CA1340037C

CA1340037C - Puncture resistant, heat-shrinkable films containing very low density polyethylene copolymer

Info

Publication number: CA1340037C
Application number: CA000506172A
Authority: CA
Inventors: Stanley Lustig; Nancy Marie Mack; Jeffrey Michael Schuetz; Stephen James Vicik
Original assignee: Union Carbide Corp
Current assignee: Curwood Inc
Priority date: 1985-06-17
Filing date: 1986-04-09
Publication date: 1998-09-08
Anticipated expiration: 2015-09-08
Also published as: GB8614347D0; US4863769A; US5439717A; US5256428A

Abstract

Heat-shrinkable films suitable for packaging food articles such as frozen poultry, primal meat cuts, and processed meat products. In one embodiment, the film may be a biaxially stretched monolayer film of a very low density polyethylene copolymer (ethylene copolymerized with higher alpha olefins containing 3 to 8 carbon atoms such as propylene, butene, pentene, hexene, heptene and octene).
In another embodiment, the film may be a biaxially stretched multilayer film comprising a first outer layer of an ethylene-vinyl acetate copolymer, a core layer of a barrier film such as a polyvinylidene chloride copolymer or an ethylene-vinyl alcohol copolymer, and a second outer layer comprising a blend of an ethylene-vinyl acetate copolymer and a very low density polyethylene copolymer.
The multilayer film is preferably made by coextrusion of the layers. The films are fabricated into bags useful for the aforementioned purposes. The bags have improved toughness.

Description

13~û037 -PUNCTURE RESISTANT. HEAT-SHRINKABLE FILMS
CO~TAINING VERY LOW DENSITY POLYETHYLENE COPOLYMER

Field of the Inventlon This inventlon relates to puncture resistant, heat-shrinkable films, and more part.icularly, to such films having high flexibility over a wide temperature range, and excellent stress crac:k resistance. The films contain very low density polyethylene copolymers.

Back:~round of the Invention The packaging of food articles such as poul.try, fresh red meat, and processed meat products requires tough, puncture resistant, yet flexible, film materisls. It ls also desirable that the film materials be suitable for use in fabricating bags for packaging such food articles by the shrink wrapping method. Generally, the shrink wrapping methlod is predicated upon the heat-shrinking proplerty of the bag l~y placing a given food article or articles into the bag, and thereafter exposing the bag to a heat sol~rce such as a flow of hot air, infrared radiation, hot water, and the like, thereby causing the bag to shrink and come into intimate contact with the contours of the food article or articles. The packaged article prepared by this pack.aging method has an attractive appearance which adds to the csmmod~ty value of the wrapped article , The contents of the ,package are kept in a hygienic conclition, and shoppers are allowed to examlne the qua].lty of the contents of the package.

2 1~ ~ 0 037 For example, in commercial poultry packaging operations, monolayer films made from polyethylene or ethylene-vinyl acetate copolymers, and multilayer films containing ethylene-vinyl acetate copolymers are ut:ilized extensively. Likewise, in the packaging of fresh red meat and processed meat products, multilayer heat-shrinkable films containing ethylene-vinyl acetate copolymers in one or more layers of the films are commonly employed. Ethylene-vinyl acetate copolymers lo have been commonly employed in such applications because of their toughness and low temperature shrinking characteristics. However, film materials in one or more fi:Lm layers which possess the shrinking characteristics of ethylene-vinyl acetate copolymers but provide additional toughness are generally very expensive mat:erials, such as ionomers or polyurethanes. Even tougher film materials are desired for varied packaging applications, but h,eretofore they have not been available.

In providing such film materials, however, it must be remembered that the film material must be stretchable in order to provide a shrinkable film that will heat-shrink within a specified range of percentages, e.g., from about 30 to 50 percent at 90~C in both the machine ancl the transverse directions. Further, the film must be heat sealable so as to enable bags to be fabricated from the film, and the heat sealed seams must not pull apart during the heat shrinking operation. In addition, the film must resist puncturing by sharp edges, such as bone edges, during lthe heat-shrinking operation; and oa37 there must be adequate adhesion between the several layers of a multilaye:r film so that delamination does not occur, either during the heat-shrinking operation, or during exposure of the film to the relatively high temperatures that may be reached during shipping and storage of the film ir~L the summertime.
Accordingly, although the known films meet many of the requirements for packaging applications, the need stil]. exists for improved heat-shrinkable films and bags fabricated therefrom.
Summary of the Invent:ion In accordance wilh an aspect of the present invention, there is provided a biaxially stretched, heat-shrinkable, thermoplastic film comprising very lowdensi.ty polyethylene copolymer. The very low density polyethylene polymer consists of ethylene copolymerized with higher alpha olefins containing from 3 to 8 carbon atoms such as propylene, butene, pentene, hexene, heptene, and octene. These ethylene copolymers have a densi.ty below about 0.91 g/cm3 and a 1% secant modulus below about 140,000 k}?a, and preferably have a density of from about 0.86 g/cm3 to about C.91 g/cm3 and a 1% secant modulus of from about 600 kPa to about 100,000 kPa.
Further, the ethylene copolymers have a standard or norma,l load melt index of up to about 25.0 g/10 minutes, and preferably of frorn about 0.2 g/10 minutes to about 4.0 g/10 minutes. In addition, the ethylene copolymers have a high load melt index (HLMI) of up to about 1000 :30 g/10 minutes.
Other aspects of this invention are as follows:
A heat-shrinkable, biaxially stretched, multi-layer thermoplastic fiLlm suitable for use in fabricating bags for packaging priLmal meat cuts and processed meat :35 products; said film comprising a first outer layer of an ethylene-vinyl acetate copolymer; a core layer comprising 13~0037 - 3a -a barrier film; and a second outer layer comprising a blend of an ethylene-vinyl acetate copolymer and a very low density polyethyle!ne copolymer comprising ethylene copolymerized with higher alpha olefins containing from 3 to 8 carbon atoms, whe!rein said film heat-shrinks from about 30 percent to about 50 percent at a temperature of about 90~C.
A heat-shrinkable!, puncture-resistant, biaxially stretched, thermoplast.ic film suitable for use in fabricating bags for packaging food articles such as frozen poultry, said fiilm having at least one layer comprising a very low density polyethylene copolymer, comprising ethylene copolymerized with higher alpha olefins containing from 3 to 8 carbon atoms, wherein said film heat-shrinks to the extent of at least 30 percent at a temperature of about 90~C.
A method of manufacturing a heat-shrinkable, puncture resistant, biaxially stretched, thermoplastic film comprising the steps of extruding a primary tube comprising a very low density polyethylene which is a linear copolymer of ethylene and higher alpha olefin containing from 3 to 8 carbon atoms, having a density below about o.9l g/cm3 and a 1~ secant modulus below about 140,000 kPa; heating the very low density polyethylene primary tube; biaxially stretching the heated primary tube using a double bubble method under conditions wherein the biaxially stretched tube is heat shrinkable from about 30% to about 50% at a temperature of about 90~C. in at least one of the transverse and machine directions.
.~ heat-shrinkable, puncture resistant, biaxially stretched, thermoplastic film suitable for use in fabricating bags for packaging food articles such as frozen poultry, said film comprising a very low density polyethylene which is a linear copolymer of ethylene and 13~0~37 - 3b -higher alpha olefin containing from 4 to 8 carbon atoms havin.g a density below about 0.91 g/cm3, a 1%
secan.t modulus below about 140,000 kPa, and said film being formed using a clouble bubble method and wherein said film heat-shrinks from about 30 percent to about 50 percent at a temperature of about 90~C, in at least one of the machine and transverse directions.
A heat-shrinkable, biaxially stretched, multilayer thermoplastic film sui.table for use in fabricating bags for packaging food art:icles wherein at least one layer of said multilayer film comprises a blend of very low density polyethylene which is a linear copolymer of ethylene and higher alpha olefin containing from 4 to 8 carbon atoms having a density below about 0.91 g/cm3 and a 1% secant modulus below about 140,000 kPa, and an ethylene-vinyl acetate copolymer, said multilayer film being formed using a clouble bubble method and wherein said film heat-shrinks from about 30 percent to about 50 percent at a temperature of about 90~C. in at least one of the mlachine and transverse directions.
A method of manuf.acturing a heat-shrinkable, puncture resistant, bi.axially stretched, thermoplastic film comprising the st:eps of extruding a primary tube comprising a very low density polyethylene which is a linear copolymer of et:hylene and higher alpha olefin containing from 4 to E, carbon atoms, having a density below about o.9l g/cm3 and a 1% secant modulus below about 140,000 kPa; heating t.he very low density polyethylene primary tube; biaxiall.y stretching the heated primary tube using a double bubble method under conditions wherein the biaxially stretched tube is heat shrinkable from about 30% to about 50% at a temperature of about go~C. in at least one of the transverse and machine directions.

