Article

Abstract

An article having recyclability properties including a combination of: (a) at least one polyolefin polymer; and (b) a waterborne adhesive composition having a recyclability property, wherein the recyclability property of the waterborne adhesive composition is such that when the article with the waterborne adhesive composition is reprocessed, the article with the waterborne adhesive composition exhibits less than a 40% decreased change in performance compared to a control article without the waterborne adhesive composition that is reprocessed the same way as the article with the waterborne adhesive composition; a recyclable laminate structure including (a) at least one first polymer film layer; and () at least one layer of the above waterborne laminating adhesive composition; and a process for manufacturing the above recyclable laminate structure.

Claims

1. A first article having a recyclability property comprising a combination of: (a) at least one polyolefin polymer; and (b) a waterborne adhesive composition having a recyclability property, wherein the recyclability property of the waterborne adhesive composition is such that when the article with the waterborne adhesive composition is reprocessed, the article with the waterborne adhesive composition exhibits less than a 40 percent decreased change in performance compared to a control article without the waterborne adhesive composition that is reprocessed the same way as the article with the waterborne adhesive composition.

2. The article of claim 1, wherein the polyolefin polymer is polyethylene.

3. The article of claim 1, wherein the waterborne laminating adhesive composition is an acrylic-based adhesive composition.

4. The article of claim 3, wherein the waterborne acrylic-based adhesive includes a water-dispersible acrylate crosslinker, an isocyanate crosslinker, and mixtures thereof.

5. The article of claim 1, wherein the first article is selected from the group consisting of monolayer or multilayer films, multilayer laminates, and packaging materials or products.

6. A second article made from any one of the first articles of claim 5.

7. The second article of claim 6, wherein the second article is selected from the group consisting of pellets, monolayer or multilayer films, multilayer laminates, and packaging materials or products.

8. A process for producing an article having a recyclability property comprising contacting together: (a) at least one polyolefin polymer; and (b) a waterborne adhesive composition having a recyclability property, wherein the recyclability property of the waterborne adhesive composition is such that when the article with the waterborne adhesive composition is reprocessed, the article with the waterborne adhesive composition exhibits less than a 40 percent decreased change in performance compared to a control article without the waterborne adhesive composition that is reprocessed the same way as the article with the waterborne adhesive composition.

9. A film structure having a recyclability property comprising: () at least one first polymer film layer; and () at least one layer of waterborne adhesive composition having a recyclability property, wherein the recyclability property of the waterborne adhesive composition is such that when the article with the waterborne adhesive composition is reprocessed, the article with the waterborne adhesive composition exhibits less than a 40 percent decreased change in performance compared to a control article without the waterborne adhesive composition that is reprocessed the same way as the article with the waterborne adhesive composition; wherein the waterborne laminating adhesive composition is compatible with the at least first polymer film layer; and wherein the waterborne laminating adhesive composition is disposed on the surface of the at least one first polymer film layer.

10. A multilayer laminate structure having a recyclability property comprising: (i) at least one first polymer film layer; (ii) at least one second polymer film layer; and (iii) at least one layer of a waterborne laminating adhesive composition having a recyclability property, wherein the recyclability property of the waterborne adhesive composition is such that when the article with the waterborne adhesive composition is reprocessed, the article with the waterborne adhesive composition exhibits less than a percent decreased change in performance compared to a control article without the waterborne adhesive composition that is reprocessed the same way as the article with the waterborne adhesive composition; wherein the waterborne laminating adhesive composition is compatible with the first and second film layers; and wherein the layer of the waterborne laminating adhesive composition is disposed on the surface of at least one of the layers of the first film layer and the second film layer for binding the first film layer and the second film layer together.

11. A process for producing a multilayer laminate structure comprising the steps of: (I) providing: (i) at least one first polymer substrate film layer; (ii) at least one second polymer substrate film layer; and (iii) at least one layer of a waterborne laminating adhesive composition compatible with the first and second substrate film layers for bonding the first film layer to the second film layer; wherein the adhesive composition has a recyclability property, wherein the recyclability property of the adhesive composition is such that when the article with the adhesive composition is reprocessed, the article with the adhesive composition exhibits less than a 30 percent decreased change in performance compared to a control article without the adhesive composition that is reprocessed the same way as the article with the adhesive composition; (II) applying the waterborne laminating adhesive composition from step (I) to at least a portion of the surface of at least one of the layers of the first and second substrate layers of step (I) to form a layer of the adhesive composition layer disposed inbetween the first film layer and the second film layer for binding the first film layer and the second film layer together; (III) combining the first and second substrate film layers together with the adhesive layer, sufficient to form a multilayer laminate structure; and (IV) curing the multilayer laminate structure of step (III) to form a cured laminate.

12. A packaging article made from the multilayer laminate structure of claim 11.

13. A process for producing a reprocessed second article from the packaging article of claim 12 comprising the steps of: (A) providing a packaging article of claim 12; (B) fragmenting the packaging article from step (A) to produce a plurality of fragments of a predetermined size; (C) pelletizing the plurality of fragments from step (B) to form a plurality of pellets of a predetermined size; and (D) processing the pellets from step (C) to form a reprocessed second article.

