 weight percent relative to the total weight of the blend of a copolyamide having a melting point within a range of from 145 °C to 215 °C, said copolyamide comprising a copolymer of nylon 6 and nylon 12 or a copolymer of nylon 6 and nylon 66 or mixtures of said copolymers, and said first and/or said second outer layer comprising ethylene vinyl acetate copolymer, very low density polyethylene or mixtures thereof. These inventive films are surprisingly easy to process and orient when being produced. For example, the blends wich according to the present invention form films which are relatively easy to biorient compared to films of the individual blend components alone. In particular, many crystalline nylons exist which are known to be extremely difficult to biaxially stretch in order to form shrinkable films. It has been presently discovered that blends of these orientation-resistant nylons with an amorphous nylon copolymer nylon 6l, 6T produce a film which may be easily unixially or biaxially oriented. For example, biorientation of a film layer formed of nylon 6/12 alone is very difficult and attempts at biorientation are often unsuccessful. However, a blend of nylon 6/12 with an amorphous nylon may be easily uniaxially or biaxially oriented according to the present invention. Surprisingly, the present invention shows successful biaxial orientation of coextruded multilayer films having a nylon containing intermediate layer, wherein the nylon layer comprises a blend of a nylon copolyamide having a melting point of at least 145 °C with an amorphous nylon defined above. These films have excellent optical and oxygen barrier properties. According to the present invention the entire multilayer film is biaxially stretched without the necessity for separately biaxially stretching the nylon containing layer independent from the non-nylon layers followed by lamination of the individual stretched layers. Unexpectedly, addition of an amorphous polyamide such as nylon EVET having a glass transition point of about 127°C to a copolyamide such as nylon 6/12 forms a blend which may be easily processed into a shrinkable film. This film exhibits high gloss and law haze and good shrinkage values at temperatures well below 127°C. Addition of amorphous nylon to nonamorphous copolyamides according to the present invention results in great improvements in one or more of such properties as haze, gloss, oxygen permeability, tensile strength, dynamic puncture or shrink percentage after extrusion. Also, unexpectedly it has been discovered that addition to the above inventive blends of a homopolymer such as nylon 11 having a relatively high O 2 permeabiltity value actually lowers O 2 permeability of the resulting film. Advantageously, blends used according to the present invention may be employed to form uniaxially or biaxially oriented single or multilayer films by a variety of orientation processes. Detailed Description of the invention Polyamides include nylon resins which are well known polymers having a multitude of uses including utility as packaging films, bags and casing. See, e.g. Modern Plastics Encyclopedia, 88 Vol. 64, No. 10A, pp 34-37 and 554-555 (McGraw-Hill, Inc., 1987). In particular, oriented multilayer films of the present invention are useful in food packaging. The invention utilizes an amorphous nylon copolymer as a component of a resin blend used to produce novel multilayer films. The term "amorphous" as used herein denotes an absence of a regular three-dimensional arrangement of molecules or subunits of molecules extending over distances which are large relative to atomic dimensions. However, regularity of structure may exist on a local scale. See, "Amorphous Polymers," Encyclopedia of Polymer Science and Engineering, 2nd Ed., pp. 789-842 (J. Wiley & Sons, Inc. 1985). In particular, the term "amorphous nylon copolymer" as used with respect to the present invention refers to a material recognized by one skilled in the art of differential scanning calorimetry (DSC) as having no measurable melting point (less than 2.1 J/g (0.5 cal/g)) or no heat of fusion as measured by DSC using ASTM 3417-83. The used amorphous nylon copolymers include hexamethyleneisophthalamide-hexamethylene terephthalamide copolymer also referred to as nylon 6l/6T. A preferred component of the invention is hexamethyleneisophthalamidehexamethylene terephthalamide copolymer which has from 65 percent to 80 percent of its polymer units derived from hexamethyleneisophthalamide. Especially preferred as the amorphous nylon copolymer component is a commercially available nylon 6l/6T sold by the DuPont Company of Wilmington, Delaware, U.S.A. under the trademarked designation Selar PA 3426. Selar PA 3426 is further characterized by DuPont Company technical bulletin E-73974 dated 12/85, as an amorphous nylon (polyamide) having superior transparency, good barrier properties to gases such as O 2 , solvents and essential oils and also the following properties according to the indicated standards: density of 1.19 g/cc (ASTM D1505); glass transition temperature of 127°C (ASTM D3418); heat deflection temperature of 126° C at 4.6 Kg/cm 2 (66 psi) and 123° C at 18.4 Kg/cm 2 (264 psi) (ASTM D648); and flexural modulus of 27,900 Kg/cm 2 (400,000 psi) at 50 percent relative humidity and 23°C (ASTM