~ 4 ~ 1340~X7 Detailed DescriPtion of the Invention More particularly, the ethylene copolymers employed ln the film materials of the instant invention are preferably prepared in a fluidized bed polymerization process by continuously contacting, in such fluidized bed, at a temperature of from 10~C
up to 80~C, a gaseous mixture containing (a) ethyLene and at least one higher slpha olefin in a molar ratio of such higher alpha olefin to ethylene of from 0.35:1 to 8.0:1, and (b) at least 25 mol perccnt of a diluent gas, with a catalyst composition prepared by forming a precursor compositlon from a magnesium compound, titanium comp~Dund, and electron donor compound; diluting said precursor composition with an inert carriet; and activating the dilute!d precursor composition with an organosluminum compound.
Fluid bed reactors suitable for continuously preparing ethylene copolymers have been previously described snd are well known in the art.
Fluid bed reactors useful for this purpose are described, e.g., in ll.S. patents 4,302,565 and 4,302,566. Said patents likewise disclose catalyst compositions sultable for preparing such copolymers.
In order to produce ethylene copolymers having a density below 0.91 g/cm3 by means of a fluid bed process, ilt is necessary to employ gaseous reaction mixtures containing higher amounts of highler alpha olefin comonomer vis-a-vis the amount of e!thylene employed, than are employed to produce copolymers having a density grester than 0.91 g/cm . By the addition of progressively larger _ 5 - 1340~31 amounts of such higher olefin to the mixture, copolymers hsving proKresslvely lower densities are obtained at any given melt index. The smount of higher olefin needed to achleve copolymers of a given density wlll vary from olefin to olefin, under the same conditions, with larger amounts of such higher olefin required as the number of carbon atoms in the olefin decreases. Generally, in order to produce copolymers having a density of less than 0.91 glcm , lt is necessary to employ reaction mixtures containing such higher olefin and ethylene in a molar ratio of higher olefln to ethylene of at least 0.35:1. Usually, mixtures containing such higher olefin and ethylene in a molar ratio of from 0.35:1 to 8.0:1 are employed for this purpose, with molar ratios of from ().6:1 to 7.0:1 being preferred.
The higher alpha olefins which can be polymerized with ethylene to produce the low density, low modulus copolymers of the pre~ent invention can contain from 3 to 8 carbon atoms.
These alpha oleflns should not contain any branching on any of their carbon atoms closer than two carbon atoms removed from the double bond. Suitable alpha olefins include propylene, butene-l, pentene-l, hexene-l, 4-methylpentene-1, heptene-l and octene-l. The preferred alpha olefins are propylene, butene-l, hexene-l, 4-methylpentene-1 and octene-l.
If desired, one or more dienes, either con~ugated or non-conlugated, may be present ln the reaction mixture. Such dienes may be employed in an amount of from 0.1 mo'L percent to 10 mol percent of - 6 - 1340~37 the total gsseous mixture fed to the fluld bed, and sre prefersbly present in an amount of from 0.1 mol percent to 8 mol percent. Such dienes msy lnclude, for example butadiene, 1,4-hexsdiene, 1,5-hexsdiene, vinyl norbornene, ethylidene norbornene and dicy~clopentsdiene.
In order to prevent the formation of poly~mer ~gglomerstes snd sustain polymeri2stion on a cont.inuous basis, when employing resction mixtures cont.sining the high ~ratios of higher alphs olefin comc,nomer to ethylene which sre required to produce the desired copolymers hsving 8 density below 0.91 g/cm3, it hss been found necessary to dilute the resc:tion mixture with a lsrge quantity of a diluent gss. Dilution of the reaction mixture with a diluent gas in this l~nsnner serves to reduce the tsc~iness of the polymers produced, which is the main cause of such agglomeration. Ordinsrily the diluent gas should make up st lesst 25 mol percent of t:he total gaseous mixture fed to the fluid bed in order to prevent such agglomerstion. Prefersbly, the gsseous mixture contsins from 33 mol percent to 95 mol percent of such gss, and most pre~ersbly from 40 mol percent to 70 mol percent. By a "diluent"
gas is mesnt 8 gss which is nonresctlve under the conditions employed in the polymerizstion reactor, i.e.., does not decompose and/or resct with the polymerizable monomers snd the components of the cst~llyst composition under the polymerizstion conditions employed in the reactor, other than to terrninate polynner chsin growth. In sddition, such gss should be insoluble in the polymer product 13'10d37 ' produced ~o as not to contrlbute to polymer tackiness. Among such gases are nitrogen, argon, helium, methane, ethane, and the like.
Hydrogen may also be employed as a diluent gss. In such event, the diluent serves not only to dilute the reaction mixture snd prevent polymer agglomeration, but also acts as a chain transfer agent to regulate the melt index of the copolymers produced. Generally, the reaction mixture contains hydrogen in an amount sufficient to produce 8 hydrogen to ethylene mol ratio of from 0.01:1 to 0.5:1. In addition to hydrogen, other chain transfer agents may be employed to regulate the melt index of the copolymers.
The gaseous reaction mixture should, of course, be substantially free of catalyst poisons, such as moisture, oxygen, carbon monoxide, carbon dioxide, acetylene and the like.
In sddition to diluting the reaction mixture with a diluent gas, it is necessary to maintain a relatively low temperature in the reactor in order to prevent polymer agglomeration and sustain polymerization on a continuous basis. The temperature which can be employed varies directly with the concentration of diluent gas present in such mixture, with higher concentrations of diluent gas permitting the use of somewhat higher temperatures without adverse effects. Likewise, the lower the concentration of the higher alpha olefin comonomer in the reaction mixture vis-a-vis the ethylene concentration, i~e., the higher the density and modulus of the copolymer being produced, the - 8 - 13'~0037 -higher the temperature which csn be employed.
Genecally, however, in order to continuously produce copolymers hsving a density below 0.91 g/cm3 and a 1~ secant modulus below 140,000 kPa while at the same time preventing polymer agglomeration, the temp*rature should not be permitted to rise above 80~C. On the other hland, the temperature employed must be sufficiently elevated to prevent substantial cond~ensation of the reaction mixture, including dilulent gas, to the liquid state, as such condensation will cause the polymer particles being produced to cohere to each other and likewise aggrQvate the polymer agglomeration problem. This difficulty is normally associated with the use of alpha olefins having S or more carbon atoms which have relstively high dew points. While some minor condensation is tolerable, anything beyond this will cause reactor fouling. Usually temperatures of from 10~C to 60~C are employed to produce copolymers having a density of from 0.86 g/cm3 to 0.90 g/cm3 and a secant modulus of from 600 kPa to 100,000 kPa. More elevated temperatures of from 60~C up to 80~C are ordinarily employed in the production of copolymers having a density of from 0.90 g/cm3 up to 0.9] g/cm3 and a 1~ secant modulus of from 100,000 kPa up to 140,000 kPa.
Pressures of up to about 7000 kPa can be employed in preparin~s the copolymers, although pressures of from about 70 kPa to 2500 kPa are preferred.
In order to maintain a viable fluidized bed, the superficial gas velocity of the gaseous .~, . , , . , . . . " . ", . . ., .. , .. .. " .. . , ," , .