14. A third article produced from the reprocessed second article made by the process of claim 13.

15. The third article of claim 14, wherein the third article is selected from the group consisting of: pellets, monolayer or multilayer films, multilayer laminates, and packaging materials or products.

Description

DETAILED DESCRIPTION

[0010] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight, all temperatures are in degrees Celsius ( C.), and all test methods are current as of the filing date of this disclosure.

[0011] The term recyclable or recyclability herein, with reference to a first article having an adhesive, means mechanical recyclable or recyclability; and means the first article with an adhesive is mechanically re-processable to generate a second article having a desirable performance range, wherein the second article has at least a <40% decreased change in performance relative to the performance of a control article that is without any adhesive and that is reprocessed the same way as the second article. An example, and not to be limited thereby, of testing methods and guidelines for determining recyclability of a plastic article can be found in publication Benchmark Polyethylene Film and Flexible Packaging Innovation Test Protocol, Film-B-01 (2018) and publication PE Film Standard Laboratory Processing Practices, Document Number FPE-P-00 (2020) of The Association of Plastic Recyclers (APR).

[0012] The term composition, as used herein, refers to a mixture of materials which comprises the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0013] Polymer means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term interpolymer as defined hereinafter. Trace amounts of impurities (for example, catalyst residues) may be incorporated into and/or within the polymer. A polymer may be a single polymer, a polymer blend or a polymer mixture, including mixtures of polymers that are formed in situ during polymerization.

[0014] The term interpolymer, as used herein, refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.

[0015] The terms olefin-based polymer or polyolefin, as used herein, refer to a polymer that comprises, in polymerized form, a majority amount of olefin monomer, for example ethylene or propylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.

[0016] The term, ethylene/-olefin interpolymer, as used herein, refers to an interpolymer that comprises, in polymerized form, a majority amount (e.g., greater than [>] 50 mole percent [mol %]) of units derived from ethylene monomer, and the remaining units derived from one or more -olefins. Typical -olefins used in forming ethylene/-olefin interpolymers are C.sub.3-C.sub.10 alkenes.

[0017] The term, ethylene/-olefin copolymer, as used herein, refers to a copolymer that comprises, in polymerized form, a majority amount (>50 mol %) of ethylene monomer, and an -olefin, as the only two monomer types.

[0018] The term -olefin, as used herein, refers to an alkene having a double bond at the primary or alpha (a) position.

[0019] Polyethylene (PE) or ethylene-based polymer shall mean polymers comprising a majority amount (>50 mol %) of units which have been derived from ethylene monomer. This includes polyethylene homopolymers, ethylene/-olefin interpolymers, and ethylene/-olefin copolymers. Common forms of polyethylene known in the art include low density polyethylene (LDPE); linear low density polyethylene (LLDPE); ultra low density polyethylene (ULDPE); very low density polyethylene (VLDPE); medium density polyethylene (MDPE); high density polyethylene (HDPE); enhanced polyethylene; polyethylene elastomers; and polyethylene plastomers. These PE materials are generally known in the art; however, the following descriptions may be helpful in understanding the differences between some of these different PE resins.

[0020] The term LDPE may also be referred to as high pressure ethylene polymer or highly branched polyethylene and is defined to mean that the polymer is partly or entirely homo-polymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500 pounds per square inch (psi) (100 megapascal [MPa]) with the use of free-radical initiators, such as peroxides (see for example U.S. Pat. Nos. 8,916,667; 8,871,887; 8,822,601; 9,228,036; and 9,765,160). LDPE resins typically have a density in the range of 0.916 grams per cubic centimeter (g/cm.sup.3) to 0.935 g/cm.sup.3.

[0021] The term LLDPE, includes both resins made using the traditional Ziegler-Natta catalyst systems and chromium-based catalyst systems as well as single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as m-LLDPE), constrained geometry catalysts (CGC), and molecular catalysts. Resins include linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. LLDPEs contain less long chain branching than LDPEs and includes the substantially linear ethylene polymers which are further defined in U.S. Pat. Nos. 5,272,236; 5,278,272; 5,582,923; and 5,733,155; the homogeneously branched linear ethylene polymer compositions such as those described in U.S. Pat. No. 3,645,992; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Pat. No. 4,076,698; and/or blends thereof (such as those disclosed in U.S. Pat. No. 3,914,342 or U.S. Pat. No. 5,854,045). The LLDPEs can be made via gas-phase, solution-phase or slurry polymerization; or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0022] The term MDPE refers to polyethylenes having densities from 0.926 g/cm.sup.3 to g/cm.sup.3. MDPE is typically made using chromium or Ziegler-Natta catalysts or using single-site catalysts including, but not limited to, bis-metallocene catalysts, constrained geometry catalysts, and molecular catalysts; and typically have a molecular weight distribution (MWD)>2.5. The term HDPE refers to polyethylenes having densities greater than 0.940 g/cm.sup.3 and up to 0.970 g/cm.sup.3, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts or single-site catalysts including, but not limited to, bis-metallocene catalysts and constrained geometry catalysts.

