Reduced blocking metallized film

Abstract

Low temperature sealable metallized packaging films are found to have reduced blocking tendencies when an oxidized polyethylene wax is blended into a low temperature sealing composition including an ethylene-carboxylic acid copolymer. The films are useful for high-speed packaging applications requiring sealability at low temperatures. The films exhibit low blocking performance during unwinding of the film while maintaining positive low temperature sealability characteristics.

Description

FIELD OF THE DISCLOSURE

[0001] This disclosure relates to metallized films having low temperature sealability characteristics with improved anti-blocking properties.

BACKGROUND INFORMATION

[0002] The modern packaging industry requires expertise in many disciplines. Packaging technology integrates elements of engineering, chemistry, food science, metallurgy, and other disciplines to provide the consumer fresh foods and non-food products. To protect product quality, it is often desirable to provide packaging films with the ability to provide a hermetic seal, i.e., a seal which does not permit gases, such as air, to enter the package.

[0003] Packages produced from flexible film, such as bags and pouches, are prevalent in the marketplace. In order to utilize continuous flexible film, the industry generally employs form/fill/seal packaging techniques. The type of product packaged dictates whether or not the technique will include horizontal form/fill/seal packaging (HFFS) or vertical form/fill/seal packaging (VFFS).

[0004] It is important for the packaging designer to be able to select a polymeric film having optimum barrier properties for storage of products and be confident of providing a high quality seal using high-speed packaging apparatus. For example, it is known that stereoregular polypropylene, e.g., oriented polypropylene, is quite useful in the manufacture of packages from flexible films. Using oriented polypropylene as a core layer, additional layers in the way of coatings, co-extrusions, laminations, and combinations thereof are added to improve barrier properties of the film. In certain cases, films can be prepared which exclude moisture and oxygen, but permit the passage of light. In other cases, it is also important to prevent light from passing through the film barrier. Barrier properties can also be modified and/or enhanced by treatments such as heat and flame treatment, electrostatic discharge, chemical treatments, halogen treatment, ultra-violet light, plasma treatment and combinations thereof.

[0005] An important issue for designing packaging films is to ensure they can be processed on high speed form/fill/seal machinery. Form/fill/seal packaging systems operate by unwinding continuous film from bulk film rolls, followed by forming pouches, filling the pouches, and, finally, sealing the pouch closed. Thus, the film must have sufficient flexibility to undergo machine folding from a flat orientation to a folded condition, and be subjected to a sealing function, which is part of high-speed packaging apparatus. In selecting the optimum packaging film for its barrier properties, high-speed unrolling and folding are the primary concern. An additional and very important aspect of the packaging process, however, is the ability to effectively seal the pouch after it is filled with the product.

[0006] High-speed horizontal and vertical form/fill/seal systems include sealing functions at various stages of the packaging process. In a horizontal form/fill/seal apparatus, individual pouches are formed by folding the multi-layer film in half followed by providing vertical seals along the length of the folded web and separating the pouches along the seals formed by vertical sealing. Optionally, the bottoms of the pouches can also be sealed. After the pouch is formed and filled, the top of the pouch is sealed. Similarly, in vertical form/fill/seal apparatus, the continuous web is formed around a tube and the web is immediately joined together by a longitudinal sealing jaw as either a lap seal or a fin seal.

[0007] A second sealing function is present in a vertical form/fill/seal configuration which consists of a combination top and bottom sealing section (with a bag cut-off device in between). The top-sealing portion seals the bottom of an empty bag suspended from the bag forming tube while the bottom portion seals the top of a filled bag.

[0008] In most processes for packaging products, the package is formed and filled by creating a heat-seal between two opposed layers of film to form a pocket and almost simultaneously sliding or dropping the product into the pocket. In these form and fill packaging techniques a continuous flat web of packaging film is fed around a form which shapes it into a tube, the tube is slipped over a hollow form and the free edges of the tube are sealed together. The tube so formed is then passed between a pair of hot sealing jaws which create a series of discrete packages by collapsing the film onto itself and forming a seal by the application of heat and pressure. The product is introduced into each package through the hollow form in the interval between the heat seals. During high operating speeds, the product is dropped into the package while the sealing jaws, which form the seal, are closed. With both vertical and horizontal form and fill sealing applications the heat seal should be strong enough to support and retain the product after the sealing jaws open to release the film. It is often desirable to release the sealing jaws soon after the seal is formed so a film which accomplishes this by exhibiting a high “hot tack” is very useful.

[0009] Additionally, in packaging applications there is a great demand for heat sealable films which can be subjected to temperatures high enough to seal the films without causing the substrate to cockle or pucker. One approach for achieving this is by coating a film substrate with a layer of heat sealable material which adheres strongly to the substrate and which can be melted at a temperature below the softening temperature of the substrate. Heat-sealable coatings with low melting temperatures are often preferred because the substrate is less likely to be damaged during heat sealing. U.S. Pat. No. 5,419,960 discloses a low temperature sealable coating.

[0010] Cold sealable pressure-sensitive adhesives have been developed. These adhesives do not require the use of a heated element to seal the packages. However, these adhesives have high surface tack characteristics making them adhere to uncoated surfaces of the packaging film which makes them difficult to use because of film blocking (i.e., sticking).