g i~40037 reaction mixture through the bed must exceed the minimum flow requlrecl for fluidization and prefersbly is at least 0.2 feet per second above the minimum flow. OrdinHrily the superficial gas velocity does not exc:éed 5.0 feet per second, and most usually no more than 2.5 feet per second is sufficient.
The catalysl: compositions employed in preparing the copolymers are produced by forming a precursor composition from a magnesium compound, titanium compound, and electron donor compound;
diluting said precursor composition with an inert carrier; and activating the diluted precursor composition with an organoaluminum compound.
The precursor composition is formed by dissolving at least one titanium compound and at least one magnesium compound in at least one electron donor compound at a temperature of from about 20~C up to the boiling point of the electron donor compound. The titanium compound(s) can be added to the electron donor compound(s) before or after the addition of the magnesium compound(s), or conc.urrent therewith.. The dissolutlon of the titanium compound(s) and the magnesium compound(s) can be facilitated by stirring, and in some inst.ances by refluxing these two compounds in the elec:tron donor compound(s). After the titanium compound(s) and the magnesium compound(s) are dissolved, the precursor composition may be isolated by c:ryst~llization or by precipitation with an aliphatic or aromatic hydrocarbon containing from 5 to E~ carbon atoms, such as hexane, isopentane or - lO - 1~0~37 benzlene. The crystallized or precipitsted precursor composition may be isolated in the form of flne, free-flowing particles having an average particle size of from about 10 microns to about 100 microns after drying at temperatures up to 60~C.
About 0.5 mol to about 56 mols, and preferably about 1 mol to about 10 mols, of the magnesium compound(s)l are used per mol of the titanium compound(s) in preparing the precursor composition.
The titanium compound(s) employed in preparing the precursor composition has the structure Ti(OR)~Xb wherein R i~ an aliphatic or aromatic hydrocarbon radical c:ontaining from 1 to 14 csrbon atoms, or COR' where R' is an aliphatic or aromatic hydrocarbon radical c:ontsining from 1 to 14 carbon atoms.
X is selected from the group consisting of Cl, Br, I, and mixtures thereof.
a is 0, 1 or 2, b is 1 to 4 inclusive, and a + b = 3 or 4.
Suitable tit;anium compounds ~nclude TiC13, TiC14, Ti(OCH~)C13, Ti(OC6H5)C13, Ti(OCO(,H3)C13 and Ti(OCOC6H5)C13. TiC13 is preferred because catalysts cont~ining this material show higher activity st the low 1;emperatures and monomer concentrations employed in prep~ring the copolymers.
The magnesium compound(s) employed in preparing the precursor composition has the structure MgX2 wherein X is selected from the group consisting of Cl Br I snd mixtures thereof.
Suitable magnesium compounds include MgCl! MgBr2 and MgI2. Anhydrous MgCl~ i8 particularly preferred.
The electron donor compound(s) employed in preparing the precursor composition is an organic compound which is liquid at 25~C snd in which the titanium ~nd magnesium compounds are soluble. The elec1:ron donor compounds are known as such or as Lewi-; bases.
Suitable electron donor compounds include the alkyl esters of aliphatic snd sromatic carboxylic acids aliphatic ethers cyclic ethers snd ~liphatic ketones. Among these electron donor compounds those preferred are alkyl esters of ssturated aliphatic carboxylic acids containing from l to 4 carbon atoms; alkyl esters of aromatic carboxylic acids containing from 7 to 8 carbon atoms; aliphstic ethers containing from 2 to 8 carbon atoms but preferably from 4 to 5 carbon atoms; cyclic ethers containing from 4 to 5 carbon atoms but preferably mono- or di-ethers containing 4 carbon atoms; and aliphatic ketones containing from 3 to 6 carbon atoms but preferably from 3 to 4 carb~n atoms. The most preferred of these electron donor compounds include methyl formate~ ethyl acetate butyl acetate ethyl ether tetrahydrofuran dioxane acetone snd methyl ethyl ketone.
After the precursor composition has been prepared it is diluted with sn inert csrrier - 12 - ~34Q037 material by (1) mech~nically mixing or (2) impregnating such composition into the carrier material.
Mechanical mixing of the inert csrrier and precursor composition i8 effected by blending these m~terials together using conventional techniques.
The blended mixture suitably contains from about 3 percent by weight to about 50 percent by weight of the precursor composition.
Impregnation of the inert carrier material with the precursor composition m~y be accomplished by dissolving the precursor composition in the electron donor compounds, and then admixing the support with the dissolved precursor composition to impregnate the support. The solvent is then removed by drying st temperatures up to about 8S~C.
The support may also be impregnated with the precursor composition by sdding the support to a solution of the chemical raw m~terials used to form the precursor composition in the electron donor compound, without isolating the precursor composition from said solution. The excess electron donor compound is then removed by drying at temperatures up to about 85~C.
When thus made a~ disclosed above, the blended or impregnated precursor composition has the formula MgmTi(oR)nxp[ED]q wherein R is an aliphatic or arom~tic hydrocarbon radical containing from 1 to 14 carbon atoms, or COR' where'Ln R' is also an aliphatic or aromatic hydrocarbon radical contsining from 1 to 14 carb~on stoms.
X is selected from the group consisting of Cl, Br, I, and mixtures thereof.
ED is an electron donor compound m is 0.5 to 56, but preferably 1.5 to 5, n is 0, 1 or 2, p is 2 to 116, but prefersbly 6 to 14, and q is 2 to 85, but preferably 3 to 10.
SuitabLy, the impregnated carrier material contains from about 3 percent by weight to about 50 percent by weight, but preferably from about 10 percent by weight to about 30 percent by weight, of the precursor composition.
The carrier materials employed to dilute the precursor composition are solid, particulate, poro,us materials which are inert to the other comp~onents of the catalyst composition, and to the othe!r active components of the reaction system.
These carrier materials include inorganic materials suchl as oxides of siLicon and/or aluminum. The carrier materials are used in the form of dry powdlers having an average psrticle size of from about 10 microns to about 250 microns, but preferably from about 20 microns to about 150 microns. These materials are also porous and have a surface ~rea of at least 3 square meters per gram, and preferably at least 50 square meters per gram.
Catalyst activity or productivity can apparently be - 14 - 134 no3 7 improved by employing a sllica support having average pore sizes of at least 80 Angstrom units, but prefersbly at least 100 Angstrom units. The carrier material should be dry, that is, free of absorbed water~ Drying of the carrier msterial can be effected by heating, e.g., at a temperature of at least 600~C when silica is employed as the support.
Alternatively, when silica is employed, it may be dried at 8 temperature of at least 200~C and treated with about 1 weight percent to about 8 weight percent of one or more of the aluminum activator compounds described below. Modification of the support with an aluminum compound in this manner provides the catalyst composition with increased activity and also improves polymer particle morphology of the resulting ethylene copolymers.
Other organometallic compounds, such as diethylzinc, may also be used to modify the support.
To be useful in producing the ethylene copolymers, the precursor composition must be activated with a compound capable of transforming the titanium atoms in the precursor composition to a ~tate which will cause ethylene to effectively copolymerize with higher alpha olefins. Such activation is effected by means of an organoaluminum compound having the structure Al(R'')dX'eHf wherein X' is Cl or OR'''.
R'' and R "' are saturated hydrocarbon radicals containing from 1 to 1~ carbon atoms, which radicals may be the same or different.

- 15 - 1 3~ 003 7 e is 0 to 1.5, f is 0 or 1, and d + e + f = 3.
Such activator compounds can be employed individually or in combinstion thereof snd include compounds such ss Al(C2H5)3, Al(C2H5)2Cl, 2 2 5)3C13, Al(C2Hs)2H~ Al(c2H5)2(oc2H5) Al(i-C4Hg)3. Al(i-C4Hg)2H, Al(C6H13)3 and Al(C8H17)3.
If desired, the precursor composition msy be partially sctivsted before it is introduced into the polymerizstion resctor. However, sny activ~tion undertsken outside of the polymerizstion resctor should be limited to the addition of an amount of activator compound which does not raise the molsr ratio of activator compound electron donor in the precursor composition beyond 1.4:1. Preferably, when sctivation is effective outside the reactor in this manner, the activator compound is employed in sn smount which will provide the precursor composition with an activstor compound:electron donor molsr rstio of from sbout 0.1:1 to about 1.0:1. Such psrtial sctivstion is csrried out in 8 hydrocsrbon solvent slurry followed by drying of the resulting mixture to remove the solvent st temperstures of from sbout 20~C to sbout 80~C., and preferably from sbout ~0~C to sbout 70~C. The resulting product is a free-flowing solid psrticulate msterisl which csn be resdlly fed to the polymerizstion resctor where the sctivation is completed with sdditional sctivator compound which csn be the ssme or a different compound.

