WO2020047218A1

WO2020047218A1 - Machine direction oriented polymeric film for labeling recyclable structures

Info

Publication number: WO2020047218A1
Application number: PCT/US2019/048755
Authority: WO
Inventors: Matt Wilkinson
Original assignee: Avery Dennison Corporation
Priority date: 2018-08-31
Filing date: 2019-08-29
Publication date: 2020-03-05

Abstract

Provided herein are machine oriented polymeric films that include one or more polypropylene polymers, one or more olefin elastomers, and one or more cavitation agents. The cavitated films are particularly useful in label constructions to be applied to recyclable materials. Also provided are labels including the films disclosed herein, and methods for producing the disclosed films.

Description

MACHINE DIRECTION ORIENTED POLYMERIC FILM FOR LABELING RECYCLABLE SUBSTRATES

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the benefit of U.S. Provisional Patent Application Nos. 62/725,735 filed August 31, 2018 and 62/732,524 filed September 17, 2018, both of which are incorporated herein by reference in their entireties.

FIELD

[0002] The present disclosure relates generally to machine direction oriented polymeric films particularly useful in the preparation of printable labels to be applied to recyclable substrates.

BACKGROUND

[0003] Labels, such as pressure-sensitive adhesive labels, are commonly fastened to articles for the purpose of presenting information such as a product description, price, or barcode, or to add decorative features to the articles. Label construction typically includes a layer of facestock material for holding and displaying the printed information or decoration. The facestock layer is usually backed by a layer of adhesive which can be covered by a release liner or carrier before the label is applied to an article. This allows the labels to be rolled or folded onto each other without the labels sticking to each other. The adhesive layer is attached to the article once the label is applied.

[0004] Some articles subject to labeling, such as glass or plastic bottles, are made from materials that can be recycled. While such articles themselves are amenable to typical recycling processes, one or both of the facestock or adhesive materials of labels attached to the articles may not be. The need exists, therefore, for face layer materials, such as polymeric films, that have an improved compatibility with conventional recycling methods.

SUMMARY

[0005] Machine direction oriented polymeric films are described herein. In some embodiments, the film has a density less than about 0.95 g/cm³, for example, from about 0.90 to about 0.95 g/cm³or 0.90 to 0.95 g/cm³. In some embodiments, the film has the density described above and contains at least one propylene homopolymer, copolymer, or blend of two or more thereof. In some embodiments, the at least one propylene homopolymer, copolymer, or blend thereof has a melt flow rate ranging from about 0.5 to about 40 g/10 minutes.

[0006] In some embodiments, the films described above further contain at least one olefin elastomer. In some embodiments, the at least one olefin elastomer contains an ethylene homopolymer or copolymer, a propylene homopolymer or copolymer, or a mixture of two or more thereof.

[0007] The films described above further contain from about 0.5 to about 10 wt% of a cavitation agent. In some embodiments, the cavitation agent is or contains polybutylene terephthalate.

[0008] In some embodiments, the films described above have an L+W machine direction stiffness greater than or equal to about 20 mN.

[0009] In some, the films described above exhibit a shrinkage of less than about 3% at 70 °C.

[0010] Methods for preparing the machine direction oriented polymeric films described above are also described herein. In some embodiments, the method includes providing at least one propylene homopolymer, copolymer, or blend of two or more thereof; at least one olefin elastomer; and a cavitation agent and combining the provided components to form a mixture. The method further includes extruding a film containing, or from, the formed mixture. The method further includes stretch orienting the extruded film in the machine direction, thereby preparing the machine direction oriented polymeric film having a density ranging less than 0.95 g/cm³, such as from 0.9 to 0.95 g/cm³.

[0011] Labels containing the film(s) described above are also described herein. The label contains a machine direction oriented polymeric film as described above. The label further contains an adhesive layer. In some embodiments, the adhesive layer is adhesively joined to the film.

[0012] Methods of applying the label described above to a surface are also described herein. The method including providing a surface having an outer face and adhering the label to the outer face of the surface, thereby applying the label to the surface. Labeled surface

[0013] Labeled surfaces including one or more labels described above are also described herein. The labeled surface contains a surface having an outer face. The labeled surface further contains a label as disclosed herein, wherein the label is adhered to the outer face of the surface. DETAILED DESCRIPTION

[0014] Uniaxial machine direction oriented polymeric films that, when employed for example in label applications, provide advantageous improvements (or combinations of improvements) in the labeling of recyclable materials to which the films are attached, are described herein.

[0015] For example, it is beneficial for labels including a polymeric film to be easily and cleanly removed from the surface of a recyclable article such that the article can be processed according to typical recycling procedures. It is also beneficial for films to have good cuttability and dispensability, to allow them to more easily be used in the manufacture of labels. Films that provide sharp and distinct cuts during manufacture can be processed with reduced die-cutting pressure, and less sharp cutting tools, than could otherwise be used. In contrast, for films having a poor cuttability, the failure to achieve a clean die- cut perimeter between a label and surrounding matrix can cause the matrix to break, in either the machine or cross directions, and remain with the label on a release liner. This defect can adversely affect dispensing operation by, for example, applying a double label or label plus matrix strip(s) to the substrate.

[0016] Another desired characteristic of label facestock films is printability, particularly with respect to UV-based inks that are most commonly used to print pressure sensitive labels. In addition, the conformability of a label material can improve its ability to be applied to a wider variety of substrate materials and shapes without significant formation of bubbles during application. Other beneficial properties of label films include a low degree of shrinkage upon exposure to temperature changes, a high strength to prevent label damage, and good adhesion properties to minimize delamination from other layers of the label.

[0017] Unfortunately, it has proven difficult for conventional films to simultaneously meet many or all of these desired characteristics. To that end, the polymeric films can surprisingly improve film performance in several advantageous aspects. In particular, it has been found that by adding cavitation agents, e.g., in specific proportions to other components of a machine oriented film, and optionally by employing particular extrusion/stretch parameters, the resultant film can beneficially have a lower construction density. In some embodiments, the combination of extrusion and stretch parameters may be synergistic. This reduced density has been found to, for example, provide label composites more suitable for use in conventional recycling processes, e.g., polyethylene terephthalate (PET) recycling processes. In addition, the use of the cavitation agents (and the optional extrusion/stretch parameters) has unexpectedly been found to provide the advantages of improving die cutting and/or die wear performance as well as the advantage of reducing overall material use, which has efficiency and cost implications. Importantly, the use of the cavitation agent does not negatively impact (and in some cases may improve) other properties of the film, such as strength.

[0018] Without being bound by theory, it is believed that the incompatibility of the cavitation agents with the surrounding polymer matrix allows the cavitation agents to serve as nuclei for cavities formed in the extrusion and stretching processes, e.g., during the extrusion of the film and/or the stretching operations. As a result, the film contains such cavities, e.g., evenly-dispersed throughout the film, which advantageously contribute to a reduction in density.

[0019] In addition to the density reduction, the cavitation also improves the ability to scatter light through the film, which increases the opacity of the film. This increase in opacity can be particularly advantageous because it, in turn, can allow for the use of lower amounts, if any, of (hard) pigmenting agents, e.g., titanium dioxide. Pigmenting agents can be used to increase opacity, for example in applications, such as labeling applications, calling for opaque films. Pigmenting agents, because of their physical properties such as hardness, are generally known to have detrimental effects on cutting operations, and often result in die degradation. Thus, the ability of the films to have lower amounts, if any, of such pigmenting agents provides for improvements in cutting operations and die degradation. Stated another way, the less dense films with lower concentrations of hard materials can be more amenable to manufacturing processes such as film cutting. In addition, the degradation of, for example, die cutting apparatus used to process the film can be reduced, providing further benefits to manufacturing costs and robustness.

[0020] Another advantage of reduced component requirements such as these for the provided cavitated films is a decrease in raw material cost. These and other benefits are affected not only by the amount of cavities present in the disclosed films, but also by the geometries of the cavities. In some embodiments, the particular parameters, e.g., stretch ratios and stretch temperatures, of the provided methods can generate these geometries and provide the aforementioned advantageous combination(s) of features.

[0021] Parameters including, but not limited to, concentration, temperature, density, viscosity, mechanical properties, etc. may be defined herein as a minimum or maximum value or as a range of values. The term "" may be used with any of the minima, maxima, or ranges described herein to indicate values just below and/or above the minima, maxima, or end points of the range. Alternatively, the minima, maxima, or end points of the range can be expressed as finite points (i.e., without the use of the term ""). I. Machine Direction Oriented Films

[0022] In some embodiments, the film contains a first component (component A), which is selected from at least one propylene homopolymer, copolymer, or blends thereof, e.g., blends of two or more thereof, and a second component (component B), which is selected from at least one olefin elastomer. In some embodiments, the second component is different from the first component. The film further contains a third component (component C), which is at least one cavitation agent. In some cases, these three components are components of a mixture that is extruded to form the polymeric film, and stretched in the machine direction to provide the extruded film with its desired uniaxial orientation. In some embodiments, the stretching is at a stretch ratio ranging from about 4 to about 8. In some embodiments, the stretching is at a stretch ratio ranging from 4 to 8. In some embodiments, the stretch in the machine direction is from 4.5 to 7.5, 4.5 to 7.0, 4.5 to 6.5, 4.5 to 6.0 or 4.5 to 5.5. In other embodiments, the stretch in the machine direction is 5.0 to 8.0, 5.0 to 7.5, 5.0 to 7.0, 5.0 to 6.5, 5.0 to 6.0, or 5.0 to 5.5. In some embodiments, the stretch in the machine direction is from about 5.0 to about 5.5 or is from 5.0 to 5.5.

[0023] The film can be oriented by stretching in the machine direction at a stretch ratio that can, for example, range from about 4 to about 8, e.g., from 4 to 6.4, from 4.4 to 6.8, from 4.8 to 7.2, from 5.2 to 7.6, or from 5.6 to 8. In terms of upper limits, the stretch ratio can be less than about 8, e.g., less than 7.8, less than 7.6, less than 7.2, less than 7.0, less than 6.8, less than 6.6., less than 6.4, less than 6.2, less than 6, less than 5.8, less than 5.6, less than 5.4, less than 5.2, less than 5.0, less than 4.8, less than 4.6, less than 4.4, or less than 4.2. In terms of lower limits, the stretch ratio can be greater than 4, e.g., greater than 4.2, greater than 4.4, greater than 4.6, greater than 4.8, greater than 5.0, greater than 5.2, greater than 5.4, greater than 5.6, greater than 5.8, greater than 6, greater than 6.2, greater than 6.4, greater than 6.6, greater than 6.8, greater than 7.0. greater than 7.2, greater than 7.4, or greater than 7.6. Higher stretch ratios, e.g., greater than 8, and lower stretch ratios, e.g., less than 4, may also be contemplated.

[0024] The cavitation of the machine direction oriented polymer film allows it to have a reduced construction density that can be advantageous in, for example, increasing the compatibility of the film with existing recycling processes. In some embodiments, the density is less than 0.95 cm³. In some embodiments, the density of the film is from 0.9 g/cm³ to 0.95 g/cm³, e.g., from 0.9 g/cm³ to 0.93 g/cm³, from 0.905 g/cm³ to 0.935 g/cm³, from 0.91 g/cm³ to 0.94 g/cm³, from 0.915 g/cm³ to 0.945 g/cm³, or from 0.92 g/cm³ to 0.95 g/cm³. In terms of upper limits, the film density can be less than 0.95 g/cm³, e.g., less than 0.945 g/cm³, less than 0.94 g/cm³, less than 0.935 g/cm³, less than 0.93 g/cm³, less than 0.925 g/cm³, less than 0.92 g/cm³, less than 0.915 g/cm³, less than 0.91 g/cm³, or less than 0.905 g/cm³. In terms of lower limits, the film density can be greater than 0.9 g/cm³, e.g., greater than 0.905 g/cm³, greater than 0.91 g/cm³, greater than 0.915 g/cm³, greater than 0.92 g/cm³, greater than 0.925 g/cm³, greater than 0.93 g/cm³, greater than 0.935 g/cm³, greater than 0.94 g/cm³, or greater than 0.945 g/cm³. Higher film densities, e.g., greater than 0.95 g/cm³, and lower film densities, e.g., less than 0.9 g/cm³, are also contemplated.