D790). The amorphous nylon copolymer used in the present invention may be manufactured by the condensation of hexamethylenediamine, terephthalic acid, and isophthalic acid according to known processes. It is preferred that a nylon 6l/6T resin be used which is manufactured such that 65 to 80 percent of the polymer units are derived from hexamethylene isophthalamide. Advantageously, such resins (which are further characterized as having a specific gravity of 1.207± 0.1, no melting point, and having the solubility and extraction values listed in Table I) have been approved for food contact in the United States by the Food and Drug Administration. (See 52 Fed. Reg. 26,666-26,667, July 16, 1987). Table 1 Nylon resin Solubility in boiling 4,2N HCl Maximum extractable (% by fraction as selected weight of resin) solvents WATER 95% Ethyl Alcohol Ethyl Acetate Benzene Nylon 6116T Insoluble after 1 hour 02 1.0 0.1 0.1 Suitable copolyamides useful in forming the blends used in the films of the present invention are copolyamides having a melting point of at least 145°C. A suitable method of determining a melting point is by using differential scanning calorimetry as above to determine the heat of fusion. The used copolyamides melt at temperatures within a range of from about 145°C to about 215°C. Copolyamides with melting points in this range have been found to form useful blends with the above noted amorphous nylon copolymers, which blends are easy to process into films including oriented films. In film packaging applications, copolyamides with melting points less than 145°C soften and distort at typical processing temperatures which indude e.g. 82-83°C (180-200°F) for shrink wrapping and 71-82°C (160-180°F) for cooking sausages. Copolyamides especially suited as components of the inventive films are copolyamides which comprise a copolymer of nylon B with at least one other polyamide whereby the copolyamide has a melting point of at least about 145°C. Preferably, these especially suited copolyamides have a melting point less than about 215°C. Mixtures of copolyamides are also contemplated. The used copolyamides are nylon 6/12 and nylon 8/86 and mixtures thereof. Nylon 6/12 and nylon 6/66 copolyamides are commercially available. For example a nylon 6/12 copolyamide which melts within a range of from about 195-200°C (ASTM D2117) is commercially available under the trademark Grilon CR 9 from Emser industries of Sumter, South Carolina, a division of EMS-Ameciran Grilon, Inc. (EMS). Mixtures of copolyamides may be usefully employed in the present invention. For example, two or more copolyamides each having a melting point of at least 145°C may be used, or a copolyamide having a melting point of at least 145°C may be mixed with one or more other copolyamides which have melting points less than 145°C or are amorphous themselves. A suitable copolyamide for mixing which has a melting point less than 145°C is another nylon 6/12 copolyamide which malts at above 134°C (DSC max.) which is commercially available from EMS under the trademark Grilon W6220. In an especially preferred embodiment of the invention, mixtures of these two nylon 6/12 copolyamides are utilized. A copolyamide of nylon 8/88 which melts at about 185°C is commercially available from Allied-Signal under the trademark Nylon 1539, mixtures of one or more nylon 6/12 copolyamides with one or more nylon 6/66 copolyamides may be usefully employed in the invention. Also, mixtures of various nylon 6/12 compositions may be employed to optimize properties. Advantageously, a most preferred nylon 6/12 copolyamide mixture may be formed from about 80 percent by weight of Grilon CR9 and 20 percent by weight of Grilon W6220. In addition to the first componant of an amorphous nylon copolymer and the second component of a copolyamide having a melting point of at least 145°C the films of the present invention may also employ as a third component a polyamide homopolymer. It has been found that a nylon homopolymer may be added to decrease gas permeability and thereby improve the gas barrier properties of the blend. Suitable homopolymers include such commercially available nylons as nylon 8, nylon 11 and nylon 12. According to the present invention, there is provided an oriented multilayer film as defined above, said film comprising a nylon resin blood, which nylon resin blend again comprises as a first composant of the blend, an amorphous nylon copolymer as described above and, as a second composant of said blood, a copolyamide as described above. The first component is preferably nylon 6I/6T which is an amorphous hexamethylenelsophthalamide-hexamethyleneterephthalamide copolymer. Advantageously, a nylon 6I/6T having from about 65 to about 60 percent of its polymer units derived from hexamethyleneisophthalemide will be employed with a commercially available composition sold under the brand name Selar PA 3428 by the Dupont Company of Wilmington, Delaware being especially preferred. The second component is preferably a nylon B/12 alone or a mixture of nylon B/12's. Advantageously, a mixture of (i) a nylon 6/12 having a malting point between about 145°C and 215°C with (ii) a nylon 6/12 having a maffing point of lass than about 145°C is employed. Especially preferred is a mixture of about 80% by weight of a nylon 6/12 known as