[0023] The term ULDPE refers to polyethylenes having densities of 0.880 g/cm.sup.3 to 0.912 g/cm.sup.3, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts, or single-site catalysts including, but not limited to, bis-metallocene catalysts and constrained geometry catalysts.

[0024] Polyethylene plastomers/elastomers are substantially linear, or linear, ethylene/-olefin copolymers containing homogeneous short-chain branching distributions comprising units derived from ethylene and units derived from at least one C.sub.3-C.sub.10 -olefin comonomer, or at least one C.sub.4-C.sub.8 -olefin comonomer, or at least one C.sub.6-C.sub.8 -olefin comonomer. Polyethylene plastomers/elastomers have a density from 0.870 g/cm.sup.3, or 0.880 g/cm.sup.3, or 0.890 g/cm.sup.3 to g/cm.sup.3, or 0.902 g/cm.sup.3, or 0.904 g/cm.sup.3, or 0.909 g/cm.sup.3, or 0.910 g/cm.sup.3, or 0.917 g/cm.sup.3. Nonlimiting examples of polyethylene plastomers/elastomers include AFFINITY plastomers and elastomers (available from The Dow Chemical Company), EXACT Plastomers (available from ExxonMobil Chemical), TAFMER (available from Mitsui Chemicals), NEXLENE (available from SK Chemicals Co.), and LUCENE (available from LG Chemical Ltd.); and mixtures thereof.

[0025] Blend, polymer blend and like terms mean a composition of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase separated. Such a blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method known in the art. Blends are not laminates, but one or more layers of a laminate may contain a blend. Such blends can be prepared as dry blends, formed in situ (e.g., in a reactor), melt blends, or using other techniques known to those of skill in the art.

[0026] The term in adhering contact and like terms mean that one facial surface of one layer and one facial surface of another layer are in touching and binding contact to one another such that one layer cannot be removed from the other layer without damage to the interlayer surfaces (i.e., the in-contact facial surfaces) of both layers.

[0027] The terms comprising, including, having, and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term comprising may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, consisting essentially of excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term consisting of excludes any component, step or procedure not specifically delineated or listed.

[0028] An objective of the present invention is to produce a first article from original components for use in a first application; and then subsequently, after the first article is used, the used first article can be reprocessed (i.e., the used first article can be subjected to, for example, a recycling process), as a whole, to form a second article from the reprocessed first article directly. The second article can then be used in another subsequent second application.

[0029] The first article includes a combination of: (a) at least one polyolefin polymer; and (b) a waterborne adhesive composition. It has been surprisingly found that the waterborne adhesive composition used in the first article has a recyclability property which is imparted to the first article; and thus, in some embodiments, the first article is recyclable and can be used to produce the second article for various other applications.

[0030] In some non-limiting embodiments, the first article of the present invention may include, for example, one or more of the following articles: a pellet, a film such as a monolayer or multilayer film, a multilayer laminate, a packaging product, and the like. In some non-limiting embodiments, the second article of the present invention may also include, for example, one or more of the following articles: a pellet, a film such as a monolayer or multilayer film, a multilayer laminate, a packaging product, and the like.

[0031] The polyolefin polymer, component (a), useful for making the first article of the present invention can include one or more polyolefins. The first article can be, for example, a polyolefin film. Generally, the polymeric portion of the film is comprised of at least 80% of a polyolefin polymer in one embodiment, at least 85% of a polyolefin polymer in another embodiment, and at least 90% of a polyolefin polymer in still another embodiment. In one embodiment, the polyolefin polymer is at least one PE polymer. For example, the PE polymer, can include one or more of HDPE, LDPE, LLDPE, and mixtures thereof. The polyolefin film may be a monolayer or a multilayer film or may be an oriented film, oriented by machine direction orientation (MDO) or biaxial orientation processes. In another preferred embodiment, the polyolefin is polypropylene (PP), oriented PP (OPP), biaxially oriented PP (BOPP), and mixtures thereof. The non-polyolefin portion of the film may be comprised of polymers such as poly(vinyl alcohol) (EVOH) or a polyamide (e.g., nylon), functionalized tie layer polymers and compatibilizers as described in U.S. Pat. No. 10,300,686.

[0032] The waterborne adhesive composition, component (b), useful for making the first article of the present invention can include one or more waterborne adhesive compositions that have a recyclability property as defined above. The waterborne adhesive composition is such that when the first article with the waterborne adhesive composition is reprocessed (recycled), the first article with the waterborne adhesive composition exhibits < a 40% decreased change in performance compared to a control first article without the waterborne adhesive composition. The first article and the control first article are both reprocessed and tested the same way to determine their respective recyclability property.

[0033] As aforementioned, the present invention can comprise a wide variety of first articles such as films, laminates, or packages and the like. Therefore, as an illustration only of the present invention and not to be limited thereby, the present invention is described herein with reference to a preferred embodiment which is a monolayer or multilayer laminate structure, and more particularly, a multilayer laminate structure. It is, however, understood by one skilled in the art that many other articles can comprise the first article other than a laminate; and that the present invention is not limited thereto.