[0025] In some embodiments, the density of the film ranges from 0.6 g/cm³ to 0.95 g/cm³, e.g., from 0.55 g/cm³ to 0.79 g/cm³, from 0.59 g/cm³ to 0.83 g/cm³, from 0.63 g/cm³ to 0.97 g/cm³, from 0.67 g/cm³ to 0.91 g/cm³, or from 0.71 g/cm³ to 0.95 g/cm³. In terms of upper limits, the film density can be less than 0.95 g/cm³, e.g., less than 0.91 g/cm³, less than 0.87 g/cm³, less than 0.83 g/cm³, less than 0.79 g/cm³, less than 0.75 g/cm³, less than 0.71 g/cm³, less than0.67 g/cm³, less than 0.63 g/cm³, or less than 0.59 g/cm³. In terms of lower limits, the film density can be greater than 0.55 g/cm³, e.g., greater than 0.59 g/cm³, greater than 0.63 g/cm³, greater than 0.67 g/cm³, greater than 0.71 g/cm³, greater than 0.75 g/cm³, greater than 0.79 g/cm³, greater than 0.83 g/cm³, greater than 0.87 g/cm³, or greater than 0.91 g/cm³. Higher film densities, e.g., greater than 0.95 g/cm³, and lower film densities, e.g., less than 0.55 g/cm³, are also contemplated.

A. Propylene Homopolymers, Co-polymers, and Combinations Thereof

[0026] In some embodiments, the film contains a first component (component A), which is selected from at least one propylene homopolymer, copolymer, or blends thereof, e.g., blends of two or more thereof.

[0027] In some embodiments, Component A is, or includes, a propylene homopolymer. Commercially available propylene homopolymers suitable for use in the films disclosed herein include, but are not limited to, SABIC^® PP 500P, having a melt flow rate of 3.1 g/10 minutes, a density of 0.905 g/cm³, and a differential scanning calorimetry melting point of 160 °C; SABIC^® PP 520P, having a melt flow rate of 10.5 g/10 minutes and a density of 0.905 g/cm³; and SABIC^® PP 575P, having a melt flow rate of 10.5 g/10 minutes, a density of 0.905 g/cm³, and a melting point of 167 °C, each of which are available from SABIC (Riyadh, Saudi Arabia). Other suitable commercially available propylene homopolymers include WRD5-1057, DX5E66, and 5A97, available from Union Carbide (Houston, TX); Z9470, Z9470HB, Z9550, 6671XBB, 3576X, 3272, APPRYL^® 3020 BTI, APPRYL^® 3030 FNI, APPRYL^® 3050 MNI, and APPRYL^® 3060 MN5, available from Total (Courbevoie, France); SF6100 and MOPLEN^® HP522J, available from LyondellBasell (Houston, TX); STAMYLAN^® P 17M 10 and STAMYLAN^® P 17U10, available from DSM (Heerlen, Netherlands); and BORMOD^® HD905CF, available from Borealis (Vienna, Austria).

[0028] In some embodiments, Component A is, or includes, a propylene copolymer. In certain aspects, Component A includes copolymers of propylene and up to 40 wt% of at least one alpha olefin selected from ethylene and alpha olefins containing from 4 to 8 carbon atoms. The alpha olefin content of the propylene copolymers can, for example, range from 0 to 24 wt%, from 4 wt% to 28 wt%, from 8 wt% to 32 wt%, from 12 wt% to 36 wt%, or from 16 wt% to 40 wt%. In terms of upper limits, the alpha olefin content can be less than 40 wt%, e.g., less than 38 wt%, less than 36 wt%, less than 34 wt%, less than 32 wt%, less than 30 wt%, less than 28 wt%, less than 26 wt%, less than 24 wt%, less than 22 wt%, less than 20 wt%, less than 18 wt%, less than 16 wt%, less than 14 wt%, less than 12 wt%, less than 10 wt%, less than 8 wt%, less than 6 wt%, less than 4 wt%, or less than 2 wt%, In terms of lower limits, the alpha olefin content can be greater than 4 wt%, e.g., greater than 6 wt%, greater than 8 wt%, greater than 10 wt%, greater than 12 wt%, greater than 14 wt%, greater than 16 wt%, greater than 18 wt%, greater than 20 wt%, greater than 22 wt%, greater than 24 wt%, greater than 26 wt%, greater than 28 wt%, greater than 30 wt%, greater than 32 wt%, greater than 34 wt%, or greater than 36 wt%. Higher contents, e.g., greater than 40 wt%, are also contemplated.

[0029] Examples of alpha olefins useful as monomers of the propylene copolymers include, but are not limited to, ethylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-heptene, and 1- octene. In some embodiments, Component A includes copolymers of propylene with ethylene, 1-butene, 1-octene, or combinations thereof. The propylene-alpha-olefin copolymers can include random copolymers as well as block copolymers. Component A can include a single propylene copolymer, a blend of two or more copolymers, or a blend of one or more copolymers with one or more propylene homopolymers.

[0030] In some embodiments, Component A propylene copolymers are propylene-ethylene copolymers with ethylene contents of up 10 wt%, e.g., from 0 to 6 wt%, from 1 wt% to 7 wt%, from 2 wt% to 8 wt%, from 3 wt% to 9 wt%, or from 4 wt% to 10 wt%. In terms of upper limits, the ethylene contents can be less than 10 wt%, e.g., less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, or less than 1 wt%. In terms of lower limits, the ethylene contents can be greater than 1 wt%, e.g., greater than 2 wt%, greater than 3 wt%, greater than 4 wt%, greater than 5 wt%, greater than 6 wt%, greater than 7 wt%, greater than 8 wt%, or greater than 9 wt%. Higher contents, e.g., greater than 10 wt%, are also contemplated. [0031] In some embodiments, the propylene copolymers are propylene-l-butene copolymers with 1-butene contents of up to 15 wt%, e.g., from 0 to 9 wt%, from 1.5 to 10.5 wt%, from 3 wt% to 12 wt%, from 4.5 wt% to 13.5 wt%, or from 6 wt% to 15 wt%. In terms of upper limits, the 1-butene contents can be less than 15 wt%, e.g., less than 13.5 wt%, less than 12 wt%, less than 10.5 wt%, less than 9 wt%, less than 7.5 wt%, less than 6 wt%, less than 4.5 wt%, less than 3 wt%, or less than 1.5 wt%. In terms of lower limits, the 1-butene contacts can be greater than 1.5 wt%, e.g., greater than 3 wt%, greater than 4.5 wt%, greater than 6 wt%, greater than 7.5 wt%, greater than 9 wt%, greater than 10.5 wt%, greater than 12 wt%, or greater than 13.5 wt%. Higher contents, e.g., greater than 15 wt%, are also contemplated.

[0032] In some embodiments, the propylene copolymers are propylene-l-octene copolymers with 1-octene contents of up to 40 wt%, e.g., from 0 to 24 wt%, from 4 wt% to 28 wt%, from 8 wt% to 32 wt%, from 12 wt% to 36 wt%, or from 16 wt% to 40 wt%. In terms of upper limits, the 1- octene contents can be less than 40 wt%, e.g., less than 38 wt%, less than 36 wt%, less than 34 wt%, less than 32 wt%, less than 30 wt%, less than 28 wt%, less than 26 wt%, less than 24 wt%, less than 22 wt%, less than 20 wt%, less than 18 wt%, less than 16 wt%, less than 14 wt%, less than 12 wt%, less than 10 wt%, less than 8 wt%, less than 6 wt%, less than 4 wt%, or less than 2 wt%. In terms of lower limits, the 1- octene contents can be greater than 4 wt%, e.g., greater than 6 wt%, greater than 8 wt%, greater than 10 wt%, greater than 12 wt%, greater than 14 wt%, greater than 16 wt%, greater than 18 wt%, greater than 20 wt%, greater than 22 wt%, greater than 24 wt%, greater than 26 wt%, greater than 28 wt%, greater than 30 wt%, greater than 32 wt%, greater than 34 wt%, or greater than 36 wt%. Higher contents, e.g., greater than 40 wt%, are also contemplated.

[0033] Commercially available propylene copolymers suitable for use in the films disclosed herein include, but are not limited to, DS4D05, DS6D20, DS6D81, SRD4-127, SRD4-104, and SRD-105, each of which is available from Union Carbide.

[0034] The concentration of Component A in the film can, for example, range from 20 wt% to 95 wt%, e.g., from 20 wt% to 65 wt%, from 27.5 wt% to 72.5 wt%, from 35 wt% to 80 wt%, from 42.5 wt% to 87.5 wt%, or from 50 wt% to 95 wt%. In terms of upper limits, the first component concentration can be less than 95 wt%, e.g., less than 90 wt%, less than 87.5 wt%, less than 85 wt%, less than 82.5 wt%, less than 80 wt%, less than 77.5 wt%, less than 75 wt%, less than 72.5 wt%, less than 70 wt%, less than 67.5 wt%, less than 65 wt%, less than 62.5 wt%, less than 60 wt%, less than 57.5 wt%, less than 55 wt%, less than 52.5 wt%, less than 50 wt%, less than 47.5 wt%, less than 45 wt%, less than 42.5 wt%, less than 40 wt%, less than 37.5 wt%, less than 35 wt%, less than 32.5 wt%, less than 30 wt%, or less than 27.5 wt%. In terms of lower limits, the first component concentration can be greater than 20 wt%, e.g., greater than 22.5 wt%, greater than 25 wt%, greater than 27.5 wt%, greater than 30 wt%, greater than 32.5 wt%, greater than 35 wt%, greater than 37.5 wt%, greater than 40 wt%, greater than 42.5 wt%, greater than 45 wt%, greater than 47.5 wt%, greater than 50 wt%, greater than 52.5 wt%, greater than 55 wt%, greater than 57.5 wt%, greater than 60 wt%, greater than 62.5 wt%, greater than 65 wt%, greater than 67.5 wt%, greater than 70 wt%, greater than 72.5 wt%, greater than 75 wt%, greater than 77.5 wt%, greater than 80 wt%, greater than 82.5 wt%, greater than 85 wt%, or greater than 87.5 wt%. Higher concentrations, e.g., greater than 95 wt%, and lower concentrations, e.g., less than 20 wt%, are also contemplated.

[0035] In some embodiments, Component A has a specific (combined) melt flow rate, as determined by ISO 1133-1:2011 at 230 °C and 2.16 kg. In some embodiments, the melt flow rate of Component A can, for example, range from 0.1 g/10 minutes to 40 g/10 minutes, e.g., from 0.1 g/10 minutes to 24 g/10 minutes, from 4 g/10 minutes to 28 g/10 minutes, from 8 g/10 minutes to 32 g/10 minutes, from 12 g/10 minutes to 36 g/10 minutes, or from 16 g/10 minutes to 40 g/10 minutes. In some embodiments, the melt flow rate of the first component ranges from 1 g/10 minutes to 20 g/10 minutes. In terms of upper limits, the first component melt flow rate can be less than 40 g/10 minutes, e.g., less than 38 g/10 minutes, less than 36 g/10 minutes, less than 34 g/10 minutes, less than 32 g/10 minutes, less than 30 g/10 minutes, less than 28 g/10 minutes, less than 26 g/10 minutes, less than 24 g/10 minutes, less than 22 g/10 minutes, less than 20 g/10 minutes, less than 18 g/10 minutes, less than 16 g/10 minutes, less than 14 g/10 minutes, less than 12 g/10 minutes, less than 10 g/10 minutes, less than 8 g/10 minutes, less than 6 g/10 minutes, less than 4 g/10 minutes, or less than 2 g/10 minutes,. In terms of lower limits, the first component melt flow rate can be greater than 0.1 g/10 minutes, e.g., greater than 1 g/10 minutes, greater than 2 g/10 minutes, greater than 4 g/10 minutes, greater than 6 g/10 minutes, greater than 8 g/10 minutes, greater than 10 g/10 minutes, greater than 12 g/10 minutes, greater than 14 g/10 minutes, greater than 16 g/10 minutes, greater than 18 g/10 minutes, greater than 20 g/10 minutes, greater than 22 g/10 minutes, greater than 24 g/10 minutes, greater than 26 g/10 minutes, greater than 28 g/10 minutes, greater than 30 g/10 minutes, greater than 32 g/10 minutes, greater than 4 g/10 minutes, or greater than 36 g/10 minutes. Higher melt flow rates, e.g., greater than 40 g/10 minutes, and lower melt flow rates, e.g., less than 0.1 g/10 minutes, are also contemplated. B. Olefin Elastomer

[0036] In some embodiments, the films described herein contain a second component (component B), which is selected from at least one olefin elastomer. In some embodiments, the films do not contain an olefin block copolymer.