Grilon CR9 and about 20% by weight of a nylon B/12 known as Grilon W6220. both nylon 6/12 copolyamides being sold by Emser industries of Sumter, South Carolina. Optionally, a third component may be advantageously employed. As noted above, a homopolymer such as nylon B, nylon 11, or nylon 12 may be added as a third component to the blend. Surprisingly, addition of a preferred homopolymer such as nylon 11 increases the barrier properties of the films of the blend to transmission of oxygen gas. A fourth component or more such as other nylon copolymers (e.g. nylon 6/68), or other amorphous nylons may also be added to the blend. Unless otherwise specified, all weight percentages herein are based upon the total weight of the resin blend. The first component (amorphous nylon copolymer) will be present in an amount of from about 10 to about 70 weight percent provided that said amorphous nylon copolymer is not present in an amount of from 60 to 90 weight percent of said blend. Use of amounts uses than 10 wt.% reduces the benefical effect of enhanced properties attributable to the amorphous nylon copolymer component. In particular, the haze of films increases noticeably at lower amounts. Also, use of amounts greater than 70 wt.% has a deleterious effect on processability. Bubbis formation becomes increasingly difficult at high levels of amorphous nylon copolymer. The second . component (copolyamide) will be present in the blend in an amount of from 10 to 90 weight, percent relative to the total weight of the blend. At amounts less than 10 percent and greater than 90 percent, orientation of a film of the blend becomes increasingly difficult, particularly for simultaneous biaxial orientation a double bubble type process. Also, use of amounts in excess of 90 percent reduces the beneficial optical properties of the blend, e.g. haze increases noticably. Optionally, a beneficial third component (homo-polymer) may be present in the blend in an amount of from 10 to 30 weight percent. At amounts under 10 percent the beneficial effect on physical proparties such as oxygen barrier properties decreases. Disadvan-tagely, amounts over 30 present increases stiffness to undesirable levels for film processing. The above range of amounts and particular components and combinations are believed to provide enhanced processing and/or resin properties, and films made from such resins show unexpected and surprising proparties and results as described balow. The present invention contemplates oriented multilayer films These thermoplastic flexible films may be made by well known conventional processes. In multilayer film applications of the present inventions, the first outer layer and second outer layer and additional optional intermediate layers may be made of suitable resins or resin blends. Suitable resins for the first and/or second outer layer include low dansity polyethylene (VLDPE). ethylene vinyl acetate copolymer (EVA) and various blends thereof. Thus, the used components of the outer layers are VLDPE, EVA and blends thereof. VLDPE is a copolymer of ethylene and at least one comonomer selected from C 4 to C 10 alpha-olefins and having a density between about 0.66 and 0.91 g/cc and a melting point of about 120°C. EVA is a copolymer of amylane and vinyl acetate. Preferred EVA resins will comprise between 1 to 20 percent vinyl acetate by weight and most preferably 3 to 12 percent by weight. Advantageously, EVA may be blended with VLDPE. Also, adhesives may be blended in the layers or adhesive layers may be coextruded. Suitable adhesive resins include anhydride based EVA and LLDPE resins. A preferred adhesive resin is an ethylene based polymer containing vinyl acetate and anhydride functionality such as that sold by DuPont Company under the brand name Bynel CXA E-162. For the multilayer films of the present invention the resins utilized are generally commercially available in pallet form and as generally recognized in the art, may be blended by well known methods using commercially available blenders. Also, if desired, well known additives such as processing aids, slip agents, antibloking agents. pigments, and mixtures thereof may be incorporated into the film, genarally in small amounts of up to about 10 percent by weight by blending prior to extrusion. The resins and any additives are introduced to an extruder (generally one extruder per layer) where the resins are melt plastified by heating and than transferred to an extrusion (or coextrusion) die for formation into a tube. Extruder and die temperatures will generally depend upon the particular resin or resin containing mb\!1Jres being processed and suitable tomwermm ranges for commercially available resins are generally known in the art, or are provided in technical bulletins made available by resin manufacturers. Processing temperatures may vary depending upon other process parameters chosen. In coextrusion. barrel and die temperatures, for example, may range between 175°C and 250° C. However, depending upon the manufacturing process used and particular equipment and other process parameters utilized. variations and actual process parameters including process temperatures will be set by one skilled in the art without undue experimentation. In a preferred coextrusion type of double bubble process as described in