Multilayer high opacity film structures and process for producing same

Abstract: A multilayer opaque, biaxially oriented polymeric film structure. The film structure includes (a) a thermoplastic polymer matrix core layer having a first surface and a second surface, within which is located a strata of voids; positioned at least substantially within a substantial number of the voids is at least one spherical void-initiating particle which is phase distinct and incompatible with the matrix material, the void space occupied by the particle being substantially less than the volume of the void, with one generally cross-sectional dimension of the particle at least approximating a corresponding cross-sectional dimension of the void; the population of the voids in the core being such as to cause a significant degree of opacity; (b) at least one thermoplastic polymer intermediate layer having a first surface and a second surface, the second surface of the intermediate layer adhering to at least the first surface of the core layer, the intermediate layer including up to about 12% by weight of titanium dioxide contact pigment; and (c) a titanium dioxide-free, non-voided thermoplastic skin layer adhering to the first surface of the intermediate layer, the void-free skin layer and the intermediate layer together being of a thickness such that the outer surface of the skin core layer does not, at least substantially, manifest the surface irregularities of the matrix core layer.

Description: This invention relates to the field of polymer films of enhanced opacity and to a method of making such films. More particularly, the invention relates to a biaxially oriented composite film structure having improved properties. In the packaging of certain types of foods, such as snack foods like potato chips, cookies and the like, it is common practice to employ a multilayer film. A desirable property in such a packaging film is an opacity which protects the packaging product from deterioration caused by exposure to light. In particular, it has been found that certain wavelengths of light, up to about 450 nm cause increased spoilage in such packaged products. Even when a degree of opacity is present in the film, spoilage occurs if the film allows passage of some light. It is conventional to provide opacity by including titanium dioxide or other inorganic particles in a layer of the film, but another technique involves forming voids within the film. In particular, there is described in EP-A-083495 and EP-A-265184, opaque biaxially oriented, polymeric film structures having a thermoplastic core matrix which includes a strata of voids created by the inclusion within the matrix of spherical void-initiating solid particles which are incompatible with the matrix material. Both those disclosures propose that the opacity of the film containing void can be enhanced by the inclusion in the thermoplastic core matrix of material such as titanium dioxide. Additionally, EP-A-265184 describes such a film in which the thermoplastic core layer contains voids and titanium oxide particles and a skin layer containing titanium dioxide as whitener is applied over the core layer. The inclusion of titanium dioxide in the outer skin layer of a film structure can provide an excellent surface for printed graphics and can permit the printing of the film structure without the need for white ink, offering a significant saving to the end user. However it can yield certain undesirable characteristics. These characteristics stem from the fact that titanium dioxide (TiO 2 ) is quite abrasive and, when present on the surface of a film, may result in excessive wear of expensive printing and coating gravure roll surfaces, as well as any other surface which is contacted by such a film. Another problem which arises from the use of TiO 2 in the outer skin layers of such films is that fine deposits are laid on converting machinery, extruder die lips, treater bar exhausts, etc. Also, appearance problems caused by streaks on the film, slippage on stretching either by roll or tentering can result. Therefore, what is needed is a film structure of high opacity which provides improved process characteristics and an improved range of process operability, while maintaining high whiteness, strength and stiffness. In particular, it is desirable to provide a multi-layer film structure of high whiteness which does not contribute to gravure roll wear. Preferably the film may be bonded to a wide variety of substrate and coatings. The invention provides novel processes and novel films. An opaque biaxially oriented coextruded film structure according to the invention comprises (a) a core layer of first thermoplastic polymeric material containing a strata of opacifying voids containing microspheres of void-initiating organic or inorganic material having incompatibility with the first thermoplastic material at least at the temperature of biaxial orientation, whereby the voids have been formed during the biaxial orientation, (b) at least one intermediate layer of second thermoplastic polymeric material containing 2 to 12% by weight titanium dioxide contact pigment, and (c) at least one void-free thermoplastic skin layer free of titanium dioxide over an intermediate layer wherein the skin and intermediate layers are of a thickness such that the outer surface of the skin layer does not, at least substantially, manifest surface irregularities of the core layer. The invention includes a process for forming the novel material. In particular, the invention provides a process for preparing an opaque, biaxially oriented polymeric film structure, comprising the steps of: (a) mixing a major proportion of a first thermoplastic polymeric material with a minor proportion of a void-initiating material which preferably often has higher melting point