[0037] The olefin elastomers in Component B can exhibit both thermoplastic and elastomeric characteristics. In some embodiments, Component B includes one or more polyethylene polymers. In certain aspects, Component B includes copolymers and/or terpolymers of ethylene or propylene with an alpha-olefin. The alpha-olefin content of the olefin elastomers includes, but is not limited to, 1-butene, 1- pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, and combinations thereof.

[0038] In some embodiments, Component B includes a low density polyethylene. The term "low density polyethylene" as used herein includes polyethylenes having a density of less than 0.930 or 0.935 g/cm³ or a density less than 0.930 or 0.935 g/cm³. The polyethylenes can include low density polyethylenes (LDPE), linear low density polyethylenes (LLDPE), very low density polyethylenes (VLDPE), ultra-low density polyethylenes (ULDPE), and combinations thereof. The low density polyethylenes can include plastomers which are VLDPEs prepared by single site catalysts.

[0039] The low density polyethylenes (LDPEs) of Component B can include homopolymers of ethylene or copolymers of ethylene with alpha olefins such as 1-butene, 1-hexene and 1-octene, or polar monomers such as vinyl acetate, methyl acrylate, or ethyl acrylate. LDPE polymers can have a density in the range of from 0.920 g/cm³ to 0.935 g/cm³, e.g. from 0.920 g/cm³ to 0.929 g/cm³, from 0.9215 g/cm³ to 0.9305 g/cm³, from 0.923 g/cm³ to 0.932 g/cm³, from 0.9245 g/cm³ to 0.9335 g/cm³, or from 0.926 g/cm³ to 0.935 g/cm³. In terms of upper limits, the LDPE density can be less than 0.935 g/cm³, e.g., less than 0.9335 g/cm³, less than 0.932 g/cm³, less than 0.9305 g/cm³, less than 0.929 g/cm³, less than 0.9275 g/cm³, less than 0.926 g/cm³, less than 0.9245 g/cm³, less than 0.923 g/cm³, or less than 0.9215 g/cm³. In terms of lower limits, the LDPE density can be greater than 0.920 g/cm³, e.g., greater than 0.9215 g/cm³, greater than 0.923 g/cm³, greater than 0.9245 g/cm³, greater than 0.926 g/cm³, greater than 0.9275 g/cm³, greater than 0.929 g/cm³, greater than 0.930 g/cm³, greater than 0.932 g/cm³, or greater than 0.933 g/cm³.

[0040] The amount of comonomers polymerized with the LDPE polymers can, for example, range from 0 to 2.4 wt%, from 0.4 wt% to 2.8 wt%, from 0.8 wt% to 3.2 wt%, from 1.2 wt% to 3.6 wt%, or from 1.6 wt% to 4 wt%. In terms of upper limits, the LDPE comonomers concentration can be less than 4 wt%, e.g., less than 3.6 wt%, less than 3.2 wt%, less than 2.8 wt%, less than 2.4 wt%, less than 2 wt%, less than 1.6 wt%, less than 1.2 wt%, less than 0.8 wt%, or less than 0.4 wt%. In terms of lower limits, the LDPE comonomer concentration can be greater than 0.4 wt%, e.g., greater than 0.8 wt%, greater than 1.0 wt%, greater than 1.2 wt%, greater than 1.4 wt%, greater than 1.6 wt%, greater than 1.8 wt%, greater than 2 wt%, greater than 2.2 wt%, greater than 2.4 wt%, greater than 2.6 wt%, greater than 2.8 wt%, greater than 3.0 wt%, greater than 3.2 wt%, greater than 3.4 wt%, or greater than 3.6 wt%. Higher contents, e.g., greater than 4 wt%, are also contemplated.

[0041] In some embodiments, the linear low density polyethylenes (LLDPEs) of Component B can include copolymers of ethylene and alpha-olefins. Although any alpha olefin containing from 3 to 20 carbon atoms can be used as a comonomer for LLDPE, in some embodiments, the alpha olefin is selected from 1-butene, 1-hexene, 4-methyl-l-pentene, and 1-octene. LLDPE polymers can have a density in the range from 0.915 g/cm³ to 0.925 g/cm³, e.g., from 0.915 g/cm³ to 0.921 g/cm³, from 0.916 g/cm³ to 0.922 g/cm³, from 0.917 g/cm³ to 0.923 g/cm³, from 0.918 g/cm³ to 0.924 g/cm³, or from 0.919 g/cm³ to 0.925 g/cm³. In terms of upper limits, the LLDPE density can be less than 0.925 g/cm³, e.g., less than 0.924 g/cm³, less than 0.923 g/cm³, less than 0.922 g/cm³, less than 0.921 g/cm³, less than 0.920 g/cm³, less than 0.919 g/cm³, less than 0.918 g/cm³, less than 0.917 g/cm³, or less than 0.916 g/cm³. In terms of lower limits, the LLDPE density can be greater than 0.915 g/cm³, e.g., greater than 0.916 g/cm³, greater than 0.917 g/cm³, greater than 0.918 g/cm³, greater than 0.919 g/cm³, greater than 0.920 g/cm³, greater than 0.921 g/cm³, greater than 0.922 g/cm³, greater than 0.923 g/cm³, or greater than 0.924 g/cm³.

[0042] The very low density (VLDPE) and ultra-low density (ULDPE) polymers of Component B can include comonomer contents ranging, for example, from 0 to 2.4 wt%, from 0.4 wt% to 2.8 wt%, from 0.8 wt% to 3.2 wt%, from 1.2 wt% to 3.6 wt%, or from 1.6 wt% to 4 wt%. In terms of upper limits, the VLDPE or ULDPE comonomer contents can be less than 4 wt%, e.g., less than 3.6 wt%, less than 3.4 wt%, less than 3.2 wt%, less than 3.0 wt%, less than 2.8 wt%, less than 2.6 wt%, less than 2.4 wt%, less than 2.2 wt%, less than 2 wt%, less than 1.8 wt%, less than 1.6 wt%, less than 1.4 wt%, less than 1.2 wt%, less than 1.0 wt%, less than 0.8 wt%, less than 0.6 wt%, or less than 0.4 wt%. In terms of lower limits, the VLDPE or ULDPE comonomer concentration can be greater than 0.4 wt%, e.g., greater than 0.6 wt%, greater than 0.8 wt%, greater than 1.0 wt%, greater than 1.2 wt%, greater than 1.4 wt%, greater than 1.6 wt%, greater than 1.8 wt%, greater than 2 wt%, greater than 2.2 wt%, greater than 2.4 wt%, greater than 2.6 wt%, greater than 2.8 wt%, greater than 3.0 wt%, greater than 3.2 wt%, greater than 3.4 wt%, or greater than 3.6 wt%. Higher contents, e.g., greater than 4 wt%, are also contemplated. VLDPE and ULDPE polymers can have a density of less than 0.915 g/cm³. Very low density polymers prepared using single site catalysts and referred to in the art as plastomers generally contain higher amounts of comonomer, i.e., up to 25% by weight. Plastomers can have a density of 0.912 g/cm³ or less. [0043] Commercially available linear low density polyethylenes suitable for use in the second component include, but are not limited to, the 1-octene LLDPEs STAMYLEX^® 1016LF, having a melt flow rate of 1.1 g/10 minutes, a density of 0.919 g/cm³, and a melting point of 123 °C; STAMYLEX^® 1026F, having a melt flow rate of 2.2 g/10 minutes, a density of 0.919 g/cm³, and a melting point of 123 °C; STAMYLEX^® 1046F, having a melt flow rate of 4.4 g/10 minutes, a density of 0.919 g/cm³, and a melting point of 122 °C; and STAMYLEX^® 1066F, having a melt flow rate of 6.6 g/10 minutes, a density of 0.919 g/cm³, and a melting point of 124 °C, each of which is available from Borealis. Other suitable commercially available linear low density polyethylenes include BORSTAR^® FB 4230 and BORSTAR^® FB 2310, available from Borealis; and the ethylene/octane-1 copolymers DOWLEX^® 2042E, DOWLEX^® 2035G, and DOWLEX^® SC2107, available from Dow (Midland Ml). Commercially available low density polyethylenes suitable for use in the second component include, but are not limited to, HIMOD™ FT 5270, available from Borealis.

[0044] Plastomers that can be used in Component B of the films disclosed herein include very low density copolymers and terpolymers of ethylene with an alpha olefin. These plastomers are characterized as having a density of 0.912 g/cm³ or less, and can include an alpha olefin content ranging from 2 wt% to 30 wt%, e.g., from 2 wt% to 18.8 wt%, from 4.8 wt% to 21.6 wt%, from 7.6 wt% to 24.4 wt%, from 10.4 wt% to 27.2 wt%, or from 13.2 wt% to 30 wt%. In terms of upper limits, the alpha olefin content can be less than 30 wt%, e.g., less than 27.2 wt%, less than 24.4 wt%, less than 21.6 wt%, less than 18.8 wt%, less than 16 wt%, less than 13.2 wt%, less than 10.4 wt%, less than 7.6 wt%, or less than 4.8 wt%. In terms of upper limits, the alpha olefin content can be greater than 2 wt%, greater than 4.8 wt%, greater than 7.6 wt%, greater than 10.4 wt%, greater than 13.2 wt%, greater than 16 wt%, greater than 18.8 wt%, greater than 21.6 wt%, greater than 24.4 wt%, or greater than 27.2 wt%. Higher alpha olefin contents, e.g., greater than 30 wt%, and lower aloha olefin contents, e.g., less than 2 wt%, are also contemplated.

[0045] The alpha olefins of the plastomers can include, but are not limited to, 1-butene, 1- pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 decene, and combinations thereof. Particularly useful alpha olefins include 1-butene and 1-hexene. An example of an ethylene terpolymer is ethylene-1- hexene-l-butene. These low density ethylene copolymers can be obtained by copolymerization of ethylene with an alpha olefin using single-site metallocene catalysts. Such copolymers are available commercially from ExxonMobil, Basell, and Dow.

[0046] Commercially available ethylene plastomers suitable for use in the second component include, but are not limited to, the linear ethylene-butene copolymers EXACT^® 3024, having a density of 0.905 g/cm³ and a melt index of 4.5 g/10 minutes; EXACT^® 3027, having a density of 0.900 g/cm³ and a melt index of 3.5 g/10 minutes; EXACT^® 4011, having a density of 0.888 g/cm³ and a melt index of 2.2 g/10 minutes; and EXACT^® 4049, having a density of 0.873 g/cm³ and a melt index of 4.5 g/10 minutes; and the ethylene-hexene copolymer EXACT^® 4150, having a density of 0.895 g/cm³ and a melt index of 3.5 g/10 min, each of which is available from ExxonMobil (Irving, TX). Other suitable plastomers include AFFINITY^® PF 1140, having a density of 0.897 g/cm³ and a melt flow index of 0.5 g/10 minutes; AFFINITY^® PF 1146, having a density of 0.90 g/cm³ and a melt index of l g/10 minutes; AFFINITY^® PL 1880, having a density of 0.902 g/cm³ and melt index of 1 g/10 minutes; AFFINITY^® EG 8100 having a density of 0.87 g/cm³ and a melt index of 1 g/10 minutes; AFFINITY^® EG 8150, having a density of 0.868 g/cm³ and a melt index of 0.5 g/10 minutes; AFFINITY^® EG 8200, having a density of 0.87 g/cm³ and a melt index of 5 g/10 minutes; and AFFINITY^® KC 8552 having a density of 0.87 g/cm³ and a melt index of 5 g/10 minutes, each of which is available from Dow. Combinations of two or more of these plastomers are also suitable for use in the second component.

[0047] Commercially available terpolymers suitable for use in the second component include, but are not limited to the ethylene-butene-hexene terpolymers EXACT^® 3006, having a density of 0.910 g/cm³ and a melt flow index of 1.2 g/10 minutes; EXACT^® 3016, having a density of 0.910 g/cm³ and a melt flow index of 4.5 g/10 minutes; EXACT^® 3033, having a density of 0.900 g/cm³ and a melt flow index of 1.2 g/10 minutes; and EXACT^® 3034, having a density of 0.900 g/cm³ and a melt flow index of 3.5 g/10 minutes, each of which is available from ExxonMobil. Other suitable terpolymers include the ethylene- propylene-butylene terpolymers AFFINITY^® PL 1840, AFFINITY^® PL 1845, and AFFINITY^® PL 1850, each of which is available from Dow; and ZCE 2005, available from ExxonMobil.