[0011] An important feature in many modern packaging films is a metallic layer or coating that is usually applied by vapor deposition methods. U.S. Pat. Nos. 5,487,940 and 6,420,041 describe and refer to numerous exemplary metallized films. Metal layers are well known in the packaging industry and can be deposited using any known method, for instance, vacuum deposition, electroplating, sputtering, etc. Preferably, the metal layer is one of vacuum deposited aluminum, copper, silver, chromium, gold, and mixtures thereof, with vacuum deposited aluminum being the most commonly used.

[0012] Metallized films are widely used for their moisture barrier properties. A disadvantage of metallized films, when the metallic layer is on the surface of the films, is the tendency of the metallic layer to stick or block to seal layers or coatings on the opposite side of the film structure when the metallized film is rolled. This sticking or blocking problem is exacerbated when the opposite seal layer or coating is a low temperature sealing material. Blocking of a film having a metallic surface layer often results in damage to or removal of the metallic surface leading to a decrease in the moisture barrier properties of the film and/or unpleasing appearance of the metallic layer. To address this problem, metallic layers are often covered with another film layer or coating to protect the metallic layer. U.S. Pat. Nos. 5,287,615 and 6,013,353 disclose application of a layer of a low temperature sealable coating on the surface of a metallic film layer to protect the metal and to provide high seal strength. The patents disclose coating an ethylene-unsaturated carboxylic acid copolymer composition on the metallic surface. The coating may also contain a dispersed wax. The disclosed films may optionally include the same type of coating on the side of the film opposite the metal layer.

[0013] A protective acrylic or other polymeric coating may be deposited over the metal layer under vacuum conditions as disclosed in U.S. Pat. No. 4,842,893. As disclosed in U.S. Pat. No. 6,420,041, it is known to laminate a polymeric film layer over the metal layer of a film to protect the metal from scratching and scuffing during use. The polymeric layer can improve the gauge, stiffness and puncture resistance of the overall film, and can further enhance the barrier properties of the film. The polymeric layer can be oriented, unoriented, transparent or opaque. The polymeric layer is laminated to the metal layer using any suitable adhesive.

BRIEF DESCRIPTION OF THE DISCLOSURE

[0014] This disclosure relates to low temperature sealing metallized films. A first surface layer of the films is provided with low temperature sealability with an ethylene-unsaturated carboxylic acid copolymer coating. A second surface layer of the film is provided with a metallized layer. An oxidized polyethylene wax is blended into the copolymer coating material to reduce blocking between the low temperature sealing coating and the metallized layer. The film is useful for high-speed packaging applications requiring sealability at low temperatures. The film exhibits low blocking performance during unwinding of the film while maintaining positive low temperature sealability characteristics.

DETAILED DESCRIPTION OF THE INVENTION

[0015] While metallized films are used widely in the packaging industry, many disadvantages arise from blocking of the metal layer to the opposite side of the film. This problem is most evident when the surface opposite the metallized surface layer is a low temperature sealable layer or coating. Providing an additional layer or coating over the metal layer to protect the metal layer and to reduce blocking is not always an acceptable solution to this problem. In certain applications, visibility of the metal layer in the final packaging product is desirable from an aesthetic or functional viewpoint. Cost considerations may also make a protective layer or coating undesirable.

[0016] The films described herein address this problem by providing a low temperature sealing metallized film that allows the metal layer to remain exposed while reducing the blocking disadvantages of conventional metallized films. The films include single or multiple layers having a metallized layer on one surface and a seal layer on the other surface. The propensity of the metallized surface layer to block is reduced by inclusion of at least one oxidized polyethylene wax emulsion in the seal layer.

[0017] The films are comprised of a substrate which may be a single or multi-layer film. The metallized layer or coating is provided on one surface of the substrate. The low temperature sealable layer or coating is provided on the opposite surface of the substrate.

[0018] A variety of ethylene-carboxylic acid copolymer compositions are useful to provide the low temperature seal functionality on the surface of the film opposite the metallized layer. The compositions include at least one ethylene copolymer comprising from about 65 wt. % to about 95 wt. % of ethylene and from about 5 wt. % to about 35 wt. % of an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated ester. Exemplary suitable carboxylic acid monomers may be selected from acrylic acid, methylacrylic acid, maleic acid, crotonic acid, itaconic acid, citraconic acid, and mixtures thereof. Exemplary suitable ester monomers are acrylic esters such as methylacrylate, methylmethacrylate, butylacrylate, and mixtures thereof. In one embodiment, the ethylene copolymer of the low temperature composition comprises from about 75 wt. % to about 90 wt. % of ethylene and from about 10 wt. % to about 25 wt. % of acrylic acid or methacrylic acid. In another embodiment, the low sealing temperature composition comprises from about 75 wt. % to about 85 wt. % of ethylene and from about 15 wt. % to about 25 wt. % of acrylic acid or methacrylic acid. The ethylene copolymer component of the composition may be comprised of one or a mixture of more than one ethylene copolymer as described above.