or higher glass transition temperature than the first thermoplastic polymeric material to produce a core layer mixture; (b) heating the core layer mixture produced in step (a) to a temperature of at least above the melting point of the first thermoplastic polymeric material; (c) dispersing the void-initiating material of higher melting point or higher glass transition temperature of the mixture produced in step (a) uniformly throughout the molten first thermoplastic polymeric material in the form of microspheres; (d) mixing a second thermoplastic polymeric material with 2 to 12% titanium dioxide contact pigment to produce an intermediate layer mixture; (e) producing a titanium dioxide-free thermoplastic skin layer mixture; and (f) forming a biaxially oriented coextruded film structure from the core layer mixture, the titanium dioxide-containing intermediate layer mixture and the titanium dioxide-free skin layer mixture, the forming step conducted at a temperature and to a degree to form a strata of opacifying voids within the core layer; wherein the thermoplastic skin layer in combination with the titanium dioxide-containing intermediate layer are of a thickness such that the outer surface of the skin layer does not, at least substantially, manifest surface irregularities of the matrix core layer. A preferred film according to the invention is a five-layer film structure, incorporating the above-described (a), (b) and (c) layers, and further including (d) a second thermoplastic polymer intermediate layer having a first surface and a second surface, the second surface of the second intermediate layer adhering to the second surface of the core layer, the second intermediate layer including up to about 12% by weight of titanium dioxide contact pigment; and (e) a second titanium dioxide-free, non-voided thermoplastic skin layer adhering to the first surface of the intermediate layer, the second void-free skin layer being of a thickness such that the outer surface of the skin layer does not, at least substantially, manifest the surface irregularities of the matrix core layer. The skin layers (c) and/or (e) can be simple, economical thin encapsulating layers or they can be more elaborate heat sealable layers. The thickness of the core layer in the film structure is preferably 60 to 95% of the thickness of the overall structure. The film structure of the invention preferably comprises a thermoplastic polymer matrix core layer which provides 60 to 95% of the overall thickness of the film structure and which has a first surface and a second surface, within which is located a strata of voids; positioned within a substantial number of each of the voids is at least one substantially spherical void-initiating particle which is phase distinct and incompatible with the matrix material, the void space occupied by the particle being substantially less than the volume of the void, with one generally cross-sectional dimension of the particle at least approximating a corresponding cross-sectional dimension of the void; the population of the voids in the core being such as to cause a significant degree of opacity. Preferably the thickness of the core layer is about 65 to 90% of the thickness of the overall structure. This, in combination with the population and configuration of the voids in a total structure at least about 25.4µm (1.0 mil) thick, will materially contribute to the overall degree of opacity of the structure. Likewise, it is advantageous to maintain the thickness of the skin layers within particular ranges in relation to the overall structure and to the thickness of the core layer. Intermediate layer (b), and, when present, intermediate layer (d) has a first surface and a second surface, the second surface of the intermediate layer adhering to at least the first surface of the core layer and the intermediate layer includes 2% to 12% by weight of titanium dioxide content pigment. Preferably the or each intermediate layer has a thickness of from about 5 to about 30% of the overall structure, with a thickness of about 5 to about 15% preferred. This layer serves an important function in reducing water vapour transmission rate (WVTR) and contains TiO 2 as a contact whitening agent. The TiO 2 -free skin layer (c) and (e) when present preferably each has a thickness of from about 0.10% to about 5.0% of the overall structure with thicknesses of from about 0.20% to about 3.0% preferred. The relative thinness of this layer adds to economy in production especially when the layer is an expensive heat-sealable material. Thus, preferably the structure includes a skin layer having a thickness of 0.1 to 5% of the thickness of the overall structure and which is titanium dioxide-free, non-voided thermoplastic skin layer adhering to the first surface of the intermediate layer, the void-free skin layer and the intermediate layer together being of a thickness such that the outer surface of the skin layer does not, at least substantially, manifest the surface irregularities of the matrix core layer. A preferred five-layer structure might include, for example, a core layer with a thickness of about 79% of the overall structure with intermediate layers (b) and (d) having thicknesses of about 8% each and skin layers (c) and (e) having thicknesses of about 2.5% each. The core is a thermoplastic polymer matrix material within which is located strata of voids. From this it is to be understood that the voids create the matrix configuration. The films of the present invention have high opacity and low light transmission. A distinction should be made between opacity and light transmission. Opacity is the opposite of transparency and is a function of the scattering and reflection of light transmitted through the film. Opacity is the ability, for example, to block out writing below it. Light