[0048] In some embodiments, Component B includes at least one medium or high density polyethylene. The terms "medium density polyethylene" or "MDPE" as used herein refers to polyethylene polymers having a density between 0.935 g/cm³ and 0.940 g/cm³, e.g., from 0.935 g/cm³ to 0.938 g/cm³, from 0.9355 g/cm³ to 0.9385 g/cm³, from 0.936 g/cm³ to 0.939 g/cm³, from 0.9365 g/cm³ to 0.9395 g/cm³, or from 0.937 g/cm³ to 0.94 g/cm³. The terms "high density polyethylene" or "HDPE" as used herein refer to polyethylene polymers having a density of 0.940 g/cm³ to 0.965 g/cm³, e.g., from 0.940 g/cm³ to 0.955 g/cm³, from 0.9425 g/cm³ to 0.9575 g/cm³, from 0.945 g/cm³ to 0.960 g/cm³, from 0.9475 g/cm³ to 0.9625 g/cm³, or from 0.950 g/cm³ to 0.965 g/cm³.

[0049] In some embodiments, Component B includes one or more olefins, e.g., polyethylenes or plastomers, having a melt flow rate, as determined by ISO 1133-1:2011, in the range from 0.1 g/10 minutes to 20 g/10 minutes, e.g., from 0.1 g/10 minutes to 12 g/10 minutes, from 2 g/10 minutes to 14 g/10 minutes, from 4 g/10 minutes to 16 g/10 minutes, from 6 g/10 minutes to 18 g/10 minutes, or from 8 g/10 minutes to 20 g/10 minutes. In terms of upper limits, the melt flow rate of the second component can be less than 20 g/10 minutes, e.g., less than 18 g/10 minutes, less than 16 g/10 minutes, less than 14 g/10 minutes, less than 12 g/10 minutes, less than 10 g/10 minutes, less than 8 g/10 minutes, less than 6 g/10 minutes, less than 4 g/10 minutes, or less than 2 g/10 minutes. In terms of lower limits, the melt flow rate of the second component can be greater than 0.1 g/10 minutes, e.g., greater than 2 g/10 minutes, greater than 4 g/10 minutes, greater than 6 g/10 minutes, greater than 8 g/10 minutes, greater than 10 g/10 minutes, greater than 12 g/10 minutes, greater than 14 g/10 minutes, greater than 16 g/10 minutes, or greater than 18 g/10 minutes. Higher melt flow rates, e.g., greater than 20 g/10 minutes, and lower melt flow rates, e.g., less than 0.1 g/10 minutes, are also contemplated. In some cases, the olefins, e.g., polyethylenes, can be tested under ISO 1133-1:2011, and at a temperature of 190 9C.

[0050] The density of Component B can, for example, range from 0.840 g/cm³ to 0.940 g/cm³, e.g., from 0.840 g/cm³ to 0.900 g/cm³, from 0.850 g/cm³ to 0.910 g/cm³, from 0.860 g/cm³ to 0.920 g/cm³, from 0.870 g/cm³ to 0.930 g/cm³, or from 0.880 g/cm³ to 0.940 g/cm³. In terms of upper limits, the second component density can be less than 0.940 g/cm³, e.g., less than 0.930 g/cm³, less than 0.920 g/cm³, less than 0.910 g/cm³, less than 0.900 g/cm³, less than 0.890 g/cm³, less than 0.880 g/cm³, less than 0.870 g/cm³, less than 0.860 g/cm³, or less than 0.850 g/cm³. In terms of lower limits, the density of Component B can be greater than 0.840 g/cm³, e.g., greater than 0.850 g/cm³, greater than 0.860 g/cm³, greater than 0.870 g/cm³, greater than 0.880 g/cm³, greater than 0.890 g/cm³, greater than 0.900 g/cm³, greater than 0.910 g/cm³, greater than 0.920 g/cm³, or greater than 0.930 g/cm³. Higher densities, e.g., greater than 0.940 g/cm³, and lower densities, e.g., less than 0.840 g/cm³, are also contemplated.

[0051] In some embodiments, the compositions described herein contain an olefin elastomer having a density less than 0.880 g/cm³or less than 0.880 g/cm³, for example, from 0.85 g/cm³ to 0.875 g/cm³ or from 0.85 g/cm³ to 0.875 g/cm³.

[0052] In some cases, Component B or the individual components that make up the total Component B, has a molecular weight distribution ( MW/MN) that ranges, for example, from 1.5 to 2.4, e.g., from 1.5 to 2.04, from 1.59 to 2.13, from 1.68 to 2.22, from 1.77 to 2.31, or from 1.86 to 2.4, wherein Mw is the weight-average molecular weight, and M_N is the number-average molecular weight. In terms of upper limits, the olefin elastomer molecular weight distribution can be less than 2.4, e.g., less than 2.31, less than 2.22, less than 2.13, less than 2.04, less than 1.95, less than 1.86, less than 1.77, less than 1.68, or less than 1.59. In terms of lower limits, the olefin elastomer molecular weight distribution can be greater than 1.5, e.g., greater than 1.59, greater than 1.68, greater than 1.77, greater than 1.86, greater than 1.95, greater than 2.04, greater than 2.13, greater than 2.22, or greater than 2.31. Larger molecular weight distributions, e.g., greater than 2.4, and smaller molecular weight distributions, e.g., less than 1.5, are also contemplated.

[0053] The concentration of Component B in the film can, for example, range from 5 wt% to 75 wt%, e.g., from 5 wt% to 47 wt%, from 12 wt% to 54 wt%, from 19 wt% to 61 wt%, from 26 wt% to 68 wt%, or from 33 wt% to 75 wt%. In terms of upper limits, the second component concentration can be less than 75 wt%, e.g., less than 72 wt%, less than 70 wt%, less than 68 wt%, less than 65 wt%, less than 63 wt%, less than 61 wt%, less than 58 wt%, less than 56 wt%, less than 54 wt%, less than 52 wt%, less than 50 wt%, less than 47 wt%, less than 45 wt%, less than 42 wt%, less than 40 wt%, less than 37 wt%, less than 35 wt%, less than 33 wt%, less than 30 wt%, less than 28 wt%, less than 26 wt%, less than 23 wt%, less than 21 wt%, less than 19 wt%, less than 17 wt%, less than 15 wt%, or less than 12 wt%. In terms of lower limits, the second component concentration can be greater than 5 wt%, e.g., greater than 12 wt%, greater than 15 wt%, greater than 17 wt%, greater than 19 wt%, greater than 21 wt%, greater than 24 wt%, greater than 26 wt%, greater than 28 wt%, greater than 30 wt%, greater than 33 wt%, greater than 35 wt%, greater than 38 wt%, greater than 40 wt%, greater than 42 wt%, greater than 45 wt%, greater than 47 wt%, greater than 50 wt%, greater than 52 wt%, greater than 54 wt%, greater than 57 wt%, greater than 59 wt%, greater than 61 wt%, greater than 63 wt%, greater than 65 wt%, or greater than 68 wt%. Higher concentrations, e.g., greater than 75 wt%, and lower concentrations, e.g., less than 5 wt%, are also contemplated.

[0054] The weight ratio of Component A to Component B can, for example, range from 0.25 to 50, e.g., from 0.25 to 6, from 0.42 to 10, from 0.72 to 17, from 1.2 to 29, or from 2.1 to 50. In terms of upper limits, the weight ratio of the first component to the second component can be less than 50, e.g., less than 47, less than 45, less than 42, less than 40, less than 38, less than 35, less than 32, less than 29, less than 27, less than 25, less than 23, less than 20, less than 17, less than 15, less than 13, less than 10, less than 8, less than 6, less than 3.5, less than 2.1, less than 1.2, less than 0.72, or less than 0.42. In terms of lower limits, the weight ratio of the first component to the second component can be greater than 0.25, e.g., greater than 0.42, greater than 0.72, greater than 1.2, greater than 2.1, greater than 3.5, greater than 6, greater than 8, greater than 10, greater than 12, greater than 15, greater than 17, greater than 20, greater than 23, greater than 25, greater than 27, or greater than 29. Higher ratios, e.g., greater than 50, and lower ratios, e.g., less than 0.25, are also contemplated.

[0055] The viscosity of Component B can be within 20% of the viscosity of the first component, e.g., within 18%, within 16%, within 14%, within 12%, within 10%, within 8%, within 6%, within 4%, or within 2%. The ratio of the viscosities of Component B to Component A can, for example, range from 0.8 to 1.2, e.g., from 0.8 to 1.04, from 0.84 to 1.08, from 0.88 to 1.12, from 0.92 to 1.16, or from 0.96 to 1.2. In terms of upper limits, the viscosity ratio of the second component to the first component can be less than 1.2, e.g., less than 1.16, less than 1.12, less than 1.08, less than 1.04, less than 1, less than 0.96, less than 0.92, less than 0.88, or less than 0.84. In terms of lower limits, the viscosity ratio of Component B to Component A can be greater than 0.8, e.g., greater than 0.84, greater than 0.88, greater than 0.92, greater than 0.96, greater than 1, greater than 1.04, greater than 1.08, greater than 1.12, or greater than 1.16. In some embodiments it is desirable for Component A and Component B of the film to each have the same viscosity at the temperature and shear rate of extrusion conditions used to form the film.

C. Cavitation Agents

[0056] In some embodiments, the compositions described herein also contain one or more cavitation agents. The cavitation agent, Component C, can include one or more inorganic and/or organic particulate solids, and generally does not include foaming agents. The cavitation agents can include an organic solid such as calcium carbonate. In some embodiments, the cavitation agents include one or more polymers, such as polyesters, polyamides, or polycarbonates. In certain aspects, the cavitation agents include polar polymers. The cavitation agents can include, for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), polycarbonate (PC), nylon, or a combination thereof. The cavitation agent can be added to the film in the form of a particulate solids concentrate or additive concentrate at 10 wt% to 90 wt% in a thermoplastic polymer carrier, such as a propylene polymer mixture. Commercial cavitation agents suitable for use in the provided films include, but are not limited to, Pearl 81, which is a resin including 30 wt% PBT in 70 wt% polypropylene homopolymer, and which is available from Ampacity (Tarrytown, NY). In some embodiments, a cavitation agent resin is added into the base layers of a multilayer film at between 5 wt% and 15 wt% of the full construction.

[0057] The concentration of Component C in the film can, for example, range from 0.5 wt% to 10 wt%, e.g., from 0.5 wt% to 6.2 wt%, from 1.45 wt% to 7.15 wt%, from 2.4 wt% to 8.1 wt%, from 3.35 wt% to 9.05 wt%, or from 4.3 wt% to 10 wt%. In terms of upper limits, the cavitation agent concentration can be less than 10 wt%, e.g., less than 9.05 wt%, less than 8.1 wt%, less than 7.15 wt%, less than 6.2 wt%, less than 5.25 wt%, less than 4.3 wt%, less than 3.35 wt%, less than 2.4 wt%, or less than 1.45 wt%. In terms of lower limits, the cavitation agent concentration can be greater than 0.5 wt%, e.g., greater than 1.45 wt%, greater than 2.4 wt%, greater than 3.35 wt%, greater than 4.3 wt%, greater than 5.25 wt%, greater than 6.2 wt%, greater than 7.15 wt%, greater than 8.1 wt%, or greater than 9.05 wt%. Higher concentrations, e.g., greater than 10 wt%, and lower concentrations, e.g., less than 0.5 wt%, are also contemplated. In some cases, when some cavitation agents are used, e.g., PBT, calcium carbonate, nylon, or combinations thereof, then lower concentrations advantageously can be employed, which results in production and cost efficiencies.

[0058] The weight ratio of Component A to Component C can, for example, range from 5 to 95, e.g., from 5 to 59, from 14 to 68, from 23 to 77, from 32 to 86, or from 41 to 95. In terms of upper limits, the weight ratio of the first component to the third component can be less than 95, e.g., less than 92, less than 90, less than 88, less than 86, less than 82, less than 80, less than 77, less than 75, less than 72, less than 70, less than 68, less than 65, less than 62, less than 59, less than 57, less than 55, less than 53, less than 50, less than 48, less than 45, less than 43, less than 41, less than 38, less than 35, less than 32, less than 30, less than 28, less than 25, less than 23, less than 20, less than 18, less than 16, or less than 14. In terms of lower limits, the weight ratio of the first component to the third component can be greater than 5, e.g., greater than 7, greater than 10, greater than 14, greater than 17, greater than 20, greater than 23, greater than 25, greater than 27, greater than 30, greater than 32, greater than 35, greater than 38, greater than 41, greater than 43, greater than 45, greater than 47, greater than 50, greater than 52, greater than 55, greater than 57, greater than 59, greater than 61, greater than 63, greater than 65, greater than 68, greater than 70, greater than 72, greater than 75, greater than 77, greater than 80, greater than 83, or greater than 86. Higher ratios, e.g., greater than 95, and lower ratios, e.g., less than 5, are also contemplated.