[0019] Within the low temperature sealing composition, in one embodiment, the at least one ethylene copolymer content ranges from about 75 wt. % to about 95 wt. %. In another embodiment, the at least one ethylene copolymer content ranges from about 80 wt. % to about 90 wt. %. In still another embodiment, the at least one ethylene copolymer content ranges from about 80 wt. % to about 85 wt. %.

[0020] The ethylene copolymer in the low temperature sealable coating may be obtained as a solution or fine dispersion of an ammonium salt of the copolymer in an ammoniacal water solution. When the copolymer is dried, ammonia is given off and the ionized and water sensitive carboxylate groups are converted to largely unionized and less water sensitive free carboxyl groups. However, there may be added to the solution or dispersion of the ethylene copolymer an amount of ions of at least one metal from Group Ia, IIa, or IIb of the Periodic Table, such as, sodium, potassium, lithium, calcium or zinc ions, and mixtures thereof, in the form of their hydroxides. In one embodiment, sodium hydroxide is used. The quantity of such metallic ions may be in the range sufficient to neutralize, for example, about 2% to about 80% of the total carboxylate groups in the copolymer in one embodiment. In another embodiment, from about 10% to about 50% of the carboxylate groups are neutralized. The presence of the metallic ions has been found in many cases to result in an improvement in certain properties, e.g., coefficient of friction (COF), hot tack, and blocking, without an unacceptable sacrifice of other properties such as low sealing temperatures as described in U.S. Pat. No. 5,419,960.

[0021] Suitable ethylene copolymers have melting points of about 65° C. to about 105° C. in one embodiment. In another embodiment, the melting points range from about 65° C. to about 95° C. In a third embodiment, the melting points range from about 70° C. to about 90° C.

[0022] Exemplary suitable ethylene copolymers for the low temperature sealing compositions described here are PRIMACOR 59801 available from Dow Chemical Company and ESCOR 5200 from ExxonMobil Chemical Company.

[0023] A variety of oxidized polyethylene waxes are useful for inclusion in the low temperature sealing coating compositions described herein. Polyethylene waxes are made from ethylene produced from natural gas or by cracking petroleum naphtha. Ethylene is then polymerized to produce waxes with various drop points, hardnesses and densities. Oxidized polyethylenes are readily subjected to emulsification, whereas non-oxidized polyethylenes largely are not. Inclusion of waxes in the formulations described herein is typically accomplished through the use of wax emulsions. However, techniques making use of waxes in other forms are within the contemplation of this disclosure.

[0024] Useful oxidized polyethylene wax materials include low molecular weight polyethylenes having a number average molecular weight of less than about 5000 in one embodiment. In another embodiment, the number average molecular weight is about 1000 to about 4000. In still another embodiment, the number average molecular weight ranges from about 1500 to about 2500.

[0025] The polyethylene waxes should generally be oxidized to an acid number of about 10 to about 41 in one embodiment. In another embodiment, the acid number ranges from about 12 to about 28. In another embodiment, the acid number is from about 12 to about 28. In a third embodiment, the acid number ranges from about 13 to about 17. The oxidized polyethylene waxes may also be blended with non-oxidized waxes.

[0026] The oxidized polyethylene waxes have a drop point range of about 85° C. to about 145° C. in one embodiment. In another embodiment, the drop point ranges from about 95° C. to about 140° C. In a third embodiment, embodiment, the drop point ranges from about 98° C. to about 115° C. In still another embodiment, the drop point ranges from about 98° C. to about 110° C. All drop points referred to herein are as determined by ASTM D3954.

[0027] The oxidized polyethylene waxes have a Brookfield viscosity at 140° C. of from about 35 centipoises (cps) to about 400 cps in one embodiment. In another embodiment, the Brookfield viscosity ranges from about 170 cps to about 250 cps.

[0028] Exemplary useful oxidized polyethylene wax materials are available under the designations AC-629, AC-656, and AC-680 from Honeywell. These waxes have drop points of 101° C., 98° C., and 108° C., respectively.

[0029] The oxidized polyethylene waxes may be emulsified in water by known methods. Exemplary methods are disclosed in U.S. Pat. Nos. 3,850,658 and 4,371,658.

[0030] The particle size of the waxes in the emulsion should generally be as small as possible. In one embodiment, the oxidized polyethylene emulsions have wax particle sizes less than one micron and up to 5 microns. Generally, the wax particles in the emulsions should not exceed 50 microns in particle size. In one embodiment, the emulsions comprise from about 10 wt. % to about 60 wt % wax. The oxidized polyethylene wax component of the composition may be comprised of one or a mixture of more than one oxidized polyethylene wax as described above.

[0031] Within the low sealing temperature coating compositions, the at least one oxidized polyethylene wax content ranges from about 5 parts per hundred (“Phr”) to about 25 Phr based upon 100 parts by weight of the ethylene copolymer. In another embodiment, the oxidized polyethylene wax content ranges from about 7 Phr to about 20 Phr. In a third embodiment, the oxidized polyethylene wax content ranges from about 8 Phr to about 18 Phr. In still another embodiment, the oxidized ethylene content is about 10 Phr. All references to Phr concentrations used herein are on a dry basis of the indicated components based upon 100 parts by weight of the ethylene copolymer component, on a dry basis.