transmission is a function of light passing more directly through the film. The invention is further described with reference to the accompanying drawing in which: Fig. 1 is a schematic diagram of a method for determining percent light transmission. Fig. 2 is a schematic diagram of a method for determining percent opacity. Referring now to Figure 1, the percent light transmission through a film is determined by using light source 2 to transmit light rays 3 directly through film 4 and measuring at light sensor 5, value T 2 . which is the amount of light which is transmitted through film 4. The amount of light rays 3 which can be directly transmitted, value T 1 , is determined by measuring the light 3 directly transmitted by light source 2 with no intervening film. The percent light transmission through the film can then be determined using the formula: % Light Transmission = T 2 T 1 where: T 2 = light transmitted through a film; and T 1 = light directly transmitted. Referring now to Figure 2, for a measure of percent opacity of a film, light source 2 transmits light through film 4 onto a white surface 9 and the same procedure used to project light onto a black surface 10. With both white and black surfaces, measurement at light sensor 5 is of all of the following: light reflected off the upper surface of the film 6; light transmitted through the film and reflected by the white or black surfaces 7 on the side of the film opposite from the light source; and, light scattered by the film 8. The percent opacity of the film can then be determined using the formula: % Opacity = 100 x R B R w where: R w = Reflected light + scattered light + light transmitted through the film and reflected off a white surface; and R B = Reflected light + scattered light + light transmitted through the film and reflected off a black surface. Accordingly, a highly reflective film may provide high opacity while allowing light transmission. This is because percent light transmission is not the equivalent of percent opacity. Light transmission is the amount of light passing directly through the film. To prevent food spoilage decreased light transmission is desirable. In forming the core layer, as in U. S. Patent No. 4,377,616, a master batch technique can be employed by either in the case of forming the void initiating particles in situ or in adding preformed spheres to a molten thermoplastic matrix material. After the formation of a master batch, appropriate dilution of the system can be made by adding additional thermoplastic matrix material until the desired proportions are obtained. However, the components may also be directly mixed and extruded instead of utilizing a master batch method. The void-initiating particles which are added as filler to the polymer matrix material of the core layer can be any suitable organic or inorganic material which is incompatible with the core material at the temperature of biaxial orientation such as polybutylene terephthalate, nylon, solid or hollow preformed glass spheres, metal beads or spheres, ceramic spheres, calcium carbonate, etc. The polyolefin contemplated as the core material includes polypropylene, polyethylene, polybutene and copolymers and blends thereof. Particularly preferred is an isotactic polypropylene containing at least about 80% by weight of isotactic polypropylene. It is also preferred that the polypropylene have a melt flow index of from about 2 to 10 g/10 min. It is preferred that the average diameter of the void initiating particles be from about 0.1 to about 10 microns. These particles may be substantially spherical in shape. This does not mean that every void is the same size. It means that, generally speaking, each void tends to be of like shape when like particles are used even though they vary in dimensions. These voids may assume a shape defined by two opposed and edge contacting concave disks. Experience has shown that optium characteristics of opacity and appearance are obtained when the two average major void dimensions are greater than about 30 microns. The void-initiating particle material, as indicated above, should be incompatible with the core material, at least at the temperature of biaxial orientation. The core has been described above as being a thermoplastic polymer matrix material within which is located a strata of voids. From this it is to be understood that the voids create the matrix configuration. The term "strata" is intended to convey the understanding that there are many voids creating the matrix and the voids themselves are oriented so that the two major dimensions are aligned in correspondence with the direction of orientation of the polymeric film structure. After each void has been formed through the initiation of the described particle, the particle generally contributes little else to the system. This is because its refractive index can be close enough to the matrix material that it makes no contribution to opacity. When this is the case, the opacity is principally a function of the light scattering effect which occurs because of the existence of the voids in the system. A typical void of the core is defined as having major dimensions X and Y and minor dimension Z, where dimension X is aligned with machine direction orientation, dimension Y is aligned with transverse direction orientation and dimension Z approximately corresponds to the cross-sectional dimension of the spherical particle which initiated the void. It is a necessary part of the present invention that orientation conditions be such that the X and Y dimensions of the voids of the core be major dimensions in comparison to the Z dimension. Thus, while the Z dimension generally approximates the cross-sectional dimension of the spherical particle initiating the void, X and Y dimensions must be significantly greater. By way