[0034] In some embodiments, the present invention includes, for example, a multilayer laminate structure; in other embodiments, the present invention includes an adhesive lamination process for manufacturing the multilayer laminate structure; and in still other embodiments, the present invention is directed to a packaging article made using the multilayer laminate structure.

[0035] In one broad embodiment, the present invention includes a multilayer laminate structure as a first article which can be used for producing a laminated packaging material that, in turn, can be recycled at the storefront for further processing. The multilayer laminate includes the combination of at least two polyolefin layer substrates adhered together by a layer of the waterborne adhesive composition described above. For example, the multilayer laminate structure comprises: (i) at least a first polymer film web such as a polyethylene (PE) film; (ii) at least a second polymer film web which can also be the same PE film as the first layer or a different material; and (iii) a layer of the waterborne acrylic-based laminating adhesive composition having a recyclability property described above for bonding the first and second polyolefin film webs together; wherein the layer of the waterborne laminating adhesive composition is compatible with the first and second film layers; and wherein the layer of the waterborne laminating adhesive composition is disposed on the surface of at least one of the layers of the first film layer and the second film layer for binding the first film layer and the second film layer together. One or more other optional film layer substrates can be added to the above laminate structure with the adhesive added inbetween multiple layers to produce a multi-layer laminate structure comprising more than two layers, if desired.

[0036] The first polyolefin film web, component (i), used for making the multilayer laminate of the present invention can include one or more polyolefins. For example, the first polyolefin web, can include one or more polyolefin layers such as HDPE, LDPE, LLDPE, MDO PE, B OPE, and mixtures thereof.

[0037] In one preferred embodiment, the polyolefin film web can include oriented single or multilayer PE films made using either machine direction or biaxial orientation processes which is bonded to a second layer.

[0038] In another preferred embodiment, the polyolefin film web can be a multilayer film comprised one or more layers of HDPE, LLDPE, and LDPE.

[0039] In still another preferred embodiment, the polyolefin film web can be a PP film web or a BOPP film web.

[0040] In yet other preferred embodiments, the polyolefin film web is comprised of at least 80% of a polyolefin polymer in one embodiment, at least 85% of a polyolefin polymer in another embodiment, and 90% of a polyolefin polymer in still another embodiment. In this embodiment, non-polyolefin polymers may be used such as EVOH and polyamides as well as functional tie layers and compatibilizers as described in U.S. Pat. No. 10,300,686.

[0041] The thickness of the first polyolefin film web used to form the recyclable laminate of the present invention can be, for example, from 10 microns (m) to 150 m in one embodiment, from 15 m to 100 m in another embodiment and from 20 m to 50 m in still another embodiment.

[0042] The second polyolefin film web, component (ii), used for making the laminate of the present invention can include one or more polyolefins that can be the same or different from the first polyolefin film web. For example, the second polyolefin film web, can include one or more polyolefin films such as LDPE, LLDPE, and mixtures thereof.

[0043] In one preferred embodiment, the second polyolefin film web can include, for example, a polyethylene film web which is bonded to a first web through an adhesive.

[0044] In another preferred embodiment the second film web is a multilayer structure comprising one or more layers of HDPE, LLDPE and LDPE as described in U.S. Pat. No. 9,421,743.

[0045] In still another preferred embodiment the second film web is a multilayer structure in which one layer is an EVOH or nylon layer as well as functional tie layers and compatibilizers as described in U.S. Pat. No. 10,200,686.

[0046] In yet another preferred embodiment the second film web has a metallized layer that is laminated to the first film web.

[0047] In even still another preferred embodiment the second film web outer layer is a sealant layer with a seal initiation temperature ranging from 75 C. to 120 C.

[0048] The thickness of the polyolefin film second layer used to form the recyclable laminate of the present invention can be, for example, from 10 m to 150 m in one embodiment, from 15 m to 100 m in another embodiment, and from 20 m to 50 m in still another embodiment.

[0049] The layer of laminating adhesive composition, component (iii), used to bind the first and second layers, components (i) and (ii), respectively, is a laminating adhesive that can advantageously be recycled after being previously used to bond the first and second layers together and forming a cured laminate structure. When an article, for example a packaging article, is manufactured from the laminate structure containing the laminating adhesive composition, the laminating adhesive composition imparts the packaging article made from the recyclable laminate structure an acceptable recyclability property to allow the packaging article, after use, to be recycled.

[0050] The waterborne laminating adhesive composition useful in the present invention includes, for example, acrylic based materials from an acrylic emulsion from acrylic monomers such as ethyl acrylate, methyl methacrylate, butyl acrylate, acrylic acid, methacrylic acid, incorporated with polypropylene glycol, and cured with isocyanate. In one preferred embodiment, the adhesive can include, for example, acrylates, isocyanates, polyesters, and mixtures thereof. The adhesive of the present invention is useful in products such as fresh and frozen produce, general snack packaging.

[0051] The thickness/adhesive weights of the adhesive layer used to bond the first and second film webs and to form the multi-layer laminate structure of the present invention can be, for example, from 2 m to 5 m in one general embodiment. Any adhesive weights that are lower than 2 m or greater than 5 m can cause issues with adhesion resulting in failures during the remainder of the converting process.