- 16 - ~3~0037 Alternatlvely, when an impregnated precursor composition ls employed, lt may, lf desired, be completely sctivated in the polymerlzatlon reactor wlthout any prlor actlvatlon outslde of the reactor, ln the manner descrlbed ln European pstent publicstion No. 12,148.
The partially sctlvated or totslly unactivated precursor composltion and the requlred amount of activator compound necessary to complete activstion of the precursor composition are preferably fed to the reactor through separate feed lines. The activator compound may be sprayed lnto the reactor in the form of a solution thereof in a hydrocarbon solvent such as isopentane, hexane or mineral oil. This solution usually contains from about 2 weight percent to sbout 30 weight percent of the activstor compound. The sctivator compound is added to the reactor in such amounts as to provide, in the reactor, a total aluminum:titanium molar ratio of from about 10:1 to about 400:1, and preferably from about 25:1 to about 60:1.
In the continuous gas phase fluid bed process, discrete portions of the psrtisll,y activated or totally unactivated precursor composition are continuously fed to the reactors, together with discrete portions of the activstor compound needed to complete the activation of the psrtially activated or totally unactivated precursor compositlon during the continuing polymerization reaction in order to replace active catalyst sites that are expended during the course of the reaction.

17 1~0037 By operating under the polymerization conditions de~cribed herein, and more fully di~closed by F.J. Karol et al in European patent publication No. 0120503 published October 3, 1984 titled UPreparation of low density, low moduluc ethylene copolymers in a fluidized bed", it iB pos~ible to continuously polymerize ethylene in a fluidized bed with one or more higher alpha olefins containing from 3 to 8 carbon atoms, and optionally also with one or more dienes, to produce ethylene copolymers having a density below 0.91 g/cm3 and a 1% secant modulus below 140,000 kPa. By "continuously polymerize", as used herein, is meant the capability of uninterrupted polymerization for weeks at a time i.e., at least in exce~s of 168 hours and usually in excess of 1000 hours, without reactor fouling due to the production of large agglomerations of polymer.
The copolymers produced in accordan¢e with the aforedescribed process usually have a density of from 0.86 g/cm3 to 0.90 g/cm3 and a 1% secant modulus of from 600 kPa to 100,000 kPa. Such copolymers contain no more than 94 mol percent of polymerized ethylene and at least 6 mol percent of polymerized alpha olefin containing from 3 to 8 carbon atoms and, optionally, polymerized diene. When polymerized diene is present, the polymer contains from 0.01 mol percent to 10 mol percent of at least one such diene, from 6 mol percent to 55 mol percent of at least one polymerized alpha olefin containing from 3 to 8 carbon atoms, and from 35 mol percent to 94 mol percent of polymerized ethylene.

- 18 - 13~0037 The molar ratios of propylene to ethylene which must be employed in the reaction mixture to produce copolymers having a given propylene content are illustrated in Table 1 below. When alphs olefins higher than propylene are employed, like results can be obtained with lower ratios of such higher alpha olefin to ethylene in the reaction mixture.

C3H6/C2H4Ratio Mol ~ C3H6 Mol % C2H4 In Reaction Mixture In CoPolYmer In CoPolYmer 0.7 6 94 1.5 12 88 3.0 25 75 6.0 50 50 8.0 62 38 The ethylene copolymers produced in accordance with the aforedescribed process have a standard or normal load melt index of from greater than O g/10 minutes to about 25.0 g/10 minutes, and preferably of from about 0.2 g/10 minutes to about 4.0 g/10 minutes. Such polymers have a high load melt index (HLMI) of from greater than O gllO
minutes to about 1000 g/10 minutes. The melt index of a polymer varies inversely with its molecular weight and is a function of the polymerization temperature of the reaction, the density of the polymer, and the hydrogen/monomer ratio in the reaction system. Thus, the melt index is raised by increasing the polymerization temperature, by increasing the ratio of higher ~lpha olefin to ethylene in the reaction system, and/or by increasing the hydrogen/monomer ratio.

- 19 - 13~0~37 The ethylene copolymers produced in accordance with the aforedescribed process have a melt flow ratio (MFR) of from about 22 to about 40, and preferably of from about 26 to about 35. Melt flow ratio is another means of indicating the molecular welght distribution (MW/Mn) of a polymer. A MFR in the range of from about 22 to about 40 corresponds to a MW/Mn of from about 2.7 to about 6.5, snd a MFR in the range of from sbout 26 to about 35 corresponds to a MW/Mn of from about 2.9 to about 4.8.
The ethylene copolymers produced, typically, have a residual catalyst content, in terms of parts per million of titanium metal, of less than 10 parts per million (ppm) at a productivity level of at least 100,000 pounds of polymer per pound of titanium. The copolymers are readily produced with such catalyst compositions at productivities of up to about 500,000 pounds of polymer per pound of titanium.
The ethylene copolymers are granular materisls hsving an ~verage particle size on the order of from about 0.01 to about 0.07 inches, and usually of from sbout 0.02 to about 0.05 inches in diameter. The psrticle size is important for the purpose of resdily fluidizing the polymer particles in the fluid bed reactor. These granular materials also contain no more than 4.0 percent of fine particles having a diameter of less thsn 0.005 inches. The ethylene copolymers typicslly have a bulk density of from sbout 16 pounds per cubic foot to about 31 pounds per cubic foot.

- - 20 - 13~037 The properties of the ethylene copolymers are determined by the following test methods:
DensitY
ASTM D-1505. A pl~que is made and conditioned for one hour at 100~C to approach equilibrium crystallinity. Measurement for density is then made in a density gradient column and density values are reported as grams/cm3.
Melt Index (MI) ASTM D-1238, Condition E. Measured at 190~C
and reported as grams per 10 minutes.
Flow Index (HLMI) ASTM D-1238, Condition F. Measured at 10 times the weight used in the melt index test above.
Melt Flow Ratio (MFR) Ratio of Flow Index : Melt Index Bulk DensitY
ASTM D-1895, Method B. The resin is poured via a 3/8" diameter funnel into a 400 ml graduated cylinder to the 400 ml line without shaking the cylinder, and weighed by difference.
Avera~e Particle Size Calculated from sieve analysis data measured according to ASTM D-1921, Method A, using a 500 g sample. Calculations are based on weight fractions retained on the screens.

Molecular Weight Distribution, ~ /Mn Gel Permeation Chromatography. Styrogel column packing: (Pore size packing sequence is - 21 ~ 003 7 107, 105, 104, 103, 60A~). Solvent is perchloroethylene at 117~C. Detection: lnfrared at 3.45~.
!

1~ Secant Mod~lus ASTM D-638. Film strips 10" x 0.5" sre clamped at a 5 inch gauge length and deformed at a ~aw separatlon rate of 0.2 in./min. A force elongation trace is determined. Secant modulus is the slope of a line drawn from the origin to the load at 1~ deformation. Deformation is determined by crosshead position. Normalizing by the specimen's undeformed cross-sectional area, secant modulus is reported in kPa.
In general, it has been found that when the very low density ethylene copolymers are formed into films, and the films are biaxially stretched, the stretched films provide exceptionally high shrinkage values at elevated temperstures, for example, such as st about 90~C, compared to films made from ethylene-vinyl acetate copolymers. The biaxially stretched, very low density ethylene copolymer films of this invention heat-shrink from about 30 percent to about 50 percent at a temperature of about 90~C
in both the machine direction and transverse direction. Further, stretched films made from very low density ethylene copolymers have excellent tensile, elongation, and puncture toughness properties. Due to these properties, the films are improved materisls for fabricating into bags for packaging food articles such as poultry, primal mest cuts, and processed meat products.