[0059] The weight ratio of Component B to third component (C) can, for example, range from 0.4 to 75, e.g., from 0.4 to 9.2, from 0.68 to 16, from 1.1 to 26, from 1.9 to 44, or from 3.2 to 75. In terms of upper limits, the weight ratio of the second component to the third component can be less than 75, e.g., less than 70, less than 65, less than 60, less than 55, less than 50, less than 44, less than 40, less than 35, less than 30, less than 26, less than 20, less than 15, less than 12, less than 9.2, less than 5.5, less than 3.2, less than 1.9, less than 1.1, or less than 0.68. In terms of lower limits, the weight ratio of the second component to the third component can be greater than 0.4, e.g., greater than 0.68, greater than 1.1, greater than 1.9, greater than 3.2, greater than 5.5, greater than 9.2, greater than 16, greater than 20, greater than 26, greater than 30, greater than 35, greater than 40, or greater than 44. Higher ratios, e.g., greater than 75, and lower ratios, e.g., less than 0.4, are also contemplated. D. Additives

1. Nucleating Agents

[0060] In some embodiments, the machine direction oriented polymeric film also includes one or more nucleating agents. The amount of nucleating agent in the film can be selected to be sufficient for modifying the film crystal structure, while not having an adverse effect on other desired properties of the film. In certain aspects, it is desirable to utilize a nucleating agent to modify the crystal structure and provide a large number of considerably smaller crystals or spherulites to improve the transparency or clarity of the film. In such cases, the amount of nucleating agent added to the film formulation should not have a deleterious effect on the clarity of the film.

[0061] The weight concentration of nucleating agent incorporated into the film formulations disclosed herein can, for example, range from 500 ppm to 5000 ppm, e.g., from 500 ppm to 3200 ppm, from 950 ppm to 3650 ppm, from 1400 ppm to 4100 ppm, from 1850 ppm to 4550 ppm, or from 2300 ppm to 5000 ppm. In terms of upper limits, the nucleating agent concentration can be less than 5000 ppm, e.g., less than 4550 ppm, less than 4100 ppm, less than 3650 ppm, less than 3200 ppm, less than 2750 ppm, less than 2300 ppm, less than 1850 ppm, less than 1400 ppm, or less than 950 ppm. In terms of lower limits, the nucleating agent concentration can be greater than 500 ppm, e.g., greater than 950 ppm, greater than 1400 ppm, greater than 1850 ppm, greater than 2300 ppm, greater than 2750 ppm, greater than 3200 ppm, greater than 3650 ppm, greater than 4100 ppm, or greater than 4550 ppm. Higher concentrations, e.g., greater than 5000 ppm, and lower concentrations, e.g., less than 500 ppm, are also contemplated.

[0062] In certain aspects, the nucleating agents include one or more mineral nucleating agents, organic nucleating agents, or combinations thereof. Examples of mineral nucleating agents include, but are not limited to, carbon black, silica, kaolin and talc. Examples of organic nucleating agents include, but are not limited to, salts of aliphatic mono-basic or di-basic acids or arylalkyl acids such as sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, aluminum phenyl acetate, and sodium cinnamate. Alkali metal and aluminum salts of aromatic and alicyclic carboxylic acids include, but are not limited to, aluminum benzoate, sodium or potassium benzoate, sodium beta- naphtholate, lithium benzoate and aluminum tertiary-butyl benzoate also are useful organic nucleating agents.

[0063] In some embodiments, the nucleating agents include one or more sorbitol derivatives, organic phosphates, or combinations thereof. Substituted sorbitol derivatives, such as bis (benzylidene) and bis (alkylbenzilidine) sorbitols wherein the alkyl groups contain from 2 to 18 carbon atoms are also useful nucleating agents. More particularly, sorbitol derivatives such as 1,3, 2,4- dibenzylidene sorbitol, and 1,3,2,4-di-para-methylbenzylidene sorbitol are effective nucleating agents for polypropylenes. Commercial nucleating agents suitable for use in the films disclosed herein include, but are not limited to, MILLAD^® 8C-41-10, MILLAD^® 3988, and MILLAD^® 3905, each of which is available from Milliken (Spartanburg, SC).

[0064] Other acetals of sorbitol and xylitol can also be used as nucleators in the provided films. Examples include dibenzylidene sorbitol (DBS), first disclosed in U.S. Pat. No. 4,016,118 by Hamada, et al. as an effective nucleating and clarifying agents for polyolefin. Since then, large number of acetals of sorbitol and xylitol have been disclosed. Such acetals are described in U.S. Pat. No. 4,314,039 (di(alkylbenzylidene) sorbitols); U.S. Pat. No. 4,371,645 (di-acetals of sorbitol having at least one chlorine or bromine substituent); U.S. Pat. No. 4,532,280 (di(methyl or ethyl substituted benzylidene) sorbitol); and U.S. Pat. No. 5,049,605 (bis(3,4-dialkylbenzylidene) sorbitols including substituents forming a carbocyclic ring).

2. Antiblocking Agents

[0065] The machine direction oriented polymeric films disclosed herein can also include one or more antiblocking agents. The addition of antiblocking agents to the film formulations can reduce the tendency of the films to block during windup, can regulate the slip and anti-static properties of the films, and can allow a smooth unwinding from reels. Non-limiting examples of antiblocking agents useful in the provided films include silicas having average particle sizes of 2 microns or less, with only small amounts, e.g., from 1000 to 5000 ppm, of the fine silica needed. Commercially available synthetic silica antiblocking agents suitable for use in the film include, but are not limited to, POLYBATCH^® ABPP-05, comprising 5% synthetic silica in a propylene homopolymer; POLYBATCH^® ABPP-10, comprising 10% synthetic silica in a propylene homopolymer; and POLYBATCH^® ABPP-05SC, comprising 5% synthetic silica and a random propylene copolymer, each of which is available from A. Schulman (Fairlawn, OH). Other suitable antiblocking agents include Seablock 1 and Seablock 4, available from Ampacet.

[0066] The weight concentration of antiblocking agents in the film can, for example, range from 500 ppm to 5000 ppm, e.g., from 500 ppm to 3200 ppm, from 950 ppm to 3650 ppm, from 1400 ppm to 4100 ppm, from 1850 ppm to 4550 ppm, or from 2300 ppm to 5000 ppm. In terms of upper limits, the antiblocking agent concentration can be less than 5000 ppm, e.g., less than 4550 ppm, less than 4100 ppm, less than 3650 ppm, less than 3200 ppm, less than 2750 ppm, less than 2300 ppm, less than 1850 ppm, less than 1400 ppm, or less than 950 ppm. In terms of lower limits, the antiblocking agent concentration can be greater than 500 ppm, e.g., greater than 950 ppm, greater than 1400 ppm, greater than 1850 ppm, greater than 2300 ppm, greater than 2750 ppm, greater than 3200 ppm, greater than 3650 ppm, greater than 4100 ppm, or greater than 4550 ppm. Higher concentrations, e.g., greater than 5000 ppm, and lower concentrations, e.g., less than 500 ppm, are also contemplated.

3. Processing Aids

[0067] In some embodiments, the machine oriented polymeric film further includes at least one processing aid to, for example, facilitate extrusion. The processing aids can include hexafluorocarbon polymers. Commercial processing aids suitable for use in the provided films include, but are not limited to, the hexafluoro carbon polymer AMPACET^® 10919, and AMPACET^® 401198, each of which is available from Ampacet.

[0068] The processing aids can be present in the film at concentrations ranging, for example from 0.03 wt% to 1.5 wt%, e.g., from 0.03 wt% to 0.91 wt%, from 0.18 wt% to 1.06 wt%, from 0.32 wt% to 1.21 wt%, from 0.47 wt% to 1.35 wt%, or from 0.62 wt% to 1.5 wt%. In terms of upper limits, the processing aid concentration can be less than 1.5 wt%, e.g., less than 1.35 wt%, less than 1.21 wt%, less than 1.06 wt%, less than 0.91 wt%, less than 0.77 wt%, less than 0.62 wt%, less than 0.48 wt%, less than 0.32 wt%, or less than 0.18 wt%. In terms of lower limits, the processing aid concentration can be greater than 0.03 wt%, e.g., greater than 0.18 wt%, greater than 0.32 wt%, greater than 0.47 wt%, greater than 0.62 wt%, greater than 0.77 wt%, greater than 1.06 wt%, greater than 1.21 wt%, or greater than 1.36 wt%. Higher concentrations, e.g., greater than 1.5 wt%, and lower concentrations, e.g., less than 0.3 wt%, are also contemplated.

4. Pigments and Opacifying Agents

[0069] The film compositions disclosed herein can also include other additives to further modify the properties of the film. For example, the film can include one or more pigments such as TiC , CaC03, etc., and combinations thereof. The presence of small amounts of T1O2, for example, can result in a white facestock. The T1O2 pigment can have a rutile structure, an anatase crystal structure, or a combination thereof. In some embodiments, the pigment is added to the base layer of a multilayer construct in the form of a concentrate containing the pigment and a resin carrier. The concentrate may contain, for example, 20 wt% to 80 wt% pigment, and 20 wt% to 80 wt% resin carrier. The resin carrier can be any thermoplastic polymer having a melting point in the range of 100 °C to 265 °C. Examples of resin carriers include polyethylene, polypropylene, polybutylene, polyester, nylon and combinations thereof. In some embodiments, a TiCh concentrate is used which includes a blend of 30% to 70% by weight polypropylene and 70 wt% to 30 wt% TiCh. Commercial pigment concentrates suitable for use in the disclosed films include, but are not limited to, Polybatch White P8555 SD available from A. Schulman; and Ampacet 110233 and Ampacet 110069, each of which is available from Ampacet.

[0070] In some embodiments, the concentration of pigment in the machine direction oriented cavitated film can be reduced relative to that in an otherwise analogous film lacking cavities, while maintaining a similar degree of film opacity. As discussed above, such reduction in pigment concentration can in some cases improve the cutting performance of the film, and can also decrease related cutting die degradation. The amount of pigment concentrate in the film can, for example, range from 0 to 40 wt%, e.g., from 0 to 24 wt%, from 4 wt% to 28 wt%, from 8 wt% to 32 wt%, from 12 wt% to 36 wt%, or from 16 wt% to 40 wt%. In terms of upper limits, the pigment concentrate amount can be less than 40 wt%, e.g., less than 38 wt%, less than 36 wt%, less than 34 wt%, less than 32 wt%, less than 30 wt%, less than 28 wt%, less than 26 wt%, less than 24 wt%, less than 22 wt%, less than 20 wt%, less than 18 wt%, less than 16 wt%, less than 14 wt%, less than 12 wt%, less than 10 wt%, less than 8 wt%, less than 6 wt%, or less than 4 wt%. In terms of lower limits, the pigment concentrate amount can be greater than 0, e.g., greater than 4 wt%, greater than 6 wt%, greater than 8 wt%, greater than 10 wt%, greater than 12 wt%, greater than 14 wt%, greater than 16 wt%, greater than 18 wt%, greater than 20 wt%, greater than 22 wt%, greater than 24 wt%, greater than 26 wt%, greater than 28 wt%, greater than 30 wt%, greater than 32 wt%, greater than 34 wt%, or greater than 36 wt%. Higher amounts, e.g. greater than 40 wt%, are also contemplated.

[0071] The amount of solid pigment in the pigment concentrate can, for example, range from 20 wt% to 80 wt%, e.g., from 20 wt% to 56 wt%, from 26 wt% to 62 wt%, from 32 wt% to 68 wt%, from 38 wt% to 74 wt%, or from 44 wt% to 80 wt%. In terms of upper limits, the solid pigment amount can be less than 80 wt%, e.g., less than 74 wt%, less than 68 wt%, less than 62 wt%, less than 56 wt%, less than 50 wt%, less than 44 wt%, less than 38 wt%, less than 32 wt%, or less than 26 wt%. In terms of lower limits, the solid pigment amount can be greater than 20 wt%, e.g., greater than 26 wt%, greater than 32 wt%, greater than 38 wt%, greater than 44 wt%, greater than 50 wt%, greater than 56 wt%, greater than 62 wt%, greater than 68 wt%, or greater than 74 wt%, Higher amounts, e.g., greater than 80 wt%, and lower amounts, e.g., less than 20 wt%, are also contemplated.