U.S. Patent 9,456,044 the primary tube leaving the die is inflated by admission of air, cooled, collapsed, and than preferably oriented by reinflaring to form a secondary bubble with reheating to the film's orientation (draw) temperature range. Machine direction (M.D.) orientation is produced by pulling e.g. by utilizing a pair of rollers travelling at different speeds and transverse direction (T.D.) orientation is obtained by radial bubble expansion The oriented film is set by cooling. Suitable machine direction and transverse direction stretch ratios are from 1.5:1 to 3.5:1 with a ratio of 2.5:1 preferred. The orientation of the multilayer film which mayimprove certain physical properties of the films creates films which are heat shrinkable. The film may be stretched sequentially (M.D. first followed by T.D. expansion) or simultaneously stretched in machine and transverse directions. Experimental results of the following examples are based on tests similar to the following test methods unless noted otherwise. Haze: ASTM D-1003-52 Gloss: ASTM D-2457, 45° Angle Tensile Strength: ASTM D-882, method A % Elongation: ASTM D-882, method A 1% Secant Modulus: ASTM D-882, method A O 2 Transmission: ASTM D-3985-81 Elmendorf Tear Strength: ASTM D-1922 Gauge: ASTM D-2103 Shrinkage Values: Shrinkage value is defined to be values obtained by measuring unrestrained shrink at 90° C for five seconds. Four test specimens are cut from a given sample of the film to be tested. The specimens are cut to 10 cm. in the machine direction by 10 cm. in the transverse direction. Each specimen is completely immersed for 5 seconds in a 90°C water bath. The distance between the ends of the shrunken specimen is measured. The difference in the measured distance for the shrunken specimen and the original 10 cm. is multiplied by ten to obtain the percent of shrinkage for the specimen. The shrinkage for the four specimens is averaged for the MD shrinkage value of the given film sample, and the shrinkage for the four specimens is averaged for the TD shrinkage value. Dynamic Puncture Resistance: Dynamic Puncture Resistance values are defined to be those obtained by the following test. The dynamic puncture-impact test procedure is used to compare films for their resistance to bone puncture. It measures the energy required to puncture a test sample with a sharp pyramidal metal point made to simulate a sharp bone end. A Dynamic Ball Burst Tester, Model No. 13-8, available from Testing Machines, Inc., Amityville, Long Island, New York, is used, and a modified tip is installed on the tester probe arm for use in this test procedure. The modified tip is constructed from a 0.95 cm (3/8 inch) diameter conical tip having a configuration of a right circular cone with the angle between the cone axis and an element of the conical surface at the vertex being about 65°. Three equally spaced and abutting planar surfaces are machined to a smooth finish on the cone surface to form a pyramidal shaped point. Six test specimens 10.2 cm (approximately 4 inches) square are prepared, a sample is placed in the sample holder, and the pendulum is released. The puncture energy reading is recorded. The test is repeated until 6 samples have been evaluated. The results are calculated in cm-kg/µm (cm-kg per mil) of film thickness and are averaged. The following are examples and comparative examples given to illustrate the present invention. In all the following examples, unless otherwise indicated herein the film compositions were produced generally utilizing the apparatus and method described in U.S. Patent No. 3,456,044 (Pahlke) which describes a coextrusion type of double bubble method and in further accordance with the detailed description above. All percentages are by weight unless indicated otherwise. Examples 1-2 and Comparative Examples 3-4 (all not of the invention) The film compositions of Examples 1-4 were produced under similar conditions. For each example listed in Table 2 the components were blended in the indicated weight ratio followed by heat plastification and extrusion of a tube as generally described above and in the procedure for making a single layer film as described in examples 7-13. Draw point temperature and bubble cooling rates were adjusted to maximize bubble stability, and properties of each film are reported in Table 2. The films were extruded in the form of a seamless tube. The tubes were wound on cardboard reels and the end of each tube was secured by tape. Examples 1 and 2 represent identical films except that in the film of Example 2 the reeled tube was then annealed in a circulating hot air oven at 37.8° C (100°F) to dimensionally stabilize the tube. During annealing, the tube flat width was reduced from 15.9 cm (about 6.25 inches) to 12.7 cm (about 5 inches) by shrinkage. Properties of an unannealed and annealed film are reported in Examples 1 and 2 respectively. The amorphous nylon copolymer and copolyamide blend of Examples 1 and 2 formed a shrinkable film which was easy to orient with unexpectedly good optical properties including very high gloss and low haze relative to comparative examples 3 and 4 which did not contain an amorphous nylon copolymer. The unannealed film of example 1 had very high shrinkage relative to the unannealed comparative examples 3 and 4. Annealing