[0052] The adhesive coating weight for the adhesive layer can be in the range of from 1.62 gsm up to 6 gsm in one general embodiment. Any adhesive weights that are lower than 1.62 gsm or higher than 6 gsm can cause issues with adhesion resulting in failures during the remainder of the converting process.

[0053] The bond value or bond strength of the adhesive, after 60 minutes (min) of lamination, may depend on the laminate structure's polyolefin film layer(s). For example, a laminate with a PE layer(s) may be greater than 50 grams per 15 millimeters (g/15 mm) in one embodiment; greater than 150 g/15 mm in another embodiment; greater than 500 g/15 mm in still another embodiment, and greater than 1,000 g/15 mm in yet another embodiment with a failure mode of film tearing. In one preferred embodiment, the bond strength of the adhesive of the present invention is, for example, from 50 g/15 mm to 2,000 g/15 mm.

[0054] The adhesive useful in the present invention has several other beneficial properties compared to other known lamination adhesives including, for example, the adhesive has superior performance with respect to clarity and runnability on lamination equipment.

[0055] The laminate structure of the present invention can include other optional layered substrates, component (iv), in addition to the above component layers (i)-(iii). For example, substrates such as EVOH, PVDC, OPA, and mixtures thereof can be laminated (bonded) to the above first and second layers, if desired.

[0056] In one general embodiment, a multilayer laminate of the present invention is produced by a process including, for example, the steps of: [0057] (I) providing: (i) a first film substrate, (ii) a second woven fabric substrate; and (iii) an adhesive composition described above; [0058] (II) applying the adhesive composition to at least a portion of the surface of the first or second substrate (also known as the carrier web) to form an adhesive layer on the surface of the first or second film substrate; [0059] (III) combining the first and second film substrates together with the adhesive layer by bringing the adhesive coated film substrate(s) together with the adhesive in contact with each of the first and second film substrates sufficient to form a laminate layer disposed inbetween the first and second substrates; and [0060] (IV) curing the adhesive composition, for example at room temperature (approximately [] 25 C.) or elevated temperature, in the structure of step (III) to bind the two film substrates together forming a multilayer laminate.

[0061] The application of the adhesive composition can be carried out by conventional means known in the art of applying adhesive compositions or formulation to a film substrate. For example, the adhesive composition can be applied using conventional laminating equipment and processes, including applying the adhesive using roto gravure lamination equipment with oven drying capabilities.

[0062] In addition to the recyclability property imparted to the multilayer laminate produced according to the above described process, another advantageous property exhibited by the resulting multilayer laminate can include, for example, the laminate having a substantially haze-free property. For example, MDO PE and BOPE films can have haze values of less than 8%; and standard blown films are typically higher than 8%. In one embodiment, the multilayer laminate of the present invention generally has a haze value of from 6% to 50%. In another embodiment the multilayer laminate generally has a haze value from 10% to 40%.

[0063] In general, the laminate of the present invention, prior to recycling, can be used in a wide range of applications including, for example, packaging applications for manufacturing various packaging materials and products. For example, the laminate can be used for bulk packaging of food grains/pulses, packaging of seeds, packaging of lentils and cereals, packaging of fertilizer, packaging of oilseed, packaging of sugar, packaging of salt, packaging of pharmaceuticals, packaging of other food stuff, and personal care items such as bath salts, detergent pods and the like. The film may also be used as a wrapper for baby wipes, feminine hygiene products, cereal bars, protein bars, cheese and confectionary products. When used for heavy duty packaging of food grain/pulses, the packaging article shows no signs of tunneling/de-lamination/deformation in the laminate after the adhesive cures for 24 hours (hr). Also, other advantageous features and applications for the recyclable laminate when used for packaging articles include, for example, resistance to severe weathering conditions, high tensile strength, robust drop test resistance, excellent optical appearance, and resistance to spills. The recycled materials of the present invention can also be used to reproduce non-packaging materials.

[0064] One of the advantages of the present invention is that a used virgin article (first article) made from the laminate of the present invention can be reprocessed, i.e., processed through a recycling process. After recycling, the recycled material from the previous virgin article can be used to make a subsequent recycled laminate, and in turn a recycled article (i.e., a second article), with properties and performances very close to the previous virgin article. One objective of the present invention is to produce a second article that performs as well as, or better than, the first article, i.e. the properties of the second article performs 100% the same as, or greater than, the properties of the first article. At a minimum, the properties of the second article are maintained at a sufficient level of performance to provide a second article that is useful in another application.