- 22 - 1 3~ o 03 7 Illustrstive, non-limiting exsmples of the festures and practice of the invention are set out below. The psrts and percentages set forth herein refer to parts by weight and percentages by weight, respectively, unless specifically stated otherwise.
In the examples, the following test methods were used to determine the properties of the resins and the films described in Example 1. Tensile strength and elongation at bresk values were obtained pursuant to ASTM Method D-882, procedure A. Density values were obtsined by ASTM Method D-1505. Dynamic puncture vslues were obtained by employing a Dynsmic Bsll Burst Tester, Model 13-8, msnufsctured by Testing Machines, Inc., Amityville, Long Islsnd, NY. A specisl tip designed to simulate a shsrp-boned surfsce wss employed to replace the spherical-shsped impsct hesd of the sppsratus. This modified testing device measured energy in units of kilogrsm-centimeters.
Shrinkage vslues were obtsined by messuring unrestrsined shrink at 90~C for five seconds. In more detail, a 1 or 2 liter beaker is filled with water which is hested to sbout 100~C. Four machine direction (MD) shrinkage test ssmples are cut to 12 cm. mschine direction by 1.27 cm. transverse direction (TD). Four trsnsverse direction shrinksge test ssmples sre cut to 12 cm. trsnsverse direction by 1.27 cm. mschine direction. Both sets of ssmples sre msrked with a short cut exsctly 10 cm. from one end for identification. The water bath temperature is brought to 90~C, and each sample is completely immersed in the wster bsth for five seconds and removed therefrom. After shrinking, the distance between the end of the sample and the 10 cm. mark i8 measured to the close6t 0.1 cm. The difference between the final length and the original 10 cm. is multiplied by 10 to obtain the percent ch~ng9. If the sample shrinks, the value is negative, and if the sample stretches, the value is positive. The average of the four samples is calculated for both of the machine direction and transverse direction samples.

EYaDDle I
This example illustrates the comparative heat-shrinking properties of a very low density polyethylene (VLDPE) film made by (1) the free or simple bubble extrusion process, and by (2) the "double bubbleH method de6crib-d in Pahlke U.S. Patent 3,555,604. The "double bubble" manufacturing method results in a film which has been biaxially stretched. ~ore particularly, in the practice of the Hdouble bubble" method, the primary tube (extrud-d film) is stretched in the machine direction, cooled, reheated, and then ~tretched in the transverse and machine directions. By comparison, in the free or simple bubble extrusion process, the tube is blown and simultaneously stretched in the machine and transverse directions, and then cooled.
The very low density polyethylene material employed to made the films had a den~ity of about 0.906 g./cm3, and a melt index of about 0.88 decigram per minute, and is available from Union Carbide Corporation, Danbury, CT
under the designation UCARTM FLX DFDA-1137. The films made - 24 - 13~fl37 by the simple bubble extrusion process and by the "double bubble" method were evaluated for percent shrinkage at 85~C, 90~C, and 95~C in accordsnce with the aforedescribed test method. The results of these evaluations are summarized below in Table 2.
Table 2 Percent Heat ShrinkaRe of SimPle Bubble and Double Bubble Production VerY Low DensitY PolYethYlene Shrinkage Simple Double TemPerature(~C) Bubble Bubble MD/TD (~) MDtTD (~) 3l3 52/53 It csn be seen from the dsta in Table 2 that the film msde from the very low denslty polyethylene material by the simple bubble extrusion process has very low heat shrinksge properties, whereas the film made by the "double bubble" method hss exceptionslly high shrinkage values for both the machine direction (MD) and the transverse direction (TD) ssmples.
ExamPle II
This exsmple illustrates the comparative properties of a biaxislly stretched very low density polyethylene (VLDPE) film, film A, with those of biaxislly stretched films made from low density polyethylene (LDPE), film B; linear, low density polyethylene (LLDPE), film C; ethylene-vinyl acetate copolymer having a vinyl acetate content of 12 weight percent (EVA-12), film D; ethylene-vinyl - 25 - 1~4~037 acetate copolymer having a vinyl acetate content of 3 weight percent (EVA-3), film E; and an ethylene-methacrylic acid ionic copolymer (ionomer) having 8 melt flow index of about 1.3 g./10 min. and a specific gravity of about 0.94 g./cm3, commercially available as Surlyn 1601 from E.I.
duPont de Nemours and Co., Wilmington, Del., film F. Film A was made from a very low density ethylene copolymer having a density of about 0.90 g./cm3, and a melt index of about 0.84 decigram per minute.
The biaxially stretched monolayer films were made pursuant to the "double bubble" method described in Pahlke U.S. Patent 3,555,604. The bisxially stretched films were evaluated for heat shrink properties, puncture resistance, tensile strength, and elongation. The results of these evaluations are summarized below in Table 3.
Table 3 PhYsical ProPerties of Biaxially Stretched MonolaYer Films Tens;le Resin Melting Shrink S 51ren~th r~ 1. e FiIm Tv~eDbnsitv Melt Indbx Point~~C) ~t 90~C) ~Dsi) Elcnqation ~kq-cm/mil) MD~TD ~S) A VLDPE 0.90 0.84 116 51~54 7650 400 2.4 B LDPE 0.917 0.1 104 18~28 6700 225 0.9 C LLDPE 0.918 0.65 118 18~25 7100 325 1.I
D EVA-12 0.940 0.25 98 37~46 7400 275 2.5 E EYA-~ 0.921 0.25 104 2~/35 8200 210 1.1 F lOhO~ER 0.950 1.3 92 57~65 8640 110 1.

- 26 - l~'iOO37 It can be seen from the data in Table 3 that a biaxially stretched monolayer film made from VLDPE has exceptionally high shrinkage values at 90~C in spite of a relatively high melting point as compared to EVA resins, and slso substantially higher shrinkage values at 90~C compared with LUPE
and LLDPE. The data for films B, C, D, E and F show that the shrlnkage values of the films generally decrease as the melting point of the resins increase, whereas although the melting point of the VLDPE resin (film A) is high, the film has high shrinkage values. In addition, a biaxially stretched monolayer film made from VL~PE has excellent tensile and elongation properties, snd exceptional puncture toughness properties. That is, from the data in Table 3, it can be seen that a biaxially stretched monolsyer film made from VLDPE
has better elongation properties than LDPE, LLDPE, EVA-12, EVA-3, and the instant ionomer material.
For example, the data shows that the VLDPE film may be stretched 400~ or about four times its original length before it breaks. Thus, a biaxially stretched monolayer film made from V~PE has the physical properties which are highly desirable for use as a heat-shrinkable bag for packaging frozen poultry, as well as other products.
ExamPle III
In this exsmple, bags for packaging poultry were evaluated for shrink tunnel performance. All bags were made from films obtained pursuant to the method described in Pahlke U.S. Patent 3,555,604.
The bags designated sample A were msde from a - 27 - ~40037 biaxially stretched monolayer film having a thickness of about 2.25 mils prepared from a VLDPE
resin having a melt index of about 0.14 decigram per minute, and a density of about 0.90 g./cm3. The bags designated sample B were conventional poultry bags employed as controls. The control bags were prepsred from a biaxially stretched monolayer film having a thickness of about 2.25 mils made with a blend containing 85 percent by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 weight percent, and a melt index of 0.25 decigram per minute, and 15 percent by weight of a high density polyethylene having a melt index of sbout 0.15 decigram per minute and a density of about 0.953 gram per cubic centimeter.
The results of the visual screening evaluations are summarized below in Table 4.

- 28 - i~O~'7 Table 4 MonolaYer Film Packa~in~ Test (Shrink Tunnel Performance) Film/PsckaRe APPearance After Shrink Shrink Tunnel Packa~e APPearance SamPle A SamPle B
Temperatwre ProPertY
165~F Shrinkage 6 4 Gloss 7 9 Haze 5 9 175~F Shrinkage 7 5 Gloss 7 9 Haze 5 9 185~F Shrinkage 9 5 Gloss 7 9 Haze 5 9 195~F Shrinkage 9 6 Gloss 7 9 Haze 5 9 205~F Shrinkage 7 7 Gloss 7 9 Haze 5 9 1 = Poor 9 = Excellent: High Shrink, High Gloss, Low Haze ~alues of st least 4 are considered acceptable.