reduces the shrinkage as seen in example 2. Also, the examples 1 and 2 demonstrated higher tensile strength relative to the comparative examples 3 and 4. A comparison of haze, gloss and tensile strength properties of the unannealed film of Example 1 with the annealed film of Example 2 indicates that annealing may modify or improve some properties relative to unannealed film. Moreover, both films (annealed and unannealed) of Examples 1 and have improved tensile strength, superior gloss, and dramatically less haze than the unannealed comparative films of Examples 3 and. In each example and comparative example the amount of component A was held the same and component B was varied by substituting two different crystalline 6/12 polyamides for the amorphous polyamide. An annealed tube according to Example 2 was used as a sausage casing. This tube was hand stuffed with a beef and pork emulsion, and cooked. The resultant sausage casing had a good yield with uniform adhesion of the casing to the stuffed meat. Table 2 # Nylon Blend Components A:B Wt. Ratio Haze % Gloss Tensile Strength MPa (X10 3 psi) M.D/T.D. Shrink % at 90° C M.D/T.D. A B 1 + 6/12 (CR9) amorphous nylon copolymer* 4:1 2.1 93.1 (23/23) 160/160 51/49 2 + + 6/12 (CR9) amorphous nylone copolymer* 4:1 1.8 97.8 (20/24) 140/170 14/9 3 6/12 (CR9) 6/12 (CA6) 4:1 >30 13.3 (15/15) 105/105 19/22 4 6/12 (CR9) 6/12 (W6220) 4:1 >30 5.0 (15/17) 105/120 15/18 *A nylon 6l/6T amorphous copolymer sold under the brand name Selar PA 3426 was used. + Unannealed film + + Annealed film Example 5 and Comparative Example 6 (all not of the invention) In Example 5 an amorphous nylon copolymer (nylon 61/6T in the form of Selar PA 3426) was added to the resin blend of comparative example 6. The blend of example 5 and the comparative blend (example 6) were both processed under similar conditions into single layer films, (See the description for examples 7-12 below) and similarly tested for tensile strength, tear strength, dynamic puncture resistance and shrinkage values. The test results as shown in Table 3 clearly demonstrate that addition of an amorphous nylon copolymer such as 6I/6T to the substantially crystalline blend prior to processing produced a film with greatly increased tear strength and puncture resistance. Tensile strength also showed improvement and shrinkage values were significantly higher. The film of example 5 was used as a tubular seamless casing by first annealing the tube at 37.8°C (100°F) as for Example 2 with a resultant reduction in flat width from 15.9 cm (about 6.25 inches) to 13.6 cm (about 5.37 inches). Then the annealed tubular casing was hand stuffed with a meat emulsion and steam cooked at 76.7°C (170°F) until the internal temperature reached 65.6°C (150°F). The resultant cooked, stuffed sausage had uniform adherence of the casing to the sausage over the entire surface and at least as good of an appearance and cooking weight yield as a similarly made sausage having a commercially available nylon casing. Table 3 # Nylon Blend Components Tensile Strength MPa (X10 3 psi) M.D/T.D. Elmendorf Tear Strength g/µm (g/mil) M.D/T.D. Dynamic Puncture Resistance cm· Kg/µm (cm·Kg/mil) Shrink % at 90° C M.D/T.D. nylon* 6/66 wt.% nylon** 6/12 wt.% nylon*** 6l/6T wt.% 5 72 18 10 (27/21) 190/140 (49/76) 1.9/3.0 (2.3) 0.09 35/32 6 75 25 - (22/24) 150/170 (15/16) 0.59/0.63 (1.6)0.06 22/25 * The nylon 6/66 used was commercially available under the brand name Nylon 1539 from Allied-Signal Engineered Plastics of Morristown, New Jersey and had a melting point of about 195 ° C. ** The nylon 6/12 used was commercially available under the brand name Grilon® W6220 from Emser Industries of Sumter, South Carolina and had a melting point of about 135°C. *** The amorphous nylon copolymer used was a nylon 6I/6T which was commercially available under the brand name Selar PA 3426 from the DuPont Company of Wilmington, Delaware and had a glass transition point of about 127°C. Examples 7-13 (all not of the invention) Bioriented films of three and four component blends may be made as demonstrated by the compositions and properties of the films described in Examples 7-13. Blends of an amorphous nylon copolymer such as nylon 6l,6T and a crystalline copolyamide having a melting point above 145°C such as a commercially available nylon 6/12 (Grilon® CR9) may be made with one or more other nylon 6/12 copolymers, nylon 6/66 copolymers or nylon homopolymers such as nylon 6, nylon 11, and nylon 12. Each single layer film was extruded and biaxially stretched (oriented) by a known double bubble extrusion process (See e.g. U.S. 3,456,044). In forming the primary film tube, the resins were conventionally blended and heat plastified in a conventional single screw extruder equipped with a standard commercially available polyethylene screw and conventional die similar to the procedure described for examples 12-21. The extruder barrel temperature ranged from 176.7°C to 232.2°C (350°F to about 450°F) and the die temperature was set at 224°C (about 435°F). The machine direction (M.D.) orientation ratio was from about 2 to 2.5 and the transverse direction (T.D.) orientation ratio was from about 2 to 3. In order to minimize equipment changes during experimental runs and provide physical support and reduce adhesion to equipment each single layer