[0065] For example, a new monolayer film structure (second article) made with recycled material from the recycled article (first article) can have properties that exhibits <40% decreased change in performance relative to a control film without any adhesive added that is reprocessed the same way as the virgin article. In some embodiments, the new monolayer film structure (second article) can have properties that exhibits a decreased change in performance at <40% in one embodiment, <30% in one embodiment, <25% in another embodiment, and <15% in still another embodiment. In some embodiments, the new monolayer film structure can have properties that exhibits a decreased change in performance in the range of from 0% to <40% in one embodiment, 0.01% to <40% in another embodiment, and from 0.1% to <40% in still another embodiment. In some embodiments, the new monolayer film structure can have properties that exhibits a decreased change in performance in the range of from 0% to <25% in one embodiment, 0.01% to <25% in another embodiment, and from 0.1% to <25% in still another embodiment. In some embodiments, the new monolayer film structure can have properties that exhibits a decreased change in performance in the range of from 0% to <% in one embodiment, 0.01% to <10% in another embodiment, and from 0.1% to <10% in still another embodiment.

[0066] In a general embodiment, the process for producing a reprocessed second article from, for example, a first packaging article (i.e., the virgin article) comprises the steps of: (A) providing a first packaging article made from the laminate of the present invention; (B) fragmenting the packaging article from step (A) to produce a plurality of fragments of a predetermined size; (C) pelletizing the plurality of fragments from step (B) to form a plurality of pellets of a predetermined size; and (D) processing the pellets from step (C) to form a reprocessed second article.

[0067] In some embodiments, a third article can be produced from the reprocessed second article made by the above general process. For example, the third article can be selected from the group consisting of: pellets, monolayer or multilayer films, multilayer laminates, and packaging materials or products.

EXAMPLES

[0068] The following examples are presented to further illustrate the present invention in detail but are not to be construed as limiting the scope of the claims. Unless otherwise indicated, all parts and percentages are by weight.

[0069] Various materials used in the Inventive Examples (Inv. Ex.) and the Comparative Examples (Comp. Ex.), which follow, are described in Table I.

TABLE-US-00001 TABLE I Raw Materials Material Brief Description Supplier ROBOND Acrylic-based material The Dow L-90M Chemical Company (Dow) ADCOTE 577 Polyurethane and isocyanate Dow Dow Polyether polyol and polyester polyol Dow CR-87-124 blend Dow CR9-101 Isocyanate curative Dow ELITE HDPE having a melt index of 0.85 Dow 5960G1 decagrams per minute (dg/min) and a density of 0.962 grams per cubic centimeter (g/cc) AGILITY LDPE having a melt index of 1.85 dg/min Dow 1021 and a density of 0.920 g/cc Slip MB Erucamide masterbatch having a melt Ampacet AMPACET index of 1 dg/min and a density of 0.916 Corpora- 10090 g/cc tion AB MB Antiblock masterbatch having a melt index Ampacet AMPACET of 1 dg/min and a density of 1.050 g/cc Corpora- 10063 tion ELITE 5400G LLDPE having a melt index of 1 dg/min Dow and a density of 0.920 g/cc AFFINITY PL Ultra linear low density polyethylene Dow 1850G (ULLDPE) (plastomer) having a melt index of 3 dg/min and a density of 0.902 g/cc

General Procedure for Production of Films

[0070] A sealant web film described in Table II, Sealant Web Film Structure; and a print web film described in Table III, Print Web Film Structure, are produced having seven layers; and the compositions of each of the seven layers are described in Tables II and III, respectively. The films were produced by using the following general process: Each of the films were made on a seven-layer blown film line (available from Hosokawa-Alpine). The line utilizes seven, 50 millimeter (mm) diameter, 30 L/D extruders that feed a 250 mm diameter spiral mandrel die with a 2 mm die gap. The output rate was 148 kilograms per hour (kg/hr) and the melt temperature ranged from 185 C. to 245 C. A 2.5 blow up ratio was used in blowing the film and the film was cooled with a single lip air ring and internal bubble cooling. The line speed was 17 meters per minute (m/min) and the film was corona treated to an average surface energy of 43 dynes/centimeter.

TABLE-US-00002 TABLE II Sealant Web Film Structure SEALANT WEB FILM Gauge = 2 mil (50 m); Layflat = 610 mm Layer Layer Ratio Ingredient Level All PE Sealant Web 1 14.0% 86.0% ELITE 5960G1 10.0% AGILITY 1021 2.0% Slip MB AMPACET 10090 2.0% AB MB AMPACET 10063 100.0% Total 2 12.0% 90.0% ELITE 5960G1 10.0% AGILITY 1021 100.0% Total 3 15.0% 100.0% ELITE 5400G 100.0% Total 4 13.0% 90.0% ELITE 5960G1 10.0% AGILITY 1021 100.0% Total 5 13.0% 90.0% ELITE 5960G1 10.0% AGILITY 1021 100.0% Total 6 13.0% 90.0% ELITE 5960G1 10.0% AGILITY 1021 100.0% Total 7 20.0% 94.0% AFFINITY PL 1850G 2.0% Slip MB AMPACET 10090 4.0% AB MB AMPACET 10063 100.0% Total 100%