The test results show that the sample A
bags had substantially improved shrinkage properties compared to the sample B bags at shrink tunnel temperatures between 165~F and 195~F, and similsr properties at 205~F. However, their gloss and haze values are somewhat lower than tho~e of the sample B
bags, but these values are still acceptable.

28a It is to be noted that in accordance with an aspect of the present invention there is provided a heat-shrinkable, puncture-resistant, biaxially stretched, thermoplastic film suitable for use in fabricating bags for packaging food articles such as frozen poultry, the film comprising a very low density polyethylene copolymer, wherein the film heat-shrinks to the extent of at least 30%, preferably about 30 to about 50%, at a temperature of about 90~C.

A film embodying the present invention may comprise a monolayer film, as previously described herein.
However, a film embodying the present invention also may comprise a multilayer film. Examples of multilayer films embodying the invention are set out hereinafter.

Exa~Dle IV

In this example, heat-shrinkable biaxially stretched multilayer films were prepared for ~3~00~7 evaluation as bags for packaging primal meat cuts.
The films were evaluated for shtink, tenslle strength, elongation, and puncture resistance properties. The following resin materials were employed to make the films.
EthYlene-vinyl Acetate (EVA) Copolymer 12 weight percent vinyl acetate, 0.25 melt index.
PolyvinYlidene Chloride ~ PYDC ) CoPolymer 84 to 87 weight percent vinylidene chloride, 13 to 16 weight percent vinyl chloride.
Very Low DensitY PolYethylene (VLDPE) CoPolYmer Ethylene copolymer having a density of 0.906 g/cm3, and a melt index of 0.92 decigram per minute.

Table 5 summarizes the re~in compositions employed to make the indicated biaxially stretched multilayer films.

Table 5 Multilayer Film Compositions First Second Outer Layer Core Outer Layer Film (Ba~ Inner LaYer) LaYer (Bs~ Outer LaYer) A (Control) EVA PVDC EVA
B EVA PVDC 9 O~ EVA
1 07. VLDPE
C EVA PVDC 75~ EVA
25~ VLDPE

1~0037 The biaxially stretched multilayer films were produced pursuant to the process disclosed ln U.S. Patent 3,55S,604 by coextrusion through multilayer die and subsequent biaxial stretching o~
the primary tube. The resultant biaxially stretched films had sn average total thickness of about 2.5 mils, wherein the first outer lsyer had an average thicknes~ of about 1.5 mils, the core layer had an average thickness of about 0 35 mil, and the second outer lsyer had an average thickness of about 0.65 mil. The results of the aforementioned evaluations sre shown below in Table 6.
Table 6 PhYsical ProPerties of BiaxiallY Stretched MultilaYer Films Tensile Shrink ~ Strength Elongation at 90~C (psi) (~) Puncture Film MD/TD MD/TD MDITD(cm-k~/mil) A 38/51 6400/9000 195/175 1.4 B 34/53 6900/9200 210/180 1.5 C 41/52 7500/9500 240/195 1.8 It can be seen from the data in Table 6 that a biaxially stretched multilayer fllm comprising ethylene-vinyl acetate outer layer blends containing V~DPE have improved tensile strengths, ultimate elongation snd puncture strength compared with an outer layer containing 100~ ethylene-vinyl acetate copolymer. Thus, a biaxially stretched multilayer fllm made wlth blends of VLDPE ln the outer layer has the properties which are highly desirable for use as a heat-shrinkable bag for packaging fresh red meat and proc~ss~ meat products.
Therefore, the novel film compositions of this invention have been shown to pos~esC the physical properties required for use in packaging food articles such as frozen poultry, primal meat cuts and processed meat products. Furthermore, the film compositions of the present invention also have the tolyhnr~s required during the biaxial stretching process, in order to provide a substantially stable operation with few bubble breaks, while providing a film possessing the requisite physical properties with respect to shrinkage characteristics.
Accordingly, the film compositions of this invention comprise a biaxially stretched very low density polyethylene copolymer. A preferred biaxially stretched monolayer film comprises a very low density polyethylene copolymer having a density of between about 0.86 g./cm.3 and about 0.91 g./cm.3 and a stAn~Ard melt index of up to about 25.0 g./10 minutes because such copolymer provides a film with improved shrinking properties. Such monolayer films are particularly suitable for use in fabricating heat-shrinkable bags for packaging poultry products.
In a further embodiment of the film compositions of this invention, the film composition comprises a biaxially stretched multilayer film containing a very low density polyethylene copolymer having a density of between about 0.86 g./cm.3 and about 0.91 g./cm.3, and a stAnAArd melt index of up to about 25.0 g./10 minutes because these films have l.~
13~0037 improved tensile strengths, ultimate elongation and puncture strength properties, and are heat-shrinkable.
Such multilayer films are especially suitable for use in fabricating heat-shrinkable bags for packaging primal meat cuts and processed meats. For example, the multilayer film composition may comprise a first outer layer of an ethylene-vinyl acetate copolymer; a core layer of a barrier film such as a polyvinylidene chloride copolymer or an ethylene-vinyl alcohol copolymer; and a second outer layer comprising a blend of an ethylene-vinyl acetate copolymer and from between about 5 weight percent and 25 weight percent, but preferably between about 10 weight percent and about 25 weight percent, of a very low density polyethylene polymer as described above.
In accordance with a preferred embodiment of this invention, the first outer layer of the multilayer film is an ethylene-vinyl acetate copolymer containing from about g to about 15 weight percent of vinyl acetate, based on the weight of the copolymer, said copolymer having a standard melt index of between about 0.1 and about 1.0 decigram per minute and being selected from the group consisting of (a) a single ethylene-vinyl acetate copolymer and (b) a blend of ethylene-vinyl acetate copolymers.
The second outer layer of the multilayer film of this invention comprises a blend of a very low density polyethylene polymer and an ethylene-vinyl acetate copolymer selected from the group consisting of (a) an ethylene-vinyl acetate copolymer having a stAn~Ard melt index of from about 0.1 to about 1.0 decigram per minute and a vinyl acetate content of from about 1~40037 3 to about 18 weight percent, and preferably from about 10 to about 15 weight percent, based on the weight of said second ethylene-vinyl acetate copolymer, and (b) a blend of at least two ethylene-vinyl acetate copolymers, wherein one of said ethylene-vinyl acetate copolymers has a st~nA~rd melt index of from about 0.1 to about 1.0 decigram per minute and a vinyl acetate content of from about 10 to about 18 weight percent, based on the weight of said copolymer, and the other ethylene-vinyl acetate copolymer has a standard melt index of from about 0.1 to about 1.0 decigram per minute and a vinyl acetate content of from about 2 to about 10 weight percent, based on the weight of said copolymer. The blend (b) of said at least two ethylene-vinyl acetate copolymers has a vinyl acetate content of from about 3 to about 18 weight percent, and preferably from about 10 to about 15 weight percent, based on the weight of said copolymers.
The heat-shrinkable films of this invention can be produced by known techniques. For example, the multilayer films may be prepared by co-extruding multiple layers into a primary tube, followed by the biaxial stretching of the tube by known techniques. The "double-bubble" technique disclosed in Pahlke U.S. Patent No. 3,456,044, is particularly useful in preparing these films. In addition, after biaxial stretching, the films of this invention may be irradiated to a dosage level of between about l megarad and about 5 megarads, such as by passing the films through an electron beam irradiation unit.