film was formed by coextrusion of the nylon containing layer with a polyethylene layer such as linear low density polyethylene to form a primary tube. The polyethylene outer layer was then stripped off after cooling of the primary tube but prior to biaxial orientation to yield a single layer film. It is expected that single layer films may be conventionally formed by one of ordinary skill in the art without need for coextrusion of a second layer. Single layer films having various nylon blend components are listed in Table 4 as Examples 7-13. In all of these examples the blends produced bioriented films having good shrink properties in both the machine direction and the transverse direction. In examples 9 and 11, shrinkage was determined to be comparable to the other examples in Table 4, however, shrinkage measurements were made of the fresh film soon after orientation whereas measurements of examples 7, 8, 10, 12 and 13 were made several days following orientation. The optional addition of nylon homopolymers may improve gas barrier properties by lowering permeability. In examples 11 and 13, the nylon 6 and nylon 12 polymers, were commercially available nylon homopolymers sold under the respective brand names Emser F40 (nylon 6) and Emser L25 (nylon 12) by Emser Industries of Sumter, South Carolina. In example 12, the nylon 11 polymer was a nylon homopolymer commercially available under the trade name Rilsan Besno nylon 11 from Rilsan Corporation of Glen Rock, New Jersey. Surprisingly, as shown in example 12, addition of nylon 11 which has a relatively high O 2 permeability 26ml·25.4 µm/24h/645 cm 2 ·1.01 bar (28ml mil/24 hrs/100 in 2 /1 atm) yielded a film with a lower oxygen permeability (relative to examples 7 and 8 which did not contain a homopolymer such as nylon 11). Table 4 Nylon Blend Components # Amorphous Nylon* wt.% Nylon 6/12** m.p.>145°C wt.% Nylon 6/12*** wt.% Other Nylon wt.% SHRINK % at 90°C M.D./T.D. O 2 TRANS. (cc mil/ 100in 2 / 24hc/l atm) 51 unit: ml.25.4µm 24h·645cm 2 ·1.01bar 7 10 72 18 32/26 5.45 8 20 72 8 48/46 4.79 9 18 57.6 14.4 nylon 6/66 + 10 N.D. N.D. 10 18 57.6 14.4 nylon 6/12 ++ 10 40/43 2.33 11 18 57.6 14.4 nylon 6 +++ 10 B.D. N.D. 12 18 57.6 14.4 nylon 11 ++++ 10 35/38 1.46 13 18 57.6 14.4 nylon 12 +++++ 10 38/38 1.76 H.D. - Not Determined * An amorphous nylon 6I/6T copolymer commercially available as Selar PA 3426 (trademark of E.I. DuPont de Nemours & Co.). ** A nylon copolyamide of nylon 6/12 commercially available as Grilon® CR9 (trademark of Emser Industries). *** A nylon copolyamide of nylon 6/12 commercially available as Grilon® W6220 (trademark of Emser Industries). + Nylon 1539 (trademark of Allied-Signal Engineered Plastics). ++ Zytel 151 (trademark of E.I. DuPont de Neumours & Co.). +++ Emser F40 (trademark of Emser Industries). ++++ Rilsan Besno (trademark of Rilsan Corporation). +++++ Emser L25 (trademark of Emser Industries). Examples 14-24 A series of multilayer films according to the present invention were made by the above described coextrusion type of double bubble process with a nylon blend intermediate layer. The physical properties of these multilayer films and two comparative examples were tested and the results are listed as examples 14-24 in Table 5. Comparative examples 14 and 15 are not of the present invention whereas the remaining examples are of the present invention. Each multilayer film was coextruded and biaxially oriented by known coextrusion and orientation processes (see e.g. U.S. 3,456.044). For the three layer films of examples 16-24 a layer thickness ratio of 12:7:6 was used which corresponds to first outer layer; intermediate layer: second outer layer, respectively. The layer ratio of example 14 was 2:1:2. In forming the blown film tube, the first outer layer, corresponds to the outermost layer of the tube and the second outer layer corresponds to the innermost layer of the tube. Three single screw extruders equipped with polyethylene metering screws were utilized with the extruders attached to a conventional coextrusion die. The die diameter was 3.2 cm (1.25 inches). The extruder barrel temperature ranged from 176.7°C to 232.2°C (about 350° to about 450°F) with the die temperature set at 224°C (about 435°F). The machine direction orientation ratio was from about 3:1 to 5:1 and transverse direction orientation ratio was from 3:1 to 5:1. The resins of examples 14-24 were coextruded and bioriented according to known methods as outlined above and the resultant oriented films tested. Examples 16, 19-23 are three layer films in which both outer layers of each film comprise a copolymer of ethylene with vinyl acetate (EVA). Each outer layer was blended with 10% by weight (relative to the weight of the outer layer) of an adhesive resin (Bynel 162-E). This adhesive was also blended in like amount with the very low density polyethylene (VLDPE) which comprised both outer layers of examples 18 and 24 as well as the second outer layer of example 17. The first outer layer of example 17 was an EVA blended with an adhesive similar to the other EVA layers in this group of examples. Both outer layers of comparative example 14 comprised a linear low density polyethylene (LLDPE), whereas both outer layers of comparative example 15 comprised VLDPE. Comparative example 15 suffered from