TABLE-US-00003 TABLE III Print Web Film Structure PRINT WEB FILM Gauge = 38 m; Layflat = 610 mm Layer Layer Ratio Ingredient Level All PE Print Web 1 14.0% 86.0% ELITE 5960G1 10.0% AGILITY 1021 2.0% Slip MB AMPACET 10090 2.0% AB MB AMPACET 10063 100.0% Total 2 12.0% 90.0% ELITE 5960G1 10.0% AGILITY 1021 100.0% Total 3 15.0% 100.0% ELITE 5400G 100.0% Total 4 15.0% 90.0% ELITE 5960G1 10.0% AGILITY 1021 100.0% Total 5 15.0% 90.0% ELITE5960G1 10.0% AGILITY 1021 100.0% Total 6 15.0% 90.0% ELITE 5960G1 10.0% AGILITY 1021 100.0% Total 7 15.0% 86.0% ELITE 5400G 10.0% AGILITY 1021 2.0% Slip MB AMPACET 10090 2.0% AB MB AMPACET 10063 100.0% Total 100%

[0071] After two separate rolls of the above two films (Sealant Web Film and Print Web Film) are produced, a first set of the two films are laminated together with a waterborne adhesive composition of the present invention and a second set of the two films are laminated together with a conventional polyurethane laminating adhesive using the process General Procedure for Film Lamination described herein below.

[0072] Each of the resulting composite film laminates are reprocessed by shredding the films, pelletizing the films, extruding/compounding the pellets, and forming a second film from the compounded pellets originating from each of the first composite film laminates using the procedures described herein below.

[0073] Subsequently, the second films are tested using the testing procedures described herein below with the results of the testing described in Tables VI and VII.

General Procedure for Film Lamination

[0074] Lamination is accomplished by using a SuperCombi 3000 series commercial laminator (available from Nordmeccanica). The laminator has a maximum film width of 1,320 mm and a minimum film width of 600 mm. Additionally, the laminator contains 2 modular coating decks: (1) a waterborne deck for waterborne lamination and (2) a Gravure deck for water-based and solvent-based adhesives/coatings. The laminator also contains 2 zone forced air dryers and a 7.5 kilowatt (KW) corona treater (available from Enercon Industries Corporation) for both a primary film and a secondary film. The maximum line speed of the laminator is 400 meters per minute (m/min) (or 1,312 feet per minute). All unwinds use a 76 mm or a 152 mm core and rewinds use only a 152-mm core. The laminator is capable of running most packing films such as polyester, oriented polypropylene, polyethylene, nylon, paper, foil (secondary only) and others. For the purposes of the present invention, the waterborne laminating adhesive of the present invention used in the Examples was ROBOND L-90M/CR9-101 (available from The Dow Chemical Company); and the films and adhesive were run on the laminator with a target adhesive application of 2.4 gsm utilizing the Gravure deck of the laminator. Upon completion of the lamination, the rolls of film were allowed to fully cure at room temperature for 7 days.

General Procedure for Film Shredding/Pelletizing

[0075] Shredding and pelletizing are accomplished using an INTAREMA 605 K pelletizer unit (available from EREMA). The barrel zone of the pelletizer is run at 171 C.; and the pelletizer zone is run at 176 C.

General Procedure for Compounding Blend Ratios

[0076] The pellets produced using the above pelletizer are compounded utilizing known standard equipment and procedures. For the films disclosed herein, a twin screw extruder, a LabTech 26 mm Twin-Screw Extruder, Type LTE26-44 (Part II) (available from LabTech Engineering Company, LTD), is. The run parameters of the above extruder are described in Table IV.

TABLE-US-00004 TABLE IV LabTech 26 mm Twin-Screw Extruder Compounding Parameters TEMPERATURE PROFILE 26 mm LabTech Extruder Run Conditions Feed Throat Chilled Zone 1 Setpoint, C. 177 Zone 2 to Zone 10 Setpoint, C. ~179-~213 Die Temperature, C. ~218 Extruder Final Melt Temperature, C. 221 Approximate Pressure (kPa) <19,305 Extruder Amps (%) 61 Extruder (rpm) 650 Hopper Feed RPM Pellet Size (mm) 2.73 Pelletizer Speed (meters per second [m/s]) 0.34 RATE Production Run Conditions Total Feed Rate (kilograms per second [kg/s]) 0.0076 Total Amount to make per sample, kilograms (kg)

Fabrication Line

[0077] Blends are generated using six gravimetric feeders (available from Movacolor) connected by a vibratory tray, which feeds a 20 mm twin-screw extruder (available from LabTech Engineering Company LTD [LabTech]). Two mixing zones ensure a consistent composition at the extruder outlet. Downstream of the extruder is a 3.0 cubic centimeters per revolution (cm.sup.3/rev) gear pump, which provides high, steady pressure to push material through the blown film die. A standard 5.08-centimer (cm) (2-inch) diameter cylindrical spiral mandrel die (LabTech) with six spiral channels and die gap of 1.0 mm was used. Pressurized air inflates the film bubble to a 2.5 blow-up ratio (BUR) to a 4 BUR (BUR is defined as maximum bubble diameter divided by die diameter). A dual lip air ring driven by a variable speed blower (Labtech) is used for all experiments. The frost line height (FLH) can vary from 127 mm to 330 mm; and is controlled by modifying blower speed and the air ring chimney. Film thickness is typically controlled within 10% by adjusting the nip roller speed. The layflat is trimmed to a width of 150 mm (6 inches) and wound up into two rolls. The standard conditions and possible ranges of conditions are summarized in Table V.