of illustration, room temperature biaxial orientation of a polypropylene matrix containing polybutylene terephthalate (PBT) spheres of the size and amount contemplated herein, could not produce the claimed structure. Either void splitting will occur, or, voids of insignificant size would result. Polypropylene must be oriented at a temperature significantly higher than its glass transition temperature. The temperature conditions must permit X and Y to be at least several multiples of the Z dimension without void splitting at least to any significant degree. If this is acccomplished, optimum physical characteristics, including low water vapor transmission rates and a high degree of light scattering are obtained without void splitting or film fibrillating. As indicated above, the matrix polymer and the void initiating particle must be incompatible and this term is used in the sense that the materials are two distinct phases. The spherical void initiating particles constitute a dispersed phase throughout the lower melting polymer which polymer will, ultimately, upon orientation, become a void-filled matrix with the spherical particles positioned somewhere in the voids. As a result of the biaxial orientation of the film structure herein, in addition to opacifying the core layer of the structure, the orientation improves other physical properties of the composite layers such as flex-crack resistance, Elmendorff tear strength, elongation, tensile strength, impact strength and cold strength properties. The resulting film can have, in addition to a rich high quality appearance and excellent opacifying characteristics, low water vapor transmission rate characteristics and low oxygen transmission rate characteristics. This makes the film ideally suited for packaging food products including liquids. The film also has attractive utility as a decorative wrap material. It is believed that because of comparative sphericity of the void-initiating particles, the voids are closed cells. This means that there is virtually no path open from one side of the core the other throughout which liquid or gas can transverse. The opacity and low light transmission of the film is further enhanced by the addition to the core layer of from about 1% by weight and up to about 10% by weight of opacifying compounds which do not contribute to void formation and which are added to the melt mixture of the core layer before extrusion. Opacifying compounds which may be used include iron oxides, carbon black, aluminum, TiO 2 , and talc. The polyolefin contemplated as the material for use in forming intermediate layers (b) and (d) includes polypropylene, polyethylene, polybutene and copolymers and blends thereof. As was the case for the core layer, particularly preferred is an isotactic polypropylene containing at least about 80% by weight of isotactic polypropylene. It is also preferred that the polypropylene have a melt flow index of from about 2 to 10 g/10 m. The opacity, whiteness and low light transmission of the film is further enhanced by the addition to intermediate layers (b) and (d) of TiO 2 in amount of from about 2% by weight and up to about 10% by weight, which is added to the melt mixture of the intermediate layer before extrusion. Preferably, the intermediate layers contain from about 2% by weight to 6% by weight of TiO 2 . Additionally, the intermediate layers may also contain talc. The whiteness resulting from the inclusion of TiO 2 provides an excellent surface for graphics. Furthermore, the whiteness allows printing of laminated or unlaminated structures without requiring white ink. Layers (c) and (e) are thin skin layers applied to the surfaces of intermediate layers (b) and (d) which are not in contact with the core layer (a). Layers (c) and (e) are preferably of a material having a low WVTR. This layer may consist of a propylene; high density polyethylene; linear low density polyethylene; block copolymer of ethylene and propylene; random copolymer of ethylene and propylene; other ethylene homopolymer, copolymer, terpolymer; or blends thereof. The homopolymer contemplated herein is formed by polymerizing the respective monomer. This can be accomplished by bulk or solution polymerization, as those skilled in the art would plainly understand. One of the preferred materials for layers (c) and/or and (e) is isotactic polypropylene. Skin layers (c) and (e) are of a thickness sufficient to encapsulate the TiO 2 -containing intermediate layers, thus achieving the desired objective of substantially eliminating processing machinery wear problems associated with TiO 2 -containing outer layers. Moreover, the combination of intermediate layer (b) and skin layer (c) and intermediate layer (d) and skin layer (e) provide a thickness such that the outer surface of each skin layer does not, at least substantially, manifest the surface irregularities of the matrix core layer (a). The copolymer contemplated herein for skin layers (c) and/or (e) can be selected from those copolymers typically employed in the manufacture of multi-layered films. For example, a block copolymer of ethylene and propylene is formed by sequential polymerization of the respective monomers. The feeding of the monomers in forming a block copolymer is controlled so that the monomer employed in one stage of the sequential polymerization is not added until the monomer employed in the preceding stage has been at least substantially consumed thereby insuring that the concentration of the monomer remaining from the preceding stage is sufficiently low to prevent formation of an excessive proportion of random copolymer. Also, as indicated above, a random copolymer of ethylene and propylene can be advantageously employed to form skin layers (c) and/or (e). The contemplated terpolymers which may be used for skin layers (c) and/or (e) are comparatively low stereoregular polymers. The terpolymers can have a melt flow rate at 230°C (446°F) ranging from about 2 to about 10 grams per 10 minutes and preferably from about 4 to about 6 grams per 10 minutes. The crystalline melting point can range from about less than 121°C (250°F) to somewhat greater than 188°C (371°F). The terpolymers will predominate in propylene, and the ethylene and 1-butene monomers can be present in approximately from 0.3:1- 1:1 mole percentage in relation to each other. If desired, the exposed surface of skin layers (c) and/or (e) can be treated in a known and conventional manner, e.g., by corona discharge to improve its receptivity to printing inks and/or its stability for such subsequent manufacturing operations as lamination. The exposed treated or untreated surface of layers (c) and/or (e) may have applied to it, coating compositions or substrates such as another polymer film or laminate; a metal foil such as aluminum foil; cellulosic webs, e.g. numerous varieties of paper such as corrugated paperboard, craft paper, glassine, cartonboard; nonwoven tissue, e.g., spunbonded polyolefin fiber, melt-blown microfibers, etc. The application may employ a suitable adhesive, e.g., a hot melt adhesive such as low density polyethylene, ethylene-methacrylate copolymer, water-based adhesive such as polyvinylidene chloride latex, and the like. Layers (c) and/or (e) may also include up to about 1% by weight, with about 500 ppm to about 5000 ppm preferred and 1000 ppm most preferred, of inorganic particles, such as amorphous silica or talc to provide antiblock properties. Skin layers (c) and/or (e) can also be fabricated from any of the heat sealable copolymers, blends of homopolymers and blends of copolymer(s) and homopolymer(s) heretofore employed for this purpose. Illustrative of heat sealable copolymers which can be used in the present invention are ethylene-propylene copolymers containing from about 1.5 to about 10, and preferably from about 3 to about 5 weight percent ethylene and ethylene- propylene-butene terpolymers containing from about 1 to about 10, and preferably from about 2 to about 6 weight percent ethylene and from about 80 to about 97, and preferably from about 88 to about 95 weight percent propylene. Heat sealable blends of homopolymer which can be utilized in providing layers (c) and/or (e) include from about 1 to about 99 weight percent polypropylene homopolymer, e.g., one which is the same as, or different from, the polypropylene homopolymer constituting core layer (a) blended with from about 99 to about 1 weight percent of a linear low density polyethylene (LDPE). If layers (c) and/or (e) are heat-sealable, corona or flame treatment of layers (c) and/or (e) is not required. Heat sealable blends of copolymer(s) and homopolymer(s) suitable for providing layers (c) and/or (e) include: a blend of from about 5 to about 19 weight percent of polybutylene and from about 95 to about 81 weight percent of a copolymer of propylene (80 to about 95 mole percent) and butylene (20 to about 5 mole percent); a blend of from about 10 to about 90 weight percent of polybutylene and from about 90 to about 10 weight percent of a copolymer of ethylene (2 to about 49 mole percent) and a higher olefin having 4 or more carbon atoms (98 to about 51 mole percent); a blend of from about 10 to about 90 weight percent polybutylene and from about 90 to about 10 weight percent of a copolymer of ethylene (10 to about 97 mole percent) and propylene (90 to about 3 mole percent); and, a blend of from about 90 to about 10 weight percent of polybutylene, and from about 10 to about 90 weight percent of a copolymer of propylene (2 to about 79 mole percent) and butylene (98 to about 21 mole percent). If skin layers (c) and/or (e) are not heat sealable, and that property is desired on one or both of those surfaces, then a heat sealable layer (f) may be applied to one or both of those surfaces. Heat sealable layer (f) may be, for example, vinylidene chloride polymer or an acrylic polymer; or it may be coextruded from any of the heat sealable materials described herein. Vinylidene chloride polymer or acrylic polymer coating are preferred materials which my be applied to the exposed exterior surfaces of the skin layers. It is preferred that all layers of the multilayer film structures of the present invention be coextruded. Thereafter, the film is biaxially oriented. For example, when employing polypropylene for the core matrix and the skin layers and employing PBT as the void initiating particles, a machine direction orientation may be from about 4 to about 8 and a transverse orientation may be from 4 to about 10 times at a drawing temperature of about 100°C to 170°C to yield a biaxially oriented film. A preferred film thickness is from about 13µm (0.5 mil) to about 89µm (3.5 mils). The films of the present invention combine the advantages of the provision of a voided core layer with the advantages of a titanium dioxide-containing skin layer whilst avoiding the disadvantages of the latter. The invention includes not only the films and the processes of making them, but also the use of the film structures in the packing of comestibles. The following specific examples are presented herein to illustrate particular embodiments of the present invention and hence are illustrative of this invention and not to be construed in a limiting sense. Comparative Example 1 This film of this example was produced for comparison with the films produced in accordance with the present invention. A mixture of 92 percent, by weight, isotactic polypropylene (MP = 160°C (320°F.), melt index = 3), containing 8 weight percent PBT (MP = 222°C (440°F.)) as the core layer void- initiating material, is melted in an extruder with a screw of L/D ratio of 20/1 to provide the core