delamination and both outer layers were removed after orientation. Therefore, the test results for example 15 are for the intermediate layer of nylon 6/12 copolymer alone. Examples 14-24 were tested for tensile strength, ultimate elongation, secant modulus at 1%, shrinkability at 90°C, dynamic puncture resistance, haze, gloss and oxygen gas transmission. The results of these tests are listed in tabular form in Table 5 along with the average gauge of the test sample, and composition of the films. Example 14 (not of the invention) contained a 100% amorphous nylon intermediate layer. It did not contain any copolyamide having a melting point greater than 145°C as required by the present invention. The film of example 14 was difficult to process and orient relative to films of the instant invention. Also, the biaxially oriented film of comparative example 14 has a very low shrinkage value (less than 5%). Also, the film of example 14 has comparatively low gloss and high haze. However, the film of example 14 does have excellent oxygen barrier properties and tensile strength. This film is the subject of a U.S. patent application Serial No. 091,172, corresponding to the Art 54(3) EPC document EP-A 305 959, filed at the EPO on August 30, 1988. Comparative example 15 (not of the invention) contained an intermediate layer having 100% by weight of a copolyamide having a malting point greater than 145°C. The test results are of the intermediate layer alone, but do not indicate or suggest the surprisingly good physical properties of the present invention as shown in Table 5 and discussed below. Examples 16-24 of the present invention demonstrate that biaxially oriented multilayer films having a nylon blend intermediate layer with multilayer film shrinkage values of 5% or greater may be made according to the present invention. Advantageously, multilayer films with shrinkage values of 20% or higher in one or more directions may be produced with shrinkage value greater than 40% obtainable for various film compositions. All of the.examples of the invention having both outer layers of EVA show excellent optical properties with very high gloss and very low haze. Increasing the proportion of the amorphous nylon in the blend, as seen in examples 19-23, exhibits a corresponding increase in 1% secant modulus values and a corresponding decrease in ultimate elongation percentages and transmission of oxygen across the film. A comparison of inventive examples 16-24 shows that shrinkability of the films may be adjusted either by variation of the amount of amorphous nylon is the blend or by changing the composition of one or more of the added layers. All the films of the present invention exhibit good tensile strength and relatively good oxygen barrier properties for nylon films. The results shown in Table 5 demonstrate that biaxially oriented coextruded multilayer films having a nylon blend as specified according to the present invention as an intermediate layer can be successfully made with useful properties and that the properties of these films can be adjusted either by changing the composition of the nylon blend or by varying the type of layer to which the nylon layer is attached. Although three layer film embodiments of the present invention have been described above, these examples are merely illustrative and four or more layer films are contemplated. These multilayer films may be formed by coextrusion In particular, it will be appreciated by one of skill in the art in view of the present disclosure that additional intermediate layers may be provided as desired to achieve additional beneficial or optimum properties or meet performance requirements. These additional intermediate layers need not contain nylon. For example, adhesive layers may be provided or other layers added which provide improved puncture resistance, strength, shrink force, or additional barrier properties. Similarly, outer layers may be formed of a variety of resins or blends e.g. to enhance heat sealability, printability, puncture resistance, or to provide additional barrier properties. Beneficially, in food packaging applications such as for meat or poultry, a thermoplastic film or film layer comprising an amorphous nylon copolymer and copolyamide blend as used according to the present invention will preferably range in thickness from 7.6 to 38 µm (about 0.3 to about 1.5 mils). Thinner and thicker films, while still of the invention, become weaker or more costly, respectively. Generally, in these food packaging applications, multilayer films having sufficient desired properties including strength will be in the range of 38 to 89 µm (1.5 to 3.5 mils). In a preferred multilayer food packaging embodiment, the multilayer film structure utilizes an intermediate layer containing an amorphous nylon copolymer and copolyamide blend which acts as an oxygen barrier layer and comprises about 20 to about 30 percent of the total thickness of the multilayer film. The outer layer adapted for placement adjacent to a food product is generally about 45 to about 55 percent of the total thickness and the opposing outer layer is typically 20 to 35 percent. Generally, in poultry and meat food packaging applications, the outer layer closest to the packaged product must have sufficient thickness to ensure heat sealing