[0072] The opacity of the machine direction oriented polymeric film can, for example, range from 65% to 100%, e.g., from 65% to 86%, from 68.5% to 89.5%, from 72% to 93%, from 75.5% to 96.5%, or from 79% to 100%. In terms of upper limits, the film opacity can be less than 100%, e.g., less than 96.5%, less than 93%, less than 89.5%, less than 86%, less than 82.5%, less than 79%, less than 75.5%, less than 72%, or less than 68.5%. In terms of lower limits, the film opacity can be greater than 65%, e.g., greater than 68.5%, greater than 72%, greater than 75.5%, greater than 79%, greater than 82.5%, greater than 86%, greater than 89.5%, greater than 93%, or greater than 96.5%. Lowe opacities, e.g., less than 65%, are also contemplated. Opacity can be measured according to the standard protocol ISO 2471:2008.

E. Film Properties

[0073] The thickness of the machine direction oriented polymeric film can be selected to balance properties of stiffness and modulus with those of conformability and ease of cutting and dispensing. The film can have a thickness ranging, for example, from 0.5 mils to 5 mils, e.g., from 0.5 mils to 3.2 mils, from 0.95 mils to 3.65 mils, from 1.4 mils to 4.1 mils, from 1.85 mils to 4.55 mils, or from 2.3 mils to 5 mils. In terms of upper limits, the film thickness can be less than 5 mils, e.g., less than 4.55 mils, less than 4.1 mils, less than 3.65 mils, less than 3.2 mils, less than 2.75 mils, less than 2.3 mils, less than 1.85 mils, less than 1.4 mils, or less than 0.95 mils. In terms of lower limits, the film thickness can be greater than 0.5 mils, e.g., greater than 0.95 mils, greater than 1.4 mils, greater than 1.85 mils, greater than 2.3 mils, greater than 2.75 mils, greater than 3.2 mils, greater than 3.65 mils, greater than 4.1 mils, or greater than 4.55 mils. Larger thicknesses, e.g. greater than 5 mils, and smaller thicknesses, e.g., less than 0.5 mils, are also contemplated.

[0074] The hot stretching of the film can be carried out at a temperature within the range from the melting temperature of Component B up to the melting temperature of Component A. The term "melting temperature" as used herein refers to the differential scanning calorimetry melting point of the polymers according to DIN 53765 (1994). It has been found that when the hot stretching is conducted at a temperature within this range, improved die-cut ability and printability can be obtained. Accordingly, typical stretching temperatures, depending upon the particular components used, can range from 115 °C to 145 °C, e.g., from 115 °C to 133 °C, from 118 °C to 136 °C, from 121 °C to 139 °C, from 124°C to 142 °C, or from 127 °C to 145 °C. In terms of upper limits, the stretching temperature can be less than 145 °C, e.g., less than 142 °C, less than 139 °C, less than 136 °C, less than 133 °C, less than 130 °C, less than 127 °C, less than 124 °C, less than 121 °C, or less than 118 °C. In terms of lower limits, the stretching temperature can be greater than 115 °C, e.g., greater than 118 °C, greater than 121 °C, greater than 124 °C, greater than 127 °C, greater than 130 °C, greater than 133 °C, greater than 136 °C, greater than 139 °C, or greater than 142 °C. Higher temperatures, e.g., greater than 145 °C, and lower temperatures, e.g., less than 115 °C, are also contemplated. [0075] In some embodiments, stretching at such temperatures can also advantageously produce an oriented film having a low shrinkage. The film shrinkage can be evaluated by conditioning the film at 23 °C and 50% relative humidity, subsequently immersing the film in water at 70 °C for 2 minutes, and measuring the resulting shrinkage. The shrinkage of the film upon heating to 70 °C can, for example be less than 4%, e.g., less than 3.6%, less than 3.2%, less than 2.8%, less than 2.4%, less than 2%, less than 1.6%, less than 1.2%, less than 0.8%, or less than 0.4%. The film shrinkage can range from 0 to 4%, e.g., from 1.6% to 4%, from 1.2% to 3.6%, from 0.8% to 3.2%, from 0.4% to 2.8%, or from 0 to 2.4%.

[0076] In certain aspects, the extruded films that have been stretch oriented in the machine direction while in a heated condition are then passed over heated annealing rolls where the stretched films are annealed or heat-set. After the heat setting or annealing operation, the film can then be passed over chill rolls to complete the stretch and heat-set operations. The temperature used in the heat setting step (as with the stretching step) depends on the particular polymers used in the blends. In some embodiments, the heat setting temperature is the same as the stretching temperature. In some embodiments, the heat setting temperature is lower than the stretching temperature. The heat setting temperature can, for example, range from 100 °C to 150 °C, e.g., from 100 °C to 130 °C, from 105 °C to 135 °C, from 110 °C to 140 °C, from 115 °C to 145 °C, or from 120 °C to 150 °C. In terms of upper limits, the heat setting temperature can be less than 150 °C, e.g., less than 145 °C, less than 140 °C, less than 135 °C, less than 130 °C, less than 125 °C, less than 120 °C, less than 115 °C, less than 110 °C, or less than 105 °C. In terms of lower limits, the heat setting temperature can be greater than 100 °C, e.g., greater than 105 °C, greater than 110 °C, greater than 115 °C, greater than 120 °C, greater than 125 °C, greater than 130 °C, greater than 135 °C, greater than 140 °C, or greater than 145 °C. Higher temperatures, e.g., greater than 150 °C, and lower temperatures, e.g., less than 100 °C, are also contemplated.

[0077] In some embodiments, the stiffness of the provided films in the machine direction is sufficiently high to provide for improved properties such as high speed dispensability, and the stiffness of the films in the cross direction is sufficiently low as to provide a die cut label that is conformable. The stiffness can be measured using an L+W Bending Resistance Tester according to ISO 2493-2:2011. The L+W machine direction stiffness of the film can, for example, be at least 20 mN, e.g., at least 23 mN, at least 26 mN, at least 29 mN, at least 32 mN, at least 35 mN, at least 38 mN, at least 41 mN, at least 44 mN, or at least 47 mN. The stiffness of the film in the machine direction can, for example, range from 20 mN to 50 mN, e.g., from 20 mN to 38 mN, from 23 mN to 41 mN, from 26 mN to 44 mN, from 29 mN to 47 mN, or from 32 mN to 50 mN. Higher machine direction stiffness values, e.g., greater than 50 mN, are also contemplated. [0078] In some embodiments, the machine direction oriented polymeric film has a significantly greater stiffness in the machine direction than in the cross direction. The ratio of the machine direction stiffness of the film to the cross direction stiffness of the film can, for example, range from 2 to 5, e.g., from 2 to 3.8, from 2.3 to 4.1, from 2.6 to 4.4, from 2.9 to 4.7, or from 3.2 to 5. In terms of lower limits, the ratio of the machine direction stiffness to the cross direction stiffness can be greater than 2, e.g., greater than 2.3, greater than 2.6, greater than 2.9, greater than 3.2, greater than 3.5, greater than 3.8, greater then 4.1, greater than 4.4, or greater than 4.7. In some embodiments, the machine direction stiffness is at least 3 times greater than the cross direction stiffness. Higher stiffness ratios, e.g., greater than 5, are also contemplated.

[0079] The machine direction oriented polymeric films disclosed herein can also have a much higher modulus in the machine direction than in the cross direction, as measured with a Zwick Z010 apparatus according to ISO 527-1:2012. The machine direction modulus can, for example, range from 500 MPa to 2500 MPa, e.g., from 500 MPa to 1700 MPa, from 700 MPa to 1900 MPa, from 900 MPa to 2100 MPs, from 1100 MPa to 2300 MPa, or from 1300 MPa to 2500 M Pa. In terms of lower limits, the machine direction modulus can be greater than 500 MPa, e.g., greater than 700 MPa, greater than 900 MPa, greater than 1100 MPa, greater than 1300 MPa, greater than 1500 MPa, greater than 1700 MPa, greater than 1900 MPa, greater than 2100 MPa, or greater than 2300 MPa. In terms of lower limits, the machine direction modulus can be less than 2500 MPa, e.g., less than 2300 MPa, less than 2100 MPa, less than 1900 MPa, less than 1700 MPa, less than 1500 MPa, less than 1300 MPa, less than 1100 MPa, less than 900 MPa, or less than 700 MPa. Higher moduli, e.g., greater than 2500 MPa, and lower moduli, e.g., less than 500 MPa, are also contemplated.

[0080] The cross direction modulus can, for example, range from 350 MPa to 1000 MPa, e.g., from 350 MPa to 740 MPa, from 415 MPa to 805 MPa, from 480 MPa to 870 MPa, from 545 MPa to 935 MPa, or from 610 MPa to 1000 MPa. In terms of upper limits, the cross direction modulus can be less than 1000 MPa, less than 950 MPa, less than 935 MPa, less than 900 MPa, less than 870 MPa, less than 850 MPa, less than 805 MPa, less than 740 MPa, less than 700 MPa, less than 675 M Pa, less than 650 MPa, less than 610 MPa, less than 545 MPa, less than 500 MPa, less than 480 MPa, less than 450 MPa, or less than 415 MPa. Lower moduli, e.g., less than 350 MPa, are also contemplated.

[0081] The ratio of the machine direction modulus to the cross direction modulus can, for example, range from 1 to 7, e.g., from 1 to 4.6, from 1.6 to 5.2, from 2.2 to 5.8, from 2.8 to 6.4, or from 3.4 to 7. In terms of upper limits, the ratio of the machine direction modulus to the cross direction modulus can be less than 7, e.g., less than 6.4, less than 5.8, less than 5.2, less than 4.6, less than 4, less than 3.4, less than 2.8, less than 2.2, or less than 1.6. In terms of lower limits, the ratio of the machine direction modulus to the cross direction modulus can be greater than 1, e.g., greater than 1.6, greater than 2.2, greater than 2.8, greater than 3.4, greater than 4, greater than 4.6, greater than 5.2, greater than 5.8, or greater than 6.4. Higher ratios, e.g., greater than 7, and lower ratios, e.g., less than 1, are also contemplated.

[0082] The machine direction tensile strength of the film can, for example, range from 10,000 psi to 50,000 psi, e.g., from 10,000 psi to 34,000 psi, from 14,000 psi to 38,000 psi, from 18,000 psi to 42,000 psi, from 22,000 psi to 46,000 psi, or from 26,000 psi to 50,000 psi. In terms of upper limits, the machine direction tensile strength can be less than 50,000 psi, e.g., less than 46,000 psi, less than 42,000 psi, less than 38,000 psi, less than 34,000 psi, less than 30,000 psi, less than 26,000 psi, less than 22,000 psi, less than 18,000 psi, or less than 14,000 psi. In terms of lower limits, the machine direction tensile strength can be greater than 10,000 psi, e.g., greater than 14,000 psi, greater than 18,000 psi, greater than 22,000 psi, greater than 26,000 psi, greater than 30,000 psi, greater than 34,000 psi, greater than 38,000 psi, greater than 42,000 psi, or greater than 46,000 psi. Higher tensile strengths, e.g., greater than 50,000 psi, and lower tensile strengths, e.g., less than 10,000 psi, are also contemplated.

[0083] The cross direction tensile strength of the film can, for example, range from 400 psi to 4000 psi, e.g., from 400 psi to 2560 psi, from 760 psi to 2920 psi, from 1120 psi to 3280 psi, from 1480 psi to 3640 psi, or from 1840 psi to 4000 psi. In terms of upper limits, the cross direction tensile strength can be less than 4000 psi, e.g., less than 3640 psi, less than 3280 psi, less than 2920 psi, less than 2560 psi, less than 2200 psi, less than 1840 psi, less than 1480 psi, less than 1120 psi, or less than 760 psi. In terms of lower limits, the cross direction tensile strength can be greater than 400 psi, greater than 760 psi, greater than 1120 psi, greater than 1480 psi, greater than 1840 psi, greater than 2200 psi, greater than 2560 psi, greater than 2920 psi, greater than 3280 psi, or greater than 3640 psi. Higher tensile strengths, e.g., greater than 4000 psi, and lower tensile strengths, e.g., less than 400, are also contemplated.