layer mixture. A second and third extruder, in association with the first extruder, are each supplied with the same isotactic polypropylene (without PBT) as the first extruder, but each containing titanium dioxide particles at 4 percent, by weight. The titanium dioxide particles are employed as a contact whitener for this intermediate layer mixture. A fourth extruder, in association with the first three extruders, is supplied with the same isotactic polypropylene/titanium dioxide as the second extruder, this extruder being used to provide the skin layer mixture. A melt coextrusion is carried out while maintaining the cylinder of the core polymer material at a temperature sufficient to melt the polymer mixture, i.e., from about 232°C (450°F) to about 288°C (550°F) or higher. The polypropylene mixtures of the second and third extruders to be extruded as intermediate layers are maintained at about the same temperature as the polypropylene used in fabricating the core layer, as are the mixtures being used to for the skin layers. The mixture of the fourth extruder is split into two streams to enable the formation of skin layers on each surface of the intermediate layers. As may be appreciated by those skilled in the art, rather than splitting the output of the fourth extruder into two streams, a fifth extruder could be used to supply the second skin layer mixture. Such an arrangement would be desired when the material used to form the second skin layer is varied from that of the first skin layer, when the thickness of the second skin layer is varied from that of the first skin layer, etc. A five-layer film laminate was coextruded with a core thickness representing about 80 percent of the overall extruded thickness, with the thicknesses of the intermediate layers representing about 16 percent and the skin layers representing about 4 percent of the film thickness. The unoriented film measured about 40 mils in thickess. The resultant film sheet was subsequently oriented eight by five and one-half times using a commercially available sequential biaxially orienting apparatus to provide a multilayer film structure. The machine direction (MD) orientation is conducted at about 141°C (285°F.) and the transverse direction (TD) orientation is conducted at about 149°C (300°F.) The resultant 33 µm (1.3 mil) multilayer film exhibits a lustrous appearance. Example 2 To form a multilayer film in accordance with the present invention, a mixture of 92 percent, by weight, isotactic polypropylene (MP = 160°C (320°F.), melt index = 3), containing 8 weight percent PBT (MP = 227°C (440°F.)) as the core layer void- initiating material, is melted in an extruder with a screw of L/D ratio of 20/1 to provide the core layer mixture. Again, a second and third extruder, in association with the first extruder, are each supplied with the same isotactic polypropylene (without PBT) as the first extruder, again containing titanium dioxide particles at 4 percent, by weight for this intermediate layer mixture. A fourth extruder, in association with the first three extruders, is supplied with the same isotactic polypropylene, this time without titanium dioxide, to provide the skin layer mixture. A melt coextrusion is carried out while maintaining the cylinder of the core polymer material at a temperature sufficient to melt the polymer mixture, i.e., from about 232°C (450°F.) to about 288°C (550°F.) or higher. Again, the polypropylene mixtures to be extruded as intermediate layers are maintained at about the same temperature as the polypropylene used in fabricating the core layer, as is the mixture being used for the skin layers. As in Example 1, the mixture of the fourth extruder is split into two streams to enable the formation of skin layers on each surface of the intermediate layers. As was the case for Example 1, rather than splitting the output of the fourth extruder into two streams, a fifth extruder could have been used to supply the second skin layer mixture so that the thickness or the material used to form the second skin layer could be varied from that of the first skin layer. A five-layer film laminate was coextruded with a core thickness representing about 80 percent of the overall extruded thickness, with the thicknesses of the intermediate layers representing about 16 percent and the skin layers representing about 4 percent of the film thicknesses. The unoriented film, once again, measured about 1016 µm (40 mils) in thickness. As in Example 1, the resultant film sheet was oriented eight by five and one-half times using a commercially available sequential biaxially orienting apparatus to provide a multilayer film structure. The machine direction (MD) orientation is conducted at about 141°C (285° F.) and the transverse direction (TD) orientation is conducted at about 149°C (300°F). The resultant 33 µm (1.3 mil) multilayer film exhibits a smooth and lustrous appearance. Example 3 Another multilayer film, in accordance with the present invention, was produced. Again, the same mixture of 92 percent, by weight, isotactic polypropylene (MP = 160°C (320°F.), melt index = 3), containing 8 weight percent PBT (MP = 227°C (440°F.) as the core layer void-initiating material, was melted in the extruder of Examples 1 and 2. The second and third extruders were supplied with the same isotactic polypropylene (without PBT), containing titanium dioxide particles at 4 percent, by weight for use as the intermediate layer mixture. A fourth extruder, in association with the first three extruders, is supplied with the same isotactic polypropylene, this time with 1000 ppm of amorphous silica added (without titanium dioxide) to provide the skin layer mixture. A melt coextrusion is carried out while maintaining the cylinder of the core polymer material at a temperature sufficient to melt the polymer