[0032] The low temperature sealable coating compositions may also contain particulate materials such as amorphous silica to reduce the tack of the coating at room temperature. Amorphous silica is composed of particles which are agglomerations of smaller particles and which have an average particle size of about 2 to about 9 microns in one embodiment. In another embodiment, the particle size is about 3 to about 5 microns. The silica may be present in the sealable coating in a concentration of about 0.1 to about 2.0 Phr in one embodiment. In another embodiment, the concentration is about 0.2 to about 0.4 Phr. Other types of particulate materials can be used instead of amorphous silica. Suitable materials include polymethylmetacrylate spheric particles with an average particle size of from about 2 μm to about 6 μm in one embodiment. Such particulates are available under the designations EPOSTAR MA 1002 AND EPOSTAR MA 1004 manufactured by Nippon Shokubai Co., LTD and CALIBRE CA 6-6 manufactured by Polymer System. Also, silicone spherical particles with an average particle size of from about 2 μm to about 6 μm in one embodiment are suitable. Exemplary silicone particles are available under the designation TOSPEARL manufactured by Toshiba Silicone Co., LTD.

[0033] Other optional additives which may be included in the sealable coating of the films include other particulate materials such as talc which may be present in an amount, for example, of about 0.1 to 2 Phr, cross-linking agents such as melamine formaldehyde resins which may be present in an amount, for example, of about 0.1 to 20 Phr, and anti-static agents such as poly(oxyethylene) sorbitan monooleate which may be present in an amount, for example, of about 0.1 to 6 Phr. An anti-bacterial agent may also be present. Sodium hydroxide may be included as well.

[0034] The low temperature sealable coating composition may be applied in any suitable manner such as by gravure coating, roll coating, dipping, spraying, etc. Squeeze rolls, doctor knives, etc., are useful to remove the excess coating solution. The coating compositions will ordinarily be applied in such an amount that there will be deposited following drying, a smooth, evenly distributed layer of from about 0.3 to about 1.8 grams per square meter of film surface in one embodiment. In another embodiment, the coating is applied at a thickness of about 0.5 g/m2 to about 1.2 g/m2. In still another embodiment, the thickness is from about 0.6 g/m2 to about 1.0 g/m2. In general, the thickness of the applied coating is such that it is sufficient to impart the desired sealability, coefficient of friction (COF), and hot slip characteristics to the substrate polymer film.

[0035] The coating, once applied to the film may be dried by hot air, radiant heat or by any other suitable means thereby providing a non-water soluble, adherent, glossy coated film product useful, for example, as a packaging film.

[0036] The substrates to which the metallized layer and the low sealing temperature layers are applied may be any single or multi-layer thermoplastic material that can be formed into a film. The substrate can be clear or opaque. The opacity of opaque films may be achieved by cavitating, creating voids, in one or more layers of the polymeric film substrate or by other means. Exemplary thermoplastic materials include any polyolefin such as polypropylene, polyethylene, polybutene, polystyrene, polyvinyl chloride, ethylene containing copolymers such as ethylene-propylene copolymers, ethylene containing terpolymers such as ethylene-butylene-propylene terpolymers, and blends thereof. Other suitable film materials include polyethylene terephthalate, other polyesters (including but not limited to polyethylene terephtalate glycol [PETG], polyethylene naphthalate [PEN] and liquid crystalline polymers [LCP]), and nylon, including oriented nylon.

[0037] In multilayer films, there is one or more skin layer located on at least one surface of a thermoplastic core layer. Exemplary skin layers comprise polyethylene, including medium and high-density polyethylene, polypropylene, copolymers of propylene and ethylene and terpolymers of propylene, ethylene and butylenes, and blends thereof.

[0038] Any of the various film layer materials can contain processing aids or inorganic particulates such as titanium dioxide or void initiating agents to enhance the whiteness or color of the substrate or to enhance anti-blocking properties. Exemplary void initiators and techniques are disclosed in U.S. Pat. Nos. 5,885,721 and 6,168,826.

[0039] As mentioned, the substrate may be a single or multiple layers. For example, the substrate may be a 3-layer polymeric film which comprises a core layer and two outer layers, the core layer comprising polypropylene. In another embodiment, the substrate may be a 5-layer polymeric film which comprises a core layer, two intermediate layers contiguous to the central core layer and two outer layers, the polymer of at least one of the intermediate layers can comprise polypropylene.

[0040] A particular type of thermoplastic film which can be advantageously used in the substrate is molecularly oriented isotactic polypropylene. After extrusion of the substrate, for example, the base polypropylene film, utilizing conventional extrusion techniques, the film is heated and molecularly oriented by stretching it both in the longitudinal and transverse directions. The resulting oriented film exhibits greatly improved tensile and stiffness properties. Typically the polyolefin resin, such as polypropylene, is extruded through a flat sheet extruder die at a temperature ranging from between about 200° C. to about 250° C., casting the film onto a cooling drum and quenching the film. The sheet is then stretched about 3 times to about 7 times in the machine direction (MD) orienter followed by stretching about 5 times to about 10 times in the transverse direction (TD) orienter.