[0084] The ratio of the machine direction tensile strength of the film to the cross direction tensile strength of the film can, for example, range from 2.5 to 125, e.g., from 2.5 to 76, from 14.75 to 88.25, from 27 to 100.5, from 39.25 to 112.75, or from 51.5 to 125. In terms of upper limits, the ratio of the machine direction tensile strength to the cross direction tensile strength can be less than 125, e.g., less than 125, less than 112.75, less than 100.5, less than 88.25, less than 76, less than 63.75, less than 51.5, less than 39.25, less than 27, or less than 14.75. In terms of lower limits, the ratio of the machine direction tensile strength to the cross direction tensile strength can be greater than 2.5, e.g., greater than 14.75, greater than 27, greater than 39.25, greater than 51.5, greater than 63.75, greater than 88.25, greater than 100.5, greater or than 112.75. Higher ratios, e.g., greater than 2.5, and lower ratios, e.g., less than 125, are also contemplated.

II. Constructions Containing Machine Direction Oriented Films

[0085] In some embodiments, the provided machine direction oriented polymeric film is used as a monolayer film. In some embodiments, the provided film is used in a multilayer film (e.g., laminate). The multilayer film can include a base layer of the machine direction oriented polymeric film as disclosed herein. The multilayer film can further include at least one skin layer on an upper surface of the base layer, or on both the upper surface and an opposite lower surface of the base layer. The skin layers can also include a machine direction oriented polymeric film as disclosed herein. The compositions of the one or more skin layers can be identical to or different from the composition of the base layer. In some embodiments, the Component A of the base layer is identical to the first component of the skin layers in terms of chemistries and concentrations. In some embodiments, Component A of the base layer differs from the first component of the skin layers. In some embodiments, Component B of the base layer is identical to the first component of the skin layers in terms of chemistries and concentrations. In some embodiments, Component B of the base layer differs from the first component of the skin layers. In some embodiments, Component C of the base layer is identical to the first component of the skin layers in terms of chemistries and concentrations. In some embodiments, Component C of the base layer differs from the first component of the skin layers.

[0086] In some embodiments, the concentration of Component A in the base layer of a multilayer film is higher than the concentration of the first component in the skin layers of the multilayer film. In some embodiments, the base layer of the multilayer film is thicker than the skin layers. The ratio of the base layer thickness to the skin layer thickness can, for example, range from 5 to 10, e.g., from 5 to 8, from 5.5 to 8.5, from 6 to 9, from 6.5 to 9.5, or from 7 to 10. In terms of upper limits, the thickness ratio of the base layer to the skin layers can be less than 10, e.g., less than 9.5, less than 9, less than 8.5, less than 8, less than 7.5, less than 7, less than 6.5, less than 6, or less than 5.5. In terms of lower limits, the thickness ratio of the base layer to the skin layers can be greater than 5, e.g., greater than 5.5, greater than 6, greater than 6.5. greater than 7, greater than 7.5, greater than 8, greater than 8.5, greater than 9, or greater than 9.5. Higher ratios, e.g., greater than 10, and smaller ratios, e.g., less than 5, are also contemplated. [0087] In some embodiments, the composition of the skin layers is different. In some embodiments, the skin layer above the core layer (i.e., the top layer when viewed from top to bottom) is formulated for print receptivity while the skin layer below the core layer (i.e., the bottom layer when viewed from top to bottom) is formulated to promote adhesion to the emulsion acrylic adhesive. In some embodiments, the skin formulated for print receptivity contains from 40% to 50%, from 42% to 48% or from 44% to 47% LLDPE.

[0088] In certain aspects, the multilayer film including a base layer and one or more skin layer can be prepared by co-extrusion of the layers. In certain aspects, the multilayer film can be prepared by laminating the layers together.

[0089] Also provided are labels including the machine direction oriented polymeric film disclosed herein. The labels can include a monolayer film construction and an adhesive layer, or a multilayer film construction and an adhesive layer.

[0090] The adhesive layer of the labels can, for example, have a thickness ranging from 0.4 mils to 1.6 mils, e.g., from 0.4 mils to 1.12 mils, from 0.52 mils to 1.24 mils, from 0.64 mils to 1.36 mils, from 0.76 mils to 1.48 mils, or from 0.88 mils to 1.6 mils. In terms of upper limits, the adhesive layer thickness can be less than 1.6 mils, e.g., less than 1.48 mils, less than 1.36 mils, less than 1.24 mils, less than 1.12 mils, less than 1 mil, less than 0.88 mils, less than 0.76 mils, less than 0.64 mils, or less than 0.52 mils. In terms of lower limits, the adhesive layer thickness can be greater than 0.4 mils, e.g., greater than 0.52 mils, greater than 0.64 mils, greater than 0.76 mils, greater than 0.88 mils, greater than 1 mil, greater than 1.12 mils, greater than 1.24 mils, greater than 1.36 mils, or greater than 1.48 mils. Larger thicknesses, e.g., greater than 1.6 mils, and small thicknesses, e.g., less than 0.4 mils, are also contemplated.

[0091] In some embodiments, the adhesive layer includes one or more pressure-sensitive adhesives, heat-activated adhesives, hot melt adhesives, or a combination thereof. Examples of pressure- sensitive adhesives (PSAs) include, but are not limited to, acrylic based adhesives as well as other elastomers such as natural rubber or synthetic rubber containing polymers or copolymers of styrene, butadiene, acrylonitrile, isoprene and isobutylene. In certain aspects, the PSAs of the label adhesive layer are based on copolymers of acrylic acid esters, such as, for example, 2-ethyl hexyl acrylate, with polar comonomers such as acrylic acid.

[0092] In certain aspects, the adhesive layer includes an adhesive composition selected for compatibility with conventional recycling processes. In some embodiments, the adhesive is a clear, permanent acrylic adhesive, designed to enable polyethylene terephthalate (PET) bottle and thermoform container recycling per the Association of Plastic Recyclers (APR) Design Guide for Plastics Recyclability. In some embodiments, the adhesive can be removed from a substrate after immersion in minimum 75 °F water. Commercial adhesives suitable for use with the labeling of recyclable substrates include, but are not limited to, FASSON^® SR3010 and FASSON^® 3020, each of which is available from Avery Dennison (Glendale, CA).

[0093] One or more additives can be added to the adhesive to obtain one or more certain desired characteristics. These additives can include, for example, pigments, waxes, surfactants, talc, powdered silicates, defoamers, colorants, UV stabilizers or absorbers, luminescents, crosslinkers, foam control agents, buffer agents, anti-blocking agents, wetting agents, matting agents, antistatic agents, acid scavengers, flame retardants, processing aids or agents, extrusion aids, thermally or electrically conductive agents, and others.

[0094] The adhesive layer can be applied directly adjacent to, and in contact with, the machine direction oriented polymeric film. There can be intervening layers between the adhesive layer and the monolayer or multilayer film. The label can include two or more layers of adhesive.

[0095] The provided labels can include the incorporation of one or more clear or transparent layers in any of the constructions described herein. The labels and constructions can also include the incorporation of one or more metallic layers or metal foils. It is also contemplated that the label constructions can include combinations of one or more transparent layers and one or more metallic layers.

[0096] In some embodiments, a release liner is connected to the adhesive layer opposite the machine direction oriented polymeric film. The releasable liner can function as a protective cover such that the release liner remains in place until the label is ready for attachment to an object or surface. If a liner or release liner is included in the label, a wide array of materials and configurations can be used for the liner. In many embodiments, the liner is a paper or paper-based material. In many other embodiments, the liner is a polymeric film of one or more polymeric materials. Typically, at least one face of the liner is coated with a release material such as a silicone or silicone-based material. As will be appreciated, the release coated face of the liner is placed in contact with the otherwise exposed face of the outer adhesive layer. Prior to application of the label to a surface of interest, the liner is removed to thereby expose the adhesive face of the label. The liner can be in the form of a single sheet. Alternatively, the liner can be in the form of multiple sections or panels.

[0097] In some embodiments, the surface to which the label is applied includes one or more recyclable materials. In certain aspects, the surface contains glass. In certain aspects, the surface contains one or more plastics. In certain aspects, the surface contains metal. In some aspects, the substrate is rigid. In certain embodiments, the substrate is a glass bottle. In some aspects, the substrate is deformable. In certain embodiments, the substrate is a squeezable or semi-squeezable plastic bottle.

[0098] The following embodiments are contemplated. All combinations of features and embodiments are contemplated.

III. Exemplary Embodiments

[0099] Embodiment 1: A machine direction oriented polymeric film containing: (A) at least one propylene homopolymer, copolymer, or blend of two or more thereof, having a melt flow rate ranging from 0.1 to 40 g/10 minutes; (B) at least one olefin elastomer; and (C) from 0.5 to 10 wt% of a cavitation agent; wherein the film has a density ranging from 0.9 to 0.95 g/cm³.

[00100] Embodiment 2: An embodiment of embodiment 1, further containing: less than 32 wt% of a pigment concentrate, wherein the pigment concentrate contains less than 80 wt% solid pigment.

[00101] Embodiment 3: An embodiment of embodiment 1 or 2, wherein the film has an opacity greater than 65%.

[00102] Embodiment 4: An embodiment of any of the embodiments of embodiments 1-3, wherein the film is oriented by stretching in the machine direction at a stretch ratio ranging from 4 to 8.

[00103] Embodiment 5: An embodiment of any of the embodiments of embodiment 1-4, wherein the concentration of (A) in the film ranges from 20 to 95 wt%.

[00104] Embodiment 6: An embodiment of any of the embodiments of embodiment 1-5, wherein the concentration of (B) in the film ranges from 5 to 75 wt%.

[00105] Embodiment 7: An embodiment of any of the embodiments of embodiment 1-6, wherein the weight ratio of (A) to (B) in the film ranges from 0.25 to 50.

[00106] Embodiment 8: An embodiment of any of the embodiments of embodiment 1-7, wherein the weight ratio of (A) to (C) in the film ranges from 5 to 95.

[00107] Embodiment 9: An embodiment of any of the embodiments of embodiment 1-8, wherein the weight ratio of (B) to (C) in the film ranges from 0.4 to 75.

[00108] Embodiment 10: An embodiment of any of the embodiments of embodiment 1-9, wherein the cavitation agent is a polymer.

[00109] Embodiment 11: An embodiment of embodiment 10, wherein the cavitation agent polymer is a polyester.

[00110] Embodiment 12: An embodiment of embodiment 11, wherein the polyester is polybutylene terephthalate. [00111] Embodiment 13: An embodiment of any of the embodiments of embodiment 1-12, further comprising a nucleating agent.

[00112] Embodiment 14: An embodiment of any of the embodiments of embodiment 1-13, wherein (A) is a propylene homopolymer.

[00113] Embodiment 15: An embodiment of any of the embodiments of embodiment 1-13, wherein (A) is a propylene copolymer prepared from propylene and an olefin having 2 or 4 to 12 carbon atoms.

[00114] Embodiment 16: An embodiment of embodiment 15, wherein the propylene copolymer is a copolymer of propylene and one or more of ethylene, butylene, hexane, heptane, octane, nonene, or decene.

[00115] Embodiment 17: An embodiment of embodiment 15 or 16, wherein (A) is a propylene ethylene copolymer or propylene butylene copolymer.

[00116] Embodiment 18: An embodiment of any of the embodiments of embodiment 1-17, wherein (B) is an ethylene homopolymer or copolymer, propylene homopolymer or copolymer, or mixture of two or more thereof.

[00117] Embodiment 19: An embodiment of any of the embodiments of embodiment 1-18, wherein (B) is an ethylene-butene copolymer, ethylene-octene copolymer, ethylene-hexene copolymer, ethylene-hexene-butene terpolymer, or mixture of two or more thereof.

[00118] Embodiment 20: An embodiment of any of the embodiments of embodiment 1-19, wherein (B) contains at least one of: a linear low density polyethylene having a density ranging from 0.915 to 0.925 g/cm³; a low density polyethylene having a density ranging from 0.92 to 0.935 g/cm³; a medium density polyethylene having a density ranging from 0.935 to 0.94 g/cm3; and a high density polyethylene having a density ranging from 0.94 to 0.965 g/cm³.

[00119] Embodiment 21: An embodiment of any of the embodiments of embodiment 1-20, wherein (B) has a density ranging from 0.915 to 0.94 g/cm³.

[00120] Embodiment 22: An embodiment of any of the embodiments of embodiment 1-21, wherein (B) has a viscosity that is within 20% of the viscosity of (A).