mixture, i.e., from about 232°C (450°F.) to about 288°C (550°F.) or higher. Again, the polypropylene mixtures to be extruded as intermediate layers are maintained at about the same temperature as the polypropylene used in fabricating the core layer, as are the mixtures being used to for the skin layers. As in Examples 1 and 2, the mixture of the fourth extruder is split into two streams to enable the formation of skin layers on each surface of the intermediate layer. A five-layer film laminate is coextruded with a core thickness representing about 80 percent of the overall extruded thickness, with the thicknesses of the intermediate layers representing about 16 percent and the skin layers representing about 4 percent of the film thickness. The unoriented film again measured about 1016 µm (40 mils) in thickness. This film sheet was also oriented eight by five and one-half times using a commercially available sequential biaxially orienting apparatus. The machine direction (MD) orientation is conducted at about 141°C (285°F.) and the transverse direction (TD) orientation is conducted at about 144°C (300°F). The resultant 33 µm (1.3 mil) multilayer film exhibits a smooth and lustrous appearance. Example 4 Another multilayer film was produced in accordance with the present invention. Again, the same mixture of 92 percent, by weight, isotactic polypropylene (MP = 160°C (320°F.) melt index = 3), containing 8 weight percent PBT (MP = 227°C (440°F.)) as the core layer void-initiating material, was melted in the extruder of the previous examples to provide the core layer mixture. The second and third extruders, in association with the first extruder, were supplied with the same isotactic polypropylene (without PBT) as the first extruder, containing titanium dioxide particles at 4 percent by weight for use in forming the intermediate layer. A fourth extruder, in association with the first three extruders, was provided with an ethylene, 1-butene, polypropylene terpolymer, instead of the isotactic polypropylene used in Examples 1 through 3. As in Example 3, 1000 ppm of amorphous silica was added to the skin layer mixture. A melt coextrusion is carried out while maintaining the cylinder of the core polymer material at a temperature sufficient to melt the polymer mixture, i.e., from about 232°C (450°F.) to about 288°C (550°F.) or higher. Again, the polypropylene mixtures to be extruded as intermediate layers are maintained at about the same temperature as the polypropylene used in fabricating the core layer, as is the terpolymer mixture being used to form the skin layers. As in the previous Examples, the mixture of the fourth extruder is split into two streams each to enable the formation of skin layers on each surface of the intermediate layer. A five-layer film laminate is coextruded with a core thickness representing about 80 percent of the overall extruded thickness, with the thicknesses of the intermediate layers representing about 16 percent and the skin layers representing about 4 percent of the film thickness. The unoriented film once again measured about 40 mils in thickness. The resultant film sheet was subsequently oriented eight by five and one-half times using a commercially available sequential biaxially orienting apparatus to provide a multilayer film structure. The machine direction (MD) orientation is conducted at about 141°C (285°F.) and the transverse direction (TD) orientation is conducted at about 149°C (300°F). The resultant 33 µm (1.3 mil) multilayer film exhibits a smooth and lustrous appearance. The films so produced were tested light transmission, gloss, whiteness index and coefficient of friction (COF), with optical thickness and film density also measured. Results obtained are presented in Table 1, below. Ex. No. Unit Weight (g/m 2 ) Optical Thick. µm (mils) Light Transmission, % Gloss % Whiteness Index Coef. of Frict. 1 20.62 32 (1.26) 22.8 69 93.5 0.46 2 20.82 33 (1.30) 20.6 82 93.9 0.80 3 20.51 32 (1.26) 21.6 79 94.5 0.60 4 19.61 32 (1.26) 20.8 74 95.0 0.80 As illustrated, films produced in accordance with the present invention exhibit the highly desirable properties of films having TiO 2 -containing skin layers. Example 5 This example demonstrates that films produced in accordance with the present invention do not possess the adverse wear characteristics of films which employ titanium dioxide- whitened outer skin layers. To illustrate the benefits of films produced in accordance with the present invention, a pilot coater experiment was established which sought to measure the changes in gravure roll cell landing width and depth with time. As those skilled in the art recognize, cell depth decreases and landing width increases with increased wear. PILOT COATER FILMS EXPERIMENT CHANGES IN GRAVURE ROLL CELL LANDING WIDTH AND DEPTH WITH TIME Time Hrs. Film of Example 1 Film of Example 2 Depth (um) Width (um) Depth (um) Width (um) 0 137 31 132 28 1 135 40 132 28 5 127 60 132 29 12 110 75 132 30 As may be appreciated, gravure roll wear occurs in reverse coating applications where the film and the gravure roll surfaces are moving in opposite directions having only a small wet contact region. For example, it has been found that when coating films having TiO 2 -containing outer layers in operations using gravure rolls having a truncated pyramid cell structure, the gravure roll will last only 8 - 10 days. The same gravure roll can be expected to last 3 - 4 months when coating films produced in accordance with the present invention. Films so produced, as demonstrated by the examples, exhibit the highly desirable propties of films having TiO 2 -containing skin layers, without the processing problems associated therewith. The data of Examples 1-5 clearly show the unexpected superiority of this invention in providing a film with exceptional properties.