integrity; the intermediate barrier layer must be sufficiently thick to provide its gas barrier properties at desired levels; and the outer layer adapted for placement opposite the packaged products must have sufficient thickness to withstand handling and other external forces. However, it is contemplated that those of ordinary skill in the art will readily vary layer and film thicknesses according to particular packaging requirements. Generally, in commercial packaging for cook-in and processed meat applications, films (including multilayer films) desirably have an oxygen permeability value of less than about 4.5 ml/645 cm 2 (100 in. 2 ) in 24 hours at 1.01 bar (1 atmosphere) as measured by ASTM 0-3985-81 in order to protect meat from deterioration due to exposure to oxygen. It is further believed that properties such as high temperature puncture resistance of the inventive multilayer films, may be improved by irradiation and/or crosslinking according to known methods. Preferably, the entire film is irradiated after orientation. A suitable irradiation dosage is irradiation up to 10 Mrad with irradiation from 1 to 5 Mrad preferred. Known irradiation procedures may be utilized. Various procedures are described in U.S. Patent 4,044,187. The multilayer film of this invention is preferably produced by a coextrusion type of double bubble method. The extruder screws and dies used in the examples were standard polyethylene screws and 3.18 cm (1 1/4") dies. These screws and dies were suitable to make films of the present invention. However special screws for use with polyamide (nylon) resins are commercially available and may provide enhanced performance as may other commercially available dies. The multilayer film of the invention may be wound up as flattened, seamless, tubular film to be used later to make bags. Bags having end seals are typically made by transverse heat sealing across the width of flattened tubing followed by severing the tubing so that the transverse seal forms the bag bottom. Alternatively, side-seal bags may be formed in which the transverse seals form the bag sides and one edge of the tubing forms the bag bottom. Various conventional additives such as processing aids slip agents, anti-block agents, plasticizers and pigments can be incorporated into multilayer films of this invention, as is well-known in the art. The above examples serve only to illustrate the invention and its advantages, and they should not be interpreted as limiting since further modifications of the disclosed invention will be apparent to those skilled in the art. All such modifications are deemed to be within the scope of the invention as defined by the following claims.

Claims: A thermoplastic flexible coextruded biaxially oriented heat shrinkable multilayer film comprising a first outer layer, a second outer layer, and at least one intermediate layer between said first outer layer and said second outer layer, said intermediate layer comprising a nylon blend containing (a) 10 to 70 weight percent of an amorphous nylon copolymer having no measurable melting point or no heat of fusion (less than 2.1 J/g (0.5 cal/g)) as measured by differential scanning calorimetry (DSC) using ASTM 3417-83, said amorphous nylon copolymer comprising hexamethyleneisophthalamide/hexamethyleneterephthalamide copolymer provided that said amorphous copolymer is not present in an amount of from 60 to 90 weight percent of said blend; and (b) 10 to 90 weight percent relative to the total weight of the blend of a copolyamide having a melting point within a range of from 145 °C to 215 °C, said copolyamide comprising a copolymer of nylon 6 and nylon 12 or a copolymer of nylon 6 and nylon 66 or mixtures of said copolymers, and said first and/or said second outer layer comprising ethylene vinyl acetate copolymer, very low density polyethylene or mixtures thereof. An oriented multilayer Film according to claim 1, wherein said nylon containing layer further comprises 10 to 30 weight percent of a polyamide homopolymer. An oriented multilayer film according to claim 2, wherein said polyamide homopolymer comprises nylon 6, nylon 11 or nylon 12. An oriented multilayer film according to any of claims 1 to 3, wherein said film has a shrinkage value of at least 20 % in both the machine direction and the transverse direction. An oriented multilayer film according to any of claims 1 to 4, wherein said film is irradiated at a dosage of 1 to 5 mrad. An oriented multilayer film according to any of claims 1 to 5, wherein said film has an O 2 permeability of less than 4.5 cm 3 /6.45-10 -2 m 2 in 24 h at 1.01 bar (4.5 cc/100 in. 2 in 24 hrs. at 1 atmosphere) as measured by ASTM D-3985-81. An oriented multilayer film according to any of claims 1 to 6, wherein said film is a three layer tubular film and said first outer layer is a heat sealable layer. An oriented multilayer film according to any of claims 1 to 7, further comprising, in said nylon blend, an additional nylon 6/12 copolyamide having a melting point less than 145 °C. An oriented multilayer film according to any of claims 1 to 8, wherein said film comprises a tubular casing.

Inventors: VICIK STEPHEN JAMES, VICIK, STEPHEN JAMES
Applicants: VISKASE CORP, VISKASE CORPORATION
Application year: 1989
Main classification: C08L77
IPC codes: C08L77, B32B27