[00121] Embodiment 23: An embodiment of any of the embodiments of embodiment 1-22, wherein: (A) is a propylene homopolymer having a melt flow rate ranging from 1 to 20 g/10 minutes; (B) is a polyethylene having a density ranging from 0.915 to 0.935 g/cm³; (C) is polybutylene terephthalate; the film is oriented by stretching in the machine direction at a stretch ratio ranging from 4 to 6.4; the film comprises less than 24 wt% of a pigment concentrate, wherein the pigment concentrate comprises less than 74 wt% solid pigment; the film has an opacity greater than 75.5%; and the film has a density ranging from 0.905 to 0.935 g/cm³.

[00122] Embodiment 24: An embodiment of any of the embodiments of embodiment 1-23, wherein one or both of (A) and (B) is prepared using a metallocene catalyst.

[00123] Embodiment 25: An embodiment of any of the embodiments of embodiment 1-24, wherein the stretching is at a stretching temperature between the melting point of (A) and the melting point of (B).

[00124] Embodiment 26: An embodiment of any of the embodiments of embodiment 1-25, having an L+W machine direction stiffness greater than or equal to 20 mN.

[00125] Embodiment 27: An embodiment of any of the embodiments of embodiment 1-26, wherein the machine direction stiffness is at least 3 times a cross direction stiffness of the film.

[00126] Embodiment 28: An embodiment of any of the embodiments of embodiment 1-27, exhibiting a shrinkage of less than 3% at 70 °C.

[00127] Embodiment 29: An embodiment of any of the embodiments of embodiment 1-28, further containing indicia printed on a surface thereof.

[00128] Embodiment 30: A method of preparing a machine direction oriented polymeric film, the method containing: providing (A) at least one propylene homopolymer, copolymer, or blend of two or more thereof, wherein the melt flow rate of (A) ranges from 0.1 to 40 g/10 minutes; (B) at least one olefin elastomer; and (C) a cavitation agent, wherein the concentration of (C) relative to the combination of (A), (B), and (C) ranges from 0.5 to 10 wt%; combining (A), (B), and (C) to form a mixture; extruding a film comprising the formed mixture; and stretch orienting the extruded film in the machine direction, thereby preparing the machine direction oriented polymeric film having a density ranging from 0.9 to 0.95 g/cm³.

[00129] Embodiment 31: An embodiment of embodiment 30, further containing: providing a pigment concentrate, wherein the pigment concentrate contains less than 80 wt% solid pigment; wherein the combining includes combining (A), (B), (C), and the pigment concentrate to form a mixture containing less than 32 wt% of the pigment concentrate.

[00130] Embodiment 32: An embodiment of embodiment 30 or 31, wherein the film has an opacity greater than 65%.

[00131] Embodiment 33: An embodiment of any of the embodiments of embodiment 30-32, wherein the stretch orienting is at a stretch ratio ranging from 4 to 8. [00132] Embodiment 34: An embodiment of any of the embodiments of embodiment 30-33, wherein the cavitation agent is polybutylene terephthalate.

[00133] Embodiment 35: An embodiment of any of the embodiments of embodiment 30-34, wherein: (A) is a propylene homopolymer having a melt flow rate ranging from 1 to 20 g/10 minutes; (B) is a polyethylene having a density ranging from 0.915 to 0.935 g/cm³; (C) is polybutylene terephthalate; the film is oriented by stretching in the machine direction at a stretch ratio ranging from 4 to 6.4; the film contains less than 24 wt% of a pigment concentrate, wherein the pigment concentrate contains less than 74 wt% solid pigment; the film has an opacity greater than 75.5%; and the film has a density ranging from 0.905 to 0.935 g/cm³.

[00134] Embodiment 36: A label containing: the machine direction oriented polymeric film of an embodiment of any of the embodiments of embodiment 1-29; and an adhesive layer adhesively joined to the film.

[00135] Embodiment 37: An embodiment of embodiment 36, wherein the adhesive layer contains a pressure-sensitive adhesive.

[00136] Embodiment 38: An embodiment of embodiment 36 or 37, wherein the adhesive layer contains a heat-activated adhesive layer or a hot-melt adhesive layer.

[00137] Embodiment 39: An embodiment of any of the embodiments of embodiment 36-38, further containing: a release liner.

[00138] Embodiment 40: A method of applying a label to a surface, the method containing: providing a surface having an outer face; providing the label of an embodiment of any of the embodiments of embodiment 36-38; and adhering the label to the outer face of the surface, thereby applying the label to the surface.

[00139] Embodiment 41: A labeled surface containing: a surface having an outer face; and the label of an embodiment of any of the embodiments of embodiment 36-38 adhered to the outer face of the surface.

[00140] While the invention has been described in detail, modifications within the spirit and scope of the invention will be readily apparent to those of skill in the art. In view of the foregoing discussion, relevant knowledge in the art and references discussed above in connection with the Background and Detailed Description, the disclosures of which are all incorporated herein by reference. In addition, it should be understood that aspects of the invention and portions of various embodiments and various features recited below and/or in the appended claims may be combined or interchanged either in whole or in part. In the foregoing descriptions of the various embodiments, those embodiments which refer to another embodiment may be appropriately combined with other embodiments as will be appreciated by one of skill in the art. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.

Claims

We claim:

1. A machine direction oriented polymeric film comprising:

(A) at least one propylene homopolymer, copolymer, or blend of two or more thereof, having a melt flow rate ranging from about 0.1 to about 40 g/10 minutes;

(B) at least one olefin elastomer; and

(C) from about 0.5 to about 10 wt% of a cavitation agent;

wherein the film has a density ranging from about 0.9 to about 0.95 g/cm³.

2. The machine direction oriented polymer film of claim 1, further comprising:

less than about 32 wt% of a pigment concentrate, wherein the pigment concentrate comprises less than about 80 wt% solid pigment.

3. The machine direction oriented polymer film of claim 1 or 2, wherein the film has an opacity greater than about 65%.

4. The machine direction oriented polymeric film of any one of claims 1-3, wherein the film is oriented by stretching in the machine direction at a stretch ratio from about 4 to about 8.

5. The machine direction oriented polymeric film of any one of claims 1-4, wherein the concentration of (A) in the film ranges from about 20 to about 95 wt%.

6. The machine direction oriented polymeric film of any one of claims 1-5, wherein the concentration of (B) in the film ranges from about 5 to about 75 wt%.

7. The machine direction oriented polymeric film of any one of claims 1-6, wherein the weight ratio of (A) to (B) in the film ranges from about 0.25 to about 50.

8. The machine direction oriented polymeric film of any one of claims 1-7, wherein the weight ratio of (A) to (C) in the film ranges from about 5 to about 95.

9. The machine direction oriented polymeric film of any one of claims 1-8, wherein the weight ratio of (B) to (C) in the film ranges from about 0.4 to about 75.

10. The machine direction oriented polymeric film of any one of claims 1-9, wherein the cavitation agent is a polymer.

11. The machine direction oriented polymeric film of claim 10, wherein the cavitation agent polymer is a polyester.

12. The machine direction oriented polymeric film of claim 11, wherein the polyester is polybutylene terephthalate.

13. The machine direction oriented polymeric film of any one of claims 1-12, further comprising a nucleating agent.

14. The machine direction oriented polymeric film of any one of claims 1-13, wherein (A) is a propylene homopolymer.

15. The machine direction oriented polymeric film of any one of claims 1-13, wherein (A) is a propylene copolymer prepared from propylene and an olefin having 2 or 4 to 12 carbon atoms.

16. The machine direction oriented polymeric film of claim 15, wherein the propylene copolymer is a copolymer of propylene and one or more of ethylene, butylene, hexane, heptane, octane, nonene, or decene.

17. The machine direction oriented polymeric film of claim 15 or 16, wherein (A) is a propylene ethylene copolymer or propylene butylene copolymer.

18. The machine direction oriented polymeric film of any one of claims 1-17, wherein (B) is an ethylene homopolymer or copolymer, propylene homopolymer or copolymer, or mixture of two or more thereof.

19. The machine direction oriented polymeric film of any one of claims 1-18, wherein (B) is an ethylene-butene copolymer, ethylene-octene copolymer, ethylene-hexene copolymer, ethylene- hexene-butene terpolymer, or mixture of two or more thereof.

20. The machine direction oriented polymeric film of any one of claims 1-19, wherein (B) comprises at least one of:

a linear low density polyethylene having a density ranging from about 0.915 to about 0.925 g/cm³; a low density polyethylene having a density ranging from about 0.92 to about 0.935 g/cm³; a medium density polyethylene having a density ranging from about 0.935 to about 0.94 g/cm³; and

a high density polyethylene having a density ranging from about 0.94 to about 0.965 g/cm³.

21. The machine direction oriented polymer film of any one of claims 1-20, wherein (B) has a density ranging from about 0.915 to about 0.94 g/cm³.

22. The machine direction oriented polymer film of any one of claims 1-21, wherein (B) has a viscosity that is within about 20% of the viscosity of (A).

23. The machine direction oriented polymer film of any one of claims 1-22, wherein:

(A) is a propylene homopolymer having a melt flow rate ranging from about 1 to about 20 g/10 minutes;

(B) is a polyethylene having a density ranging from about 0.915 to about 0.935 g/cm³;

(C) is polybutylene terephthalate;

the film is oriented by stretching in the machine direction at a stretch ratio ranging from about 4 to about 6.4;

the film comprises less than about 24 wt% of a pigment concentrate, wherein the pigment concentrate comprises less than about 74 wt% solid pigment;

the film has an opacity greater than about 75.5%; and

the film has a density ranging from about 0.905 to about 0.935 g/cm³.

24. The machine direction oriented polymeric film of any one of claims 1-23, wherein one or both of (A) and (B) is prepared using a metallocene catalyst.

25. The machine direction oriented polymeric film of any one of claims 1-24, wherein the stretching is at a stretching temperature between the melting point of (A) and the melting point of (B).

26. The machine direction oriented polymeric film of any one of clams 1-25, having an L+W machine direction stiffness greater than or equal to about 20 mN.

27. The machine direction oriented polymeric film of any one of claims 1-26, wherein the machine direction stiffness is at least about 3 times a cross direction stiffness of the film.

28. The machine direction oriented polymeric film of any one of claims 1-27, exhibiting a shrinkage of less than about 3% at 70 °C.

29. The machine direction oriented polymeric film of any one of claims 1-28, further comprising indicia printed on a surface thereof.

30. A method of preparing a machine direction oriented polymeric film, the method comprising:

providing (A) at least one propylene homopolymer, copolymer, or blend of two or more thereof, wherein the melt flow rate of (A) ranges from about 0.1 to about 40 g/10 minutes; (B) at least one olefin elastomer; and (C) a cavitation agent, wherein the concentration of (C) relative to the combination of (A), (B), and (C) ranges from about 0.5 to about 10 wt%;

combining (A), (B), and (C) to form a mixture;

extruding a film comprising the formed mixture; and

stretch orienting the extruded film in the machine direction, thereby preparing the machine direction oriented polymeric film having a density ranging from about 0.9 to about 0.95 g/cm³.

31. The method of claim 30, further comprising:

providing a pigment concentrate, wherein the pigment concentrate comprises less than about 80 wt% solid pigment; wherein the combining includes combining (A), (B), (C), and the pigment concentrate to form a mixture comprising less than about 32 wt% of the pigment concentrate.

32. The method of claim 30 or 31, wherein the film has an opacity greater than about 65%.

33. The method of any one of claims 30-32, wherein the stretch orienting is at a stretch ratio ranging from about 4 to about 8.

34. The method of any one of claims 30-33, wherein the cavitation agent is polybutylene terephthalate.

35. The method of any one of claims 30-34, wherein:

(B) is a polyethylene having a density ranging from about 0.915 to 0.935 g/cm³;

(C) is polybutylene terephthalate;

the film has an opacity greater than about 75.5%; and

the film has a density ranging from about 0.905 to about 0.935 g/cm³.

36. A label comprising:

the machine direction oriented polymeric film of any one of claims 1-29; and

an adhesive layer adhesively joined to the film.

37. The label of claim 36, wherein the adhesive layer comprises a pressure-sensitive adhesive.

38. The label of claim 36 or 37, wherein the adhesive layer comprises a heat-activated adhesive layer or a hot-melt adhesive layer.

39. The label of any one of claims 36-38, further comprising:

a release liner.

40. A method of applying a label to a surface, the method comprising:

providing a surface having an outer face;

providing the label of any one of claims 36-38; and

adhering the label to the outer face of the surface, thereby applying the label to the surface.

41. A labeled surface comprising:

a surface having an outer face; and

the label of any one of claims 36-38 adhered to the outer face of the surface.