Claims: An opaque biaxially oriented coextruded film structure comprising (a) a core layer of first thermoplastic polymeric material containing a stratum of opacifying voids containing microspheres of a void-initiating organic or inorganic material having incompatibility with the first thermoplastic material at least at the temperature of biaxial orientation, whereby the voids were formed during the biaxial orientation, (b) at least one intermediate layer of second thermoplastic polymeric material containing 2 to 12% by weight titanium dioxide contact pigment, and (c) at least one void-free thermoplastic skin layer free of titanium dioxide over an intermediate layer wherein the skin and the intermediate layers are of a thickness such that the outer surface of the skin layer does not, at least substantially, manifest surface irregularities of the core layer. A film structure according to claim 1 wherein the core layer (a) has a thickness of 60 to 95% of the overall thickness of the structure and has a first surface and a second surface, within which is located a stratum of voids; positioned within a substantial number of each of the voids is at least one substantially spherical void-initiating particle which is phase distinct and incompatible with the matrix material, the void space occupied by the particle being substantially less than the volume of the void, with one generally cross-sectional dimension of said particle at least approximating a corresponding cross-sectional dimension of the void; the population of the voids in the core being such as to cause a significant degree of opacity; and the intermediate layer (b) has a thickness of 5 to 30% of the thickness of the overall structure and has a first surface and a second surface, the second surface of the intermediate layer adhering to at least the first surface of the core layer; and in which the skin layer (c) has a thickness of 0.1 to 5% of the thickness of the overall structure. A film structure according to either preceding claim additionally comprising (d) a second thermoplastic polymer intermediate layer having a first surface and a second surface, the second surface of the second intermediate layer adhering to the second surface of the core layer, the second intermediate layer including 2 to 12% by weight of titanium dioxide contact pigment; and (e) a second titanium dioxide-free, non-voided thermoplastic skin layer adhering to the first surface of the intermediate layer, the second void-free skin layer and the second intermediate layer together being of a thickness such that the outer surface of the skin layer does not, at least substantially, manifest the surface irregularities of the matrix core layer. A film structure according to any preceding claim in which the core layer has a thickness of 65 to 90% of the thickness of the overall structure. A film structure according to any preceding claim in which the or each intermediate layer has a thickness of 5 to 15% of the thickness of the overall structure. A film structure according to any preceding claim in which the or each skin layer has a thickness of 0.2 to 3% of thickness of the overall structure. A film structure according to any preceding claim in which the or each intermediate layer contains from 2 to 6% by weight titanium dioxide. A film structure according to any preceding claim having at least one skin layer which comprises an anti-blocking agent. A film structure according to any preceding claim in which the void initiating particles are selected from polybutylene terephthalate and calcium carbonate. A film structure according to any preceding claim in which the core layer and/or at least one said intermediate layer and/or at least one said skin layer comprises isotactic polypropylene. A film structure according to any preceding claim in which at least one said skin layer comprises a heat sealable material. A film structure according to any preceding claim wherein at least one said skin layer comprises a homopolymer of propylene, a linear density polyethylene, a high density polyethylene, a random polymer of propylene and ethylene, a block copolymer of propylene and ethylene, a copolymer of propylene and butylene, a terpolymer of ethylene, propylene and butylene, a terpolymer of ethylene, propylene and butylene, or a mixture thereof. Use of a film structure according to any preceding claim in the packaging of comestibles. A process for making a film structure according to any of claims 1 to 12 comprising: (a) mixing a major proportion of a first thermoplastic material with a minor proportion of a void initiating material to produce a core layer mixture; (b) heating the core layer mixture produced in step (a) to a temperature of at least above the melting point of the first thermoplastic polymeric material; (c) dispersing the void forming material in the molten mixture in the form of microspheres; (d) mixing a second thermoplastic material with 2 to 12% titanium dioxide contact pigment to produce an intermediate layer mixture; (e) producing a titanium dioxide-free skin layer mixture, and (f) forming a biaxially oriented coextruded film structure from the core layer mixture, the titanium dioxide containing intermediate layer mixture and the titanium dioxide free skin layer mixture, the forming step being conducted at a temperature and to a degree to form a strata of opacifying voids within the core layer, wherein the thermoplastic skin layer in combination with the titanium dioxide-containing intermediate layer are of a thickness such that the outer surface of the skin layer does not, at least substantially, manifest surface irregularities of the matrix core layer.

Inventors: FROGNET JEAN-PIERRE, KELLER LAJOS EDWARD, PETITJEAN MAURICE, FROGNET, JEAN-PIERRE, KELLER, LAJOS EDWARD, PETITJEAN, MAURICE
Applicants: MOBIL OIL CORP, MOBIL OIL CORPORATION
Application year: 1992
Main classification: B32B27
IPC codes: C08J9, B32B7, B32B27, B29C47, B29C55, B29L7, B65D65, B29L9, B32B5, B29K105