TABLE-US-00005 TABLE V Blown Film Fabrication Conditions Condition Value Twin screw speed 300 rpm Die temperature 230 C. Die gap 1.0 mm Film speed 0.102 m/s Film thickness 2 mil Die diameter 51 mm BUR 2.5 Output 0.00189 kg/s FLH 236 mm

Film Testing

[0078] The films prepared in the Examples were tested for the following physical properties: Dart, Tear, Secant Modulus and Tensile. The tests were conducted as described in the following ASTM test methods: ASTM D1709 was used to measure Drop Dart; ASTM D1922 was used to measure Elmendor Tear; ASTM D882 was used to measure Secant Modulus; ASTM D822 was used to measure Tensile; and ASTM D1003 was used to measure Haze.

Examples 1-3 and Comparative Examples A-D

[0079] Tables VI and VII provide the results of testing films of the present invention (Inv. Ex. 1-3) compared to the Control Film (Comp. Ex. A). The reprocessed Control Film consists of a 1:1 blend of Print Web and Sealant Web film and contains no laminating adhesive. The sample Control Film is the sample for which all laminated films are compared to.

[0080] All Laminated Containing Films were laminated to the Print Web and Sealant Web to make one resultant film. This resultant film was then shredded and pelletized and blended with multiple ratios of control pellets made from the Control Film.

[0081] The parameters of the films include the film thickness for each of the films of Inv. Ex. 1-3 and Comp. Ex. A-D which was a thickness of no more than 2 mils0.5 mils. All other properties of the films of Inv. Ex. 1-3 cannot have more than a 40% decreased change in performance relative to the Control Film sample.

[0082] An alternative laminating adhesive used as a comparative sample was ADCOTE 577; and such adhesive was used in the film samples of Comparative Examples B-D.

Results

[0083] Each of the tested adhesive compositions of the present invention (Table VI, Inv. Ex. 1-3) is a waterborne laminating adhesive with acrylic functionality. The results described in Table VI show that the adhesive compositions of the present invention pass the <40% decreased change in performance test, for example, in all categories as set forth in Table VI. For instance, the Dart performance is well within the performance boundaries being no less than 40% decreased change in performance relative to the performance of Comp. Ex. A. It has been determined that the adhesive compositions of the present invention pass the recyclability test when pellets containing the adhesive compositions of the present invention are used in amounts of from 10% to 50%.

[0084] Two solvent-borne samples containing a laminating adhesive, ADCOTE 577/CR87-124, were tested as described in Table VII. The laminating adhesive used in Comp. Ex. B-D is a high crosslinked PU system. The samples of Comp. Ex. B-D failed the Dart test with a performance decreased change of greater than 30% (see Table VII, Comp. Ex B-D). It is theorized that the failure of Comp. Ex. B-D is likely due to the rigidity imparted by the highly crosslinked adhesive material. The drop in Dart greater than 40% at amounts of from 10% to 50% results in the adhesive of Comp. Ex. B-D not meeting the criteria for recyclability.

TABLE-US-00006 TABLE VI Examples Using Recyclable Laminating Adhesive Thickness of Film No more than a 40% decreased change compared to the Control Film Example (2 Dart Tear MD Tear TD 1% Secant TD 1% Secant Tensile MD No. 0.5 mils) Haze (J) (g.sub.f) (g.sub.f) (GPa) MD (GPa) (GPa) Comp. Ex. A; 1.9 27 0.914 177 989 0.57 0.56 0.018 Control Inv. Ex. 1 1.9 32 17% 0.629 31% 166 6% 1049 6% 0.56 3% 0.55 2% 0.017 8% ROBOND L-90M; 10% Inv. Ex. 2 1.9 37 35% 0.641 30% 187 6% 896 9% 0.61 7% 0.57 3% 0.016 9% ROBOND L-90M; 25% Inv. Ex. 3 1.8 38 38% 0.544 40% 139 21% 966 2% 0.51 11% 0.51 8% 0.016 13% ROBOND L-90M; 50%

TABLE-US-00007 TABLE VII Comparative Examples Using Conventional Polyurethane Laminating Adhesive Thickness of Film No more than a 40% decreased change compared to the Control Film Example (2 Dart Tear MD Tear TD 1% Secant TD 1% Secant MD Tensile MD No. 0.5 mils) Haze (J) (g.sub.f) (g.sub.f) (GPa) (GPa) (GPa) Comp. Ex. A 1.9 27 0.914 177 989 0.57 0.56 0.018 Control Comp. Ex. B 2.0 34 24% 0.512 44% 181 2% 1057 7% 0.59 2% 0.55 1% 0.016 10% ADCOTE 577; 10% Comp. Ex. C 2.1 41 49% 0.428 53% 150 15% 467 53% 0.55 4% 0.52 8% 0.016 12% ADCOTE 577; 25% Comp. Ex. D 2.0 50 82% 0.421 54% 155 12% 852 14% 0.49 15% 0.50 11% 0.014 22% ADCOTE 577; 50%