[0041] The substrates may be oriented or hot-blown shrink films made from any of a number of processes. The oriented films may be manufactured in a variety of processes including machine direction orientation (MDO), double bubble, LISIM®, tape bubble, trapped bubble or tenter framing. The hot-blown films are typically manufactured in a simple bubble process.

[0042] The following examples are illustrative of specific embodiments of low temperature sealing metallized films. All parts and percentages are by weight unless otherwise noted.

EXPERIMENTAL EVALUATIONS

[0043] A useful low temperature sealing metallized film should demonstrate a variety of favorable characteristics including the ability to provide an adequate seal at low temperatures and resistance to blocking following storage and transport. Evaluations were conducted on six oxidized polyethylene waxes to determine suitability for inclusion in low temperature sealable coatings on a flexible substrate opposite a metallized layer. The waxes were evaluated in the form of aqueous emulsions available from Michelman, Inc. under the designations indicated in Table I which also contains physical properties of the emulsions. Table I also identifies the specific designations of the waxes used to make the emulsions. All wax designations having the prefix “AC” are available from Honeywell. Two waxes are available from Carroll Scientific, Inc. or Eastman Chemical Company, as indicated. The low temperature sealable coatings are referred to simply as “Coating” in the following test results.

TABLE I
Wax Emulsion	ME	ME	ME	MGRD/PE Micronised	ME	No emulsion
Designation/Wax	6135E/AC-	74040/East-	10325/AC-	from	20325/AC-	designation/
Designation	316	man E/20	629	Caroll Scientific	656	AC-680
Solids %	35	40	25	41	25	25
Particle Size (nm)	40	35	45	12000	45	45
Wax Drop Point	140	111 (softening	101	136 (melting point)	98	108
(° C.)		point)

[0044] Selected sealability characteristics of these emulsions as determined after blending into an ethylene acrylic acid copolymer (“EAA”) low temperature sealing coating with a constant wax concentration of 15 Phr are set forth in Tables II-V. The EAA based coatings were formulated as follows with all component parts calculated by weight on a dry basis:

Michem Prime 4983 (25% solids EAA formulation) 100 Phr
Sodium hydroxide (10% solids)    1.5 Phr
Oxidized polyethylene wax        15 Phr
Syloid 4 μm                      0.2 Phr
Talc                             0.4 Phr

[0045] A comparative formulation was produced with 4 Phr carnauba wax in place of the 15 Phr oxidized polyethylene wax. A suitable carnauba wax is available from Michelman, Inc. under the designation ML 160. The formulations were adjusted to 15% solids with demineralized water and coated with a kiss coating head, with the gravure roll turning in reverse to achieve a coating weight of 0.75 g/m2. The coatings were applied on a 29 μm 3 layer base film, corona treated and primed with polyethyleneimine. The base film outer skin layers were a propylene-ethylene-butylene terpolymer resin.

TABLE II
Flat Jaw Sealability (Coating/Coating)
	Temperature (° C.)
	90	95	100	105	110	120	130	140	145
Comparative	390	420	500	510	430	390	460	430	400
MGRD 25	0	0	40	40	60	110	220	200	220
ME 10325	0	20	140	140	300	140	240	260	160
ME 74040	300	280	430	370	480	480	480	480	460
ME 61336.E	150	180	180	220	250	340	340	330	330
Sealability determined on one heated flat jaw Asko brand sealer for 2 seconds dwell time at 165.4 kPa.
Values are in g/25 mm.

[0046]

TABLE III
Crimp Sealability (Coating/Coating)
	Temperature (° C.)
		80	85
	Comparative	380	410
	MGRD 25	220	330
	ME 10325	130	475
	ME 74040	480	565
	ME 61335.E	480	450
	Sealbility determined on a crimp sealer for .75 second dwell time at a pressure of 137.8 kPa.
	Values are in g/25 mm.

[0047]

TABLE IV
Flat Jaw Sealability (Coating/aluminum foil)
	Temperature
	90	95	100	105	110	120	130	140	145
Comparative	0	30	60	90	220	240	380	270	290
MGRD 25	0	0	0	20	70	70	80	90	80
ME 10325	0	0	0	0	0	0	10	10	10
ME 74040	0	0	20	20	20	150	180	90	60
ME 61335.E	0	0	0	0	10	50	140	80	40
Sealability determined on one heated flat jaw Asko brand sealer for 2 seconds dwell time at 165.4 kPa.
Values are in g/25 mm.

[0048]

TABLE V
Haze Gloss COF
		Haze	Gloss	COF	Metal Adhesion
	Comparative	1.9	88	N/A	No metal transfer
	MGRD 25	7.2	78	0.3	No metal transfer
	ME 10325	2.2	85	0.35	Metal transfer
	ME 74040	2.2	86	0.38	No metal transfer
	ME 61335.E	2.1	87	0.47	Metal transfer

[0049] Metal adhesion testing was conducted by metallizing the wax modified coatings and evaluating their affinity towards metal by testing metal adhesion to the coatings with an adhesive tape after two pulls. No metal transfer means a high affinity of the coating to metal and provides an indication about the blocking that can be expected when the coatings are in contact with metallized surface on reels. Metal transfer indicates lower blocking tendency to metal.