_ 34 - 1~40037 The biaxially stretched, heat-shrinkable, thermoplastic monolsyer film, when employed to fabricate bags for packaging frozen poultry, will generally hsve a thickness of from about 1.5 mils to sbout 2.75 mil~. A film having a thickness of less than about 1.5 mils tends to be physlcally weak for use in the poultry packaging industry, while a film having a thickness greater than about 2.75 mils tends to csuse clipping problems and loss of vacuum in the end use application. A film thickness range of between about 2.0 mils and about 2.4 mils is a preferred balance of these opposing considerations.
The biaxially stretched, heat-shrinkable, thermoplastic multilayer film will generally have a total thickness of from about 1.75 mils to about 3.0 mils. For example, when the multilayer film is a three-lsyer film, the first outer layer will normally have a thickness of from about l.l mils to about 1.6 mils, the core layer will normally have a thickness of from about 0.25 mll to about 0.45 mil;
and the second outer layer will normally have 8 thickness of from about 0.4 mil to sbout l.0 mil.
The thlckness of the first outer layer, which is the inner layer of the bag, should be within the aforementioned range because the sealing and processability properties of the film layer would otherwise be diminished. The thickness of the core layer should be within the above-indicated range because the film would provide inadequate barrier properties if the core layer thickness is less than about 0.25 mil. The upper limit of 0.45 mil for the core layer is primarily due to economic - 35 - ~ ~40037 considerstions. The thickness of the second outer lsyer, which is the outer layer of the bag, is selected in order to provide a total thickness of the multilsyer film in the range of from about 1.75 mils to sbout 3.0 mils. When the total film thickness of the multilayer film exceeds about 3.0 mils, clipping problems are encountered in thst it is difficult to gather together the open end of a bag made therefrom. When the thickness o~ the multilsyer film is less thsn about 1.75 mils, the bag will generally have diminished puncture resistance.
When the core layer of the multilayer film of this invention comprises a polyvinylidene chloride copolymer, it must contsin at least 65 weight percent o~ vinylidene chloride and a maximum o~ 5 weight percent of plasticizer, based upon the weight of the polyvinylidene chloride copolymer.
The remainder o~ the polyvinylidene chloride copolymer is preferably vinyl chloride, but it may also include acrylonitrile, an acrylate ester such as methyl methacrylste, or the like. More preferably, the polyvinylidene chloride copolymer will contsin at least about 70 weight percent, snd not more than about 95 weight percent, o~
polymerized vinylidene chloride because when the polyvinylidene chloride copolymer contains less than about 70 weight percent vinylidene chloride the oxygen barrier property o~ the copolymer is diminished. I~ the vinylidene chloride content is more than 95 weight percent, the polyvinylidene chloride copolymer is generally not extrudable. The -36- 13~0037 polyvinylidene chloride copolymer preferably contains less than 5 weight percent plasticizer, and more ~rer~ably less than 4 weight percent plasticizer, the percentages being based on the weight of the total blend, including the copolymer and all additives such as the plasticizer, in order to 5 maximize the barrier properties of the thin film. Conventional plasticizers such as dibutyl sebacate and epoxidized soybean oil can be used.
After biaxial stretching by any suitable method well known in the art, in order to provide improved heat sealing characteristics thereto, the films of this invention are preferably irradiated to a dosage level of between about 1 10 megarad and about 5 megarads, and preferably between about 2 megarads and about 3 megarads, by a suitable method such as by employing an electron beam. Irradiation at a dosage level within this range is necessary in order to achieve improved heat sealing characteristics without film discoloration. That is, when the energy level is below the indicated range, the 15 cross-linking obtained is not sufficient to improve the heat sealing characteristics of the films or to have any enhanced effect upon the toughness properties of the films. When the energy level is above the afore-menffoned range, film discoloration occurs due to degradation of some layers, particularly when a core layer of polyvinylidene chloride copolymer is 20 present. Additionally, when the energy level of irradiation exceeds about 5 megarads, the degree of film shrinkage is significantly reduced, and further mprovements In . ~-.
,.~

13~0o~7 the heat sealing characteristics snd toughness propertles of the film are not achieved.
In another aspect of this invention, bags suitable for the shrink-packaging of food articles such as poultry, primal meat cuts, and processed meats are provided from the afore-described films.
The bags are produced from the monolayer and multilayer films of this invention by heat sealing.
For instance, if the films of this invention are produced in the form of tubular film, bags can be produced therefrom by heat sealing one end of a length of the tubular film or by sealing both ends of the tube end, then slitting one edge to form the bag mouth. If the films of this invention are made in the form of flat sheets, bags can be formed therefrom by heat sealing three edges of two superimposed sheets of film. When carrying out the heat sealing operation, the surfaces which are heat sealed to each other to form seams are the aforedescribed first outer layers of the multilayer films of the invention. Thus, for example, when forming a bag by heat sealing one edge of a length of tubular film, the inner surfsce of the tube, i.e., the surface which will be heat sealed to itself, will be the first outer layer of the film.
In general, various conventional additives such as ~lip agents, anti-blocking agents, and pigments can be incorporated in the films in accordance with conventional practice.
Although preferred embodiments of this invention have been described in detail, it is contemplated that modifications thereof msy be made and some preferred festures msy be employed without others, 811 within the spirit snd scope of the brosd invention.

Claims

1. A heat-shrinkable, biaxially stretched, multilayer thermoplastic film suitable for use in fabricating bags for packaging primal meat cuts and processed meat products;
said film comprising a first outer layer of an ethylene-vinyl acetate copolymer; a core layer comprising a barrier film; and a second outer layer comprising a blend of an ethylene-vinyl acetate copolymer and a very low density polyethylene copolymer comprising ethylene copolymerized with higher alpha olefins containing from 3 to 8 carbon atoms, wherein said film heat-shrinks from about 30 percent to about 50 percent at a temperature of about 90°C.

2. A film as in Claim 1 wherein said barrier film is selected from the group consisting of a polyvinylidene chloride copolymer, and an ethylene-vinyl alcohol copolymer.

3. A film as in Claim 1 wherein said blend comprises from about 5 weight percent to about 25 weight percent of said very low density polyethylene copolymer, based on the weight of said blend.

4. A film as in Claim 1 wherein said alpha olefins are selected from the group consisting of propylene, butene-1, pentene-1, 4-methylpentene-1, hexene 1, heptene-1 and octene-1.

5. A film as in Claim 1 wherein said polyethylene copolymer has a density below about 0.91 g./cm.3, and a 1%
secant modulus below about 140,000 kPa.

6. A film as in Claim 1 wherein said polyethylene copolymer has a density of from about 0.86 g./cm.3 to about 0.91 g./cm.3, and a 1% secant modulus of from about 600 kPa to about 100,000 kPa.

7. A film as in Claim 1 wherein said polyethylene copolymer has a standard load melt index of up to about 25.0 g./10 minutes.

8. A film as in Claim 1 wherein said polyethylene copolymer has a high load melt index of up to about 1000 g./10 minutes.

9. A film as in Claim 1 wherein said film has a thickness of from about 1.75 mils to about 3.0 mils.

10. A film as in Claim 1 wherein said film has been irradiated to a dosage level of between about 1 megarad and about 5 megarads.

11. A film as in Claim 1 fabricated in the form of a bag.

12. A film as in claim 1 wherein said ethylene-vinyl acetate copolymer in said second outer layer comprises a blend of two ethylene-vinyl acetate copolymers wherein one of said ethylene-vinyl acetate copolymers has a melt index of from about 0.1 to about 1.0 decigram per minute and a vinyl acetate content of from about 10 to about 18 weight percent, based on the weight of said copolymer, and the other ethylene-vinyl acetate copolymer has a melt index of from about 0.1 to about 1.0 decigram per minute and a vinyl acetate content of from about 2 to about 10 weight percent, based on the weight of said copolymers.

13. A film as in Claim 12 fabricated in the form of a bag.

14. A film as in Claim 12 wherein said blend of ethylene-vinyl acetate copolymers has a vinyl acetate content of from about 3 weight percent to about 18 weight percent, based on the weight of said blend of ethylene-vinyl acetate copolymers.

15. A film as in Claim 1 wherein said first outer layer comprises an ethylene-vinyl acetate copolymer having a vinyl acetate content of from about 9 weight percent to about 15 weight percent, based on the weight of said copolymer.

16. A heat-shrinkable, puncture-resistant, biaxially stretched, thermoplastic film suitable for use in fabricating bags for packaging food articles such as frozen poultry, said film having at least one layer comprising a very low density polyethylene copolymer, comprising ethylene copolymerized with higher alpha olefins containing from 3 to 8 carbon atoms, wherein said film heat-shrinks to the extent of at least 30 percent at a temperature of about 90°C.

17. A film as in Claim 16 wherein said film is a multilayer film including a barrier layer.

18. A film as in Claim 16 wherein said film heat-shrinks to the extent of at least 30 percent in the machine direction at a temperature of about 90°C.

19. A film as in Claim 16 wherein said film heat-shrinks to the extent of at least 30 percent in the transverse direction at a temperature of about 90°C.

20. A film as in Claim 16 wherein said film heat-shrinks to the extent of at least 30 percent in each of the machine direction and the transverse direction at a temperature of about 90°C.

21. A film as in Claim 16 wherein said very low density polyethylene copolymer is Union Carbide TM DFDA-1137 having a density of about 0.906 g./cm.3 and a melt index of about 0.88 decigram per minute.

22. A film as in Claim 16 wherein said polyethylene copolymer has a density of about 0.90 g./cm.3.

23. A film as in Claim 16 wherein said film has a thickness of at least 1.5 mils.

24. A film as in Claim 16 fabricated in the form of a bag.

25. A film as in Claim 16 or Claim 17 wherein said film has a thickness of at least 1.75 mils.

26. A film as in Claim 16 wherein said polyethylene copolymer has a density below about 0.91 g./cm.3, and a 1% secant modulus below about 140,000 kPa.

27. A film as in Claim 16 wherein said polyethylene copolymer has a density of from about 0.86 g./cm.3 to about 0.91 g./cm3, and a 1% secant modulus of from about 600 kPa to about 100,000 kPa.

28. A film as in Claim 16 wherein said polyethylene copolymer has a standard load melt index of up to about 25.0 g./10 minutes.

29. A film as in Claim 16 wherein said polyethylene copolymer has a high load melt index of up to about 1000 g./10 minutes.

30. A film as in Claim 16 wherein said film is a monolayer film.

31. A film as in Claim 16 wherein said very low density polyethylene copolymer is blended with an ethylene-vinyl acetate copolymer.

32. A film as in Claim 17 wherein at least one layer of said multilayer film comprises a blend of said very low density polyethylene copolymer and an ethylene-vinyl acetate copolymer.

33. A film as in Claim 32 wherein said blend comprises from about 5 weight percent to about 25 weight percent of said very low density polyethylene copolymer, based on the weight of said blend.

34. A method of manufacturing a heat-shrinkable, puncture resistant, biaxially stretched, thermoplastic film comprising the steps of extruding a primary tube comprising a very low density polyethylene which is a linear copolymer of ethylene and higher alpha olefin containing from 3 to 8 carbon atoms, having a density below about 0.91 g/cm3 and a 1% secant modulus below about 140,000 kPa; heating the very low density polyethylene primary tube; biaxially stretching the heated primary tube using a double bubble method under conditions wherein the biaxially stretched tube is heat shrinkable from about 30% to about 50% at a temperature of about 90°C in at least one of the transverse and machine directions.

35. A method according to Claim 34 wherein said biaxially stretched tube is heat shrinkable from about 30% to about 50% at a temperature of about 90°C in the transverse direction.

36. A method according to Claim 34 wherein said biaxially stretched tube is heat shrinkable from about 30% to about 50% at a temperature of about 90°C in the machine direction.

37. A method according to Claim 34 wherein said biaxially stretched tube is heat shrinkable from about 30% to about 50% at a temperature of about 90°C in both the transverse and machine directions.

38. A method according to Claim 34 wherein the film comprises a monolayer film.

39. A method according to Claim 34 wherein the film comprises a multilayer film.

40. A method according to Claim 39 wherein the primary multilayer film is prepared by coextrusion.

41. A method according to Claim 39 wherein at least one layer of said multilayer film comprises a blend of said very low density polyethylene and an ethylene-vinyl acetate copolymer.

42. A method according to Claim 39 wherein the multilayer film comprises a first outer layer of an ethylene-vinyl acetate copolymer, a core layer comprising a barrier film, and a second outer layer comprising a blend of said very low density polyethylene and an ethylene-vinyl acetate copolymer.

43. A method according to Claim 39 wherein said film is irradiated to a dosage level of between about 1 megarad and about 5 megarads.

44. A method according to Claim 34 wherein the polyethylene copolymer has a standard load melt index of up to about 25.0 g/10 minutes.

45. A method according to Claim 34 wherein the polyethylene copolymer has a high load melt index of up to about 1000 g/10 minutes.

46. A method according to Claim 39 wherein the multilayer film has a thickness of from about 1.75 mils to about 3.0 mils.

47. A method according to Claim 39 wherein at least one layer of said multilayer film comprises an oxygen barrier layer.

48. A method according to Claim 47 wherein said oxygen barrier layer is a core layer.

49. A method according to Claim 47 wherein said oxygen barrier layer comprises a copolymer of vinylidene chloride and at least one comonomer selected from the group of comprising vinyl chloride, acrylonitrile and an acrylate ester.

50. A method according to Claim 47 wherein said oxygen barrier layer comprises a copolymer of vinylidene chloride and an acrylate ester wherein vinylidene chloride constitute at least 65 weight percent of the copolymer.

51. A method according to Claim 47 wherein said oxygen barrier layer comprises a copolymer of vinylidene chloride and a vinyl chloride wherein at least 65 weight percent of the copolymer comprises vinylidene chloride.

52. A method according to Claim 47 wherein said oxygen barrier layer comprises a copolymer of vinylidene chloride and methyl methacrylate.

53. A method according to Claim 49 wherein said oxygen barrier layer copolymer comprises between about 70 to 95 weight percent of vinylidene chloride.

54. A method according to Claim 49 wherein said oxygen barrier layer comprises ethylene-vinyl alcohol copolymer.

55. A method according to Claim 49 wherein said oxygen barrier layer comprises a copolymer of vinylidene chloride and acrylonitrile.

56. A method according to Claim 49 wherein said oxygen barrier is a copolymer having at least 65 weight percent of said copolymer derived from vinylidene chloride.

57. A method according to Claim 56 wherein from 70 to about 95 weight percent of said copolymer is derived from vinylidene chloride.

58. A film as in claim 16 wherein the very low density polyethylene copolymer is Union CarbideTM DFDA-1137 having a density of about 0.906 g./cm3.

59 A film as in claim 17 wherein at least one layer comprises an ethylene-vinyl acetate copolymer.

60. A heat-shrinkable, puncture resistant, biaxially stretched, thermoplastic film suitable for use in fabricating bags for packaging food articles such as frozen poultry, said film comprising a very low density polyethylene which is a linear copolymer of ethylene and higher alpha olefin containing from 4 to 8 carbon atoms having a density below about 0.91 g/cm3, a 1% secant modulus below about 140,000 kPa, and said film being formed using a double bubble method and wherein said film heat-shrinks from about 30 percent to about 50 percent at a temperature of about 90°C, in at least one of the machine and transverse directions.

61. A heat-shrinkable, biaxially stretched, multilayer thermoplastic film suitable for use in fabricating bags for packaging food articles wherein at least one layer of said multilayer film comprises a blend of very low density polyethylene which is a linear copolymer of ethylene and higher alpha olefin containing from 4 to 8 carbon atoms having a density below about 0.91 g/cm3 and a 1% secant modulus below about 140,000 kPa, and an ethylene-vinyl acetate copolymer, said multilayer film being formed using a double bubble method and wherein said film heat-shrinks from about 30 percent to about 50 percent at a temperature of about 90°C. in at least one of the machine and transverse directions.

62. A method of manufacturing a heat-shrinkable, puncture resistant, biaxially stretched, thermoplastic film comprising the steps of extruding a primary tube comprising a very low density polyethylene which is a linear copolymer of ethylene and higher alpha olefin containing from 4 to 8 carbon atoms, having a density below about 0.91 g/cm3 and a 1% secant modulus below about 140,000 kPa; heating the very low density polyethylene primary tube; biaxially stretching the heated primary tube using a double bubble method under conditions wherein the biaxially stretched tube is heat shrinkable from about 30%
to about 50% at a temperature of about 90°C. in at least one of the transverse and machine directions.

63. A method according to claim 62 wherein the film comprises a multilayer film.

64. A method according to claim 63 wherein at least one layer of said multilayer film comprises an oxygen barrier layer.