[0050] As seen from Tables II-V, all of the polyethylene waxes contributed to a low sealability between the low temperature sealing coating and aluminum foil which simulated a metallized coating. The low sealability was observed over a wide range. The ME10325 formulation demonstrated the most dramatic reduction in sealabilty between the low temperature sealing coating and the aluminum foil.

[0051] To determine the impact of the concentration of the wax in the EAA blend on the sealability, blocking and general film characteristics, the concentrations of three of the waxes were varied and the data in Table VI-XI were observed.

TABLE VI
Flat Jaw Sealability (Coating/Coating)
	Temperature (° C.)
	90	95	100	105	110	120	130	140	145
Comparative	390	420	500	510	430	390	460	430	400
ME 10325 10 Phr	0	110	370	450	350	420	430	430	370
ME 74040 15 Phr	350	340	410	510	510	490	410	410	400
ME 61335.E 10 Phr	380	380	440	420	430	430	450	400	450
ME 61335.E 15 Phr	320	370	420	450	450	450	450	450	430
Sealability determined on one heated flat jaw Asko brand sealer for 2 seconds dwell time at 165.4 kPa.
Values are in g/25 mm.

[0052]

TABLE VII
Flat Jaw Sealability (Coating/Aluminum Foil)
	Temperature (° C.)
	90	95	100	105	110	120	130	140	145
Comparative	0	30	60	90	220	240	380	270	290
ME 10325 10 Phr	0	0	0	0	0	0	20	60	20
ME 74040 15 Phr	80	20	50	50	100	170	50	50	40
ME 61335.E 10 Phr	60	40	70	50	60	200	190	150	300
ME 61335.E 15 Phr	10	20	40	50	90	90	100	170	300
Sealability determined on one heated flat jaw Asko brand sealer for 2 seconds dwell time at 165.4 kPa.
Values are in g/25 mm.

[0053]

TABLE VIII
Flat Jaw Sealability (Coating/Metal Side of a Metallized Film)
	Temperature (° C.)
	90	95	100	105	110	120	130	140	145
Comparative	100	130	170	200	230	240	260	260	270
ME 10325 10 Phr	0	0	0	0	0	0	0	0	0
ME 74040 15 Phr	0	0	20	110	30	40	110	120	250
ME 61335.E 10 Phr	40	30	80	90	110	130	140	170	220
ME 61335.E 15 Phr	0	0	20	20	60	90	130	150	130
Sealability determined on one heated flat jaw Asko brand sealer for 2 seconds dwell time at 165.4 kPa.
Values are in g/25 mm.

[0054]

TABLE IX
Crimp Sealability (Coating/Coating)
	Temperature (° C.)
		80	85
	Comparative	380	410
	ME 10325 10 Phr	370	560
	ME 74040 15 Phr	490	610
	ME 61335.E 10 Phr	470	560
	ME 61335.E 15 Phr	485	495
	Sealability determined on a crimp sealer for .75 second dwell time at a pressure of 137.8 kPa.
	Values are in g/25 mm.

[0055]

TABLE X
Haze/Gloss
		Haze	Gloss	Metal Adhesion
	Comparative	1.9	88	No metal transfer
	ME 10325 10 Phr	1.95	86	Metal transfer
	ME 74040 15 Phr	1.95	86	No metal transfer
	ME 61335.E 10 Phr	1.9	86	Metal transfer
	ME 61335.E 15 Phr	1.9	86	Metal transfer
	Metal adhesion was conducted in the same manner as described for the data of Table V.

[0056]

TABLE XI
Blocking (Coating/Metal Side of a Metallized Film)
			Pulled by
	Peel Tester	Metal Transfer	Hand (fast)
Comparative	100	Yes	Tearing
ME 10325 10 Phr	7	No	Smooth
ME 74040 15 Phr	21	Yes	Tearing
ME 61335.E 10 Phr	26	Yes	Tearing
ME 61335.E 15 Phr	18	Yes	Tearing
Coating/metal blocking was evaluated in accelerated test (60° C., 5171 kPa and 1 hour). The test is conducted using a heated press Model C, manufactured by Carver, Menomonee Falls WI, USA. The peel tester figures in column 2 indicate the force recorded for a very slow pulling speed (15 cm/min), column 3 indicates the level of metal transfer from the metallized side to the Coating side, and column 4 simulates the behavior when unwinding a reel where separation speed is high.
Blocking values are in g/25 mm.

[0057] It is seen that generally the addition of the wax emulsions lowered the sealability of the low temperature coating to itself. However, the reduction was slight. When compared to the Comparative low temperature seal coating, inclusion of the polyethylene waxes, resulted in significant reductions in sealability between the low temperature coating and aluminum at all concentrations. Generally, the lower the drop point of the wax, the greater the reduction in sealability between the low temperature coating and the metal. The metal adhesion test results reported in Table X were determined on the four low temperature sealable coatings to provide an indication of the affinity of each coating to metal. Under the severe testing conditions reported in Table XI, ME 10325 demonstrated the greatest resistance to blocking. However, the testing conditions are more severe than likely to be encountered in practical applications. Therefore, the formulations other than ME 10325 are useful as antiblocking formulations in many applications, particularly those benefiting from the other characteristics of a particular formulation. Comparative formulations incorporating 15 Phr and 25 Phr carnauba wax were also prepared and evaluated. However, no improvement for these formulations towards metal affinity/blocking was observed but significant coating to coating sealability deterioration was observed.

[0058] Emulsion ME 10325 was subjected to additional testing to evaluate the impact of wax concentration on the performance of this emulsion. The results of the additional testing are reported in the following Tables XII-XVI. A new batch of comparative coating was prepared for these tests in the same manner as described above for the data in Tables II-XI.

TABLE XII
Flat Jaw Sealability (Coating/Coating)
	Temperature (° C.)
	90	95	100	105	110	120
Comparative	550	400	550	N/A	N/A	N/A
ME 10325 8 Phr	300	300	320	450	500	620
ME 10325 10 Phr	300	350	400	500	550	N/A
ME 10325 12 Phr	320	340	550	500	N/A	N/A
Sealability determined on one heated flat jaw Asko brand sealer for 2 seconds dwell time at 165.4 kPa.
Values are in g/25 mm.

[0059]

TABLE XIII
Flat Jaw Sealability (Coating/Metal Side of a Metallized Film)
Temperature (° C.)
	90	95	100	105	110	120	130	140	145
Comparative	140	150	200	200	250	270	250	N/A	N/A
ME 10325 8 Phr	0	10	20	50	70	80	150	150	270
ME 10325 10 Phr	0	0	0	20	0	80	100	100	250
ME 10325 12 Phr	0	0	0	0	0	0	10	50	130
Sealability determined on one heated flat jaw Asko brand sealer for 2 seconds at 165.4 kPa.
Values are in g/25 mm.

[0060]

TABLE XIV
Flat Jaw Sealability (Coating/Aluminum Foil)
	Temperature (° C.)
	90	95	100	105	110	120	130	140	145
Comparative	270	220	300	310	350	450	500	450	500
ME 10325 8 Phr	100	80	130	150	70	140	250	280	150
ME 10325 10 Phr	20	50	40	60	100	50	150	150	200
ME 10325 12 Phr	0	0	0	40	0	20	20	0	20
Sealability determined on one heated flat jaw sealer for 2 seconds dwell time at 165.4 kPa.
Values are in g/25 mm.

[0061]

TABLE XV
Crimp Sealability (Coating/Coating)
	Temperature (° C.)
		80	85
	Comparative	380	410
	ME 10325 8 Phr	370	380
	ME 10325 10 Phr	350	440
	ME 10325 12 Phr	220	500
	Sealbility determined on a crimp sealer for .75 second dwell at a pressure of 137.8 kPa.
	Values are in g/25 mm.

[0062]

TABLE XVI
Blocking (Coating/Metal Side of a Metallized Film)
	Comparative	100	Tearing
	ME 10325 8 Phr	10	Slight sticking, some metal transfer
	ME 10325 10 Phr	7	No metal transfer
	ME 10325 12 Phr	5	No metal transfer
	These tests were conducted under the same conditions as for the data of Table XI.
	Values are in g/25 mm.

[0063] Significant reductions in metal sealability and blocking were observed at all levels of the ME 10325 emulsion evaluated. However, it was generally observed that the higher the level of wax, the greater the reduction in sealability and blocking. In the next series of evaluations, the ME 10325 wax emulsion was compared to two similar wax emulsions, ME 20325 and AC-680. These comparisons are reported in Tables XVII and XVIII.

TABLE XVII
Flat Jaw Sealability
(Coating/Metal Side of a Metallized Film)
	Temperature	Metal
	90	95	100	105	110	120	130	140	145	Transfer
Comparative	100	130	170	200	230	240	260	260	270	Yes
ME 10325	0	0	0	0	0	0	0	0	0	No
ME 20325	0	0	0	0	0	0	0	0	0	No
AC-680	0	0	50	60	50	90	100	70	80	Yes
Sealability determined on one heated flat jaw Asko brand sealer for 2 seconds dwell time at 165.4 kPa.
Values are in g/25 mm.

[0064]

TABLE XVIII
Blocking Tests Against Metal Side
Of a Metallized Film
Comparative	100	Tearing
ME 10325 (AC 629) 10 Phr	12	Pinholing after film separation
ME 10325 (AC 629) 12 Phr	10	Pinholing
ME 20325 (AC 656) 10 Phr	10	Very slight Pinholing
ME 20325 (AC 656) 12 Phr	8	Very slight Pinholing
These tests were conducted under the same conditions as for the data of Table XI.
Values are in g/25 mm.

[0065] Once again it was observed that all formulations resulted in significant reductions of sealability and blocking of the low temperature coating containing the waxes and metallized films. However, the reduction was more significant the lower the drop point of the wax.

[0066] A trial run on a 25 μm film printed on the metallized side and coated with a low temperature sealable coating formulation including 10 Phr of ME 20325 wax on the other side provided very good machinability on a HFFS Rekord machine and showed a slight increase of 5° C. to 10° C. in minimum sealing temperature compared to the unmodified low temperature sealable coating formulation. This testing demonstrates that the formulation is suitable for use on a reel of a HFFS packaging machine.

[0067] All patents and publications referred to herein are hereby incorporated by reference in their entireties.

[0068] This application includes references to certain trademarks. Although the use of trademarks is permissible in patent applications, the proprietary nature of the marks should be respected and every effort made to prevent their use in any manner which might adversely affect their validity as trademarks.

[0069] Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions, and alterations could be made without departing from the spirit and scope of the invention as defined by the following claims.

Claims

1. A film comprising: (a) a substrate having a first surface and a second surface; (b) a metallic layer on the first surface; and (c) a coating on the second surface comprised of at least one ethylene copolymer and at least one oxidized polyethylene wax.

2. The film of claim 1 wherein the coating is comprised of from about 5 Phr to about 25 Phr of the at least one oxidized polyethylene wax based upon 100 parts by weight of the ethylene copolymer.

3. The film of claim 2 wherein the metallic layer is uncoated and is comprised of a metal selected from the group consisting of aluminum, copper, silver, chromium, gold, and mixtures thereof.

4. The film of claim 3 wherein the at least one oxidized polyethylene wax has a drop point from about 85° C. to about 145° C.

5. The film of claim 4 wherein the substrate is comprised of a material selected from the group consisting of polypropylene, polyethylene, polybutene, polystyrene, polyvinyl chloride, polyesters, polyethylene terephtalate glycol, polyethylene naphthalate, and oriented nylon.

6. The film of claim 5 wherein the ethylene copolymer is selected from the group consisting of a copolymer of ethylene and a carboxylic acid and a copolymer of ethylene and an acrylic ester.

7. The film of claim 6 wherein the at least one ethylene copolymer has a melting point from about 65° C. to about 105° C.

8. The film of claim 7 wherein the at least one oxidized polyethylene wax has a drop point of from about 95° C. to about 140° C.

9. The film of claim 8 wherein the at least one ethylene copolymer is a copolymer of ethylene and carboxylic acid and the carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, citraconic acid, and mixtures thereof.

10. The film of claim 7 wherein the coating is comprised of from about 7 Phr to about 20 Phr of the at least one polyethylene wax based upon 100 parts by weight of the at least one ethylene copolymer.

11. The film of claim 9 wherein the carboxylic acid of the ethylene-carboxylic acid copolymer is selected form the group consisting of acrylic acid and methylacrylic acid, and mixtures thereof.

12. The film of claim 11 wherein the copolymer of ethylene and carboxylic acid comprises ions selected from the group consisting of sodium ions, potassium ions, lithium ions, calcium ions, zinc ions, and mixtures thereof.

13. The film of claim 10 wherein the at least one ethylene copolymer is a copolymer of ethylene and acrylic ester, wherein the acrylic ester is selected from the group consisting of methylacrylate, methylmethacrylate, butylacrylate, and mixtures thereof.

14. The film of claim 11 wherein the metallic layer is comprised of aluminum.

15. The film of claim 14 wherein the at least one oxidized polyethylene wax has a drop point of from about 98° C. to about 115° C.

16. The film of claim 15 wherein the substrate is comprised of a biaxially oriented polypropylene film.

17. The film of claim 16 wherein the substrate is a three layer film.

18. The film of claim 17 wherein the three layer film is comprised of a core layer comprised of biaxially oriented film and at least one skin layer.

19. The film of claim 18 wherein the skin layer of the film is comprised of a polymer selected from the group consisting of a copolymer of propylene and ethylene and a terpolymer of propylene, ethylene, and butylene.

20. The film of claim 17 wherein the film is opaque.

21. The film of claim 17 wherein at least one layer of the film is voided.

22. The film of claim 16 wherein the substrate is a five layer biaxially oriented film.

23. The film of claim 15 wherein the coating is comprised of from about 8 Phr to about 18 Phr of the at least one oxidized polyethylene wax based upon 100 parts by weight of the ethylene-carboxylic acid copolymer.

24. The film of claim 14 wherein the coating is comprised of about 10 Phr of the at least one oxidized polyethylene wax based upon 100 parts by weight of the ethylene-carboxylic acid copolymer and the at least one oxidized polyethylene wax has a drop point from about 98° C. to about 110° C.

25. A package comprised of a film comprising: (a) a substrate having a first surface and a second surface; (b) a metallic layer on the first surface; and (c) a coating on the second surface comprised of at least one ethylene copolymer and from about 5 Phr to about 25 Phr of a polyethylene wax based upon 100 parts by weight of the at least one ethylene copolymer.

26. The packaged product of claim 25 wherein the at least one ethylene copolymer is selected from the group consisting of a copolymer of ethylene and a carboxylic acid and a copolymer of ethylene and an acrylic ester.

27. The packaged product of claim 26 wherein the substrate is comprised of a material selected from the group consisting of polypropylene, polyethylene, polybutene, polystyrene, polyvinyl chloride, polyesters, polyethylene terephtalate glycol, polyethylene naphthalate, and oriented nylon and the polyethylene wax has a drop point of from about 95° C. to about 140° C.