HK1187585B

HK1187585B - Sustainable packaging for consumer products

Info

Publication number: HK1187585B
Application number: HK14100699.8A
Authority: HK
Inventors: C ‧博斯韦尔 E‧; ‧I ‧科里亚斯 D; ‧E ‧麦格内斯 R; D‧A‧齐默尔曼; J‧M‧雷曼; J‧A‧麦克丹尼尔; H‧B‧劳克霍斯特; A‧B‧沃森; A‧J‧伯恩斯; B‧M‧邓菲; A‧E‧尼尔特纳
Original assignee: 宝洁公司
Priority date: 2011-01-25
Filing date: 2011-11-16
Publication date: 2016-05-06

Description

Sustainable packaging for consumer products

Technical Field

The present invention relates to sustainable articles that are substantially free of virgin petroleum-based compounds. The article includes a container, a lid, and a label, each made from a recyclable material, a recycled material, a regrind material, or a mixture thereof. The article has a shelf life of at least two years and can be fully recycled according to typical recycling systems.

Background

Plastic packaging uses 40% of almost all polymers, a substantial portion being used in consumer products such as personal care packaging (e.g., shampoo, conditioner, and soap bottles) and household packaging (e.g., for laundry detergent and cleaning compositions). Most materials used to produce polymers for plastic packaging applications (e.g., polyethylene terephthalate, and polypropylene) are derived from monomers (e.g., ethylene, propylene, terephthalic acid, ethylene glycol) that are obtained from non-renewable fossil-based resources such as petroleum, natural gas, and coal. Thus, the price and availability of petroleum, natural gas and coal feedstocks ultimately have a significant impact on the price of polymers used in plastic packaging materials. As the worldwide price of oil, gas and/or coal escalates, so does the price of plastic packaging materials. In addition, many consumers represent a reluctance to purchase products derived from petrochemicals. In some cases, consumers are hesitant to purchase products made from limited non-renewable resources (e.g., oil, gas, and coal). Other consumers may have a poor view of products derived from petrochemicals, which are considered "unnatural" or environmentally unfriendly.

In this regard, manufacturers of plastic packages have begun to use polymers derived from renewable resources to produce their packaging components. For example, about 30% of the poly-p-phenylene that is renewable (i.e., 30% of the monomers used to form the PET (e.g., ethylene glycol) are derived from renewable resources)Ethylene Terephthalate (PET) has been used to form soft drink bottles. In addition, polylactic acid (PLA) derived from corn has been used for plastic packaging applications. While containers made of PLA are biodegradable and environmentally friendly, they are currently not suitable for long-term storage because they are sensitive to heat, shock and moisture. Packages derived from PLA also tend to shrink, and use chemicals (i.e., Mr) on contact when the PLA is in direct contact with the product.Active ingredient in (b) often decompose. Food packaging components and containers for containing personal care products have also been formed from polyethylene derived from renewable resources.

While current state of the art plastic packaging may be comprised in part of polymers derived from renewable materials, such current packaging contains at least one component (e.g., container, lid, label) that comprises at least some virgin petroleum-based material, such as polyethylene, polyethylene terephthalate, or polypropylene. None of the current plastic packaging is substantially free of virgin petroleum-based compounds, 100% sustainable, and 100% recyclable while having a shelf life of at least two years.

Current plastic packaging also presents difficulties during recycling. In the first few steps of a typical recovery procedure, the polymer in the mixture is separated on a density basis using the commonly used float process. Polymers that are denser than water (e.g., polyethylene terephthalate) sink to the bottom of the solution, while polymers that are less dense than water (e.g., polyethylene and polypropylene) rise to the top of the solution. Contamination problems often arise during recycling because current plastic packaging is highly filled or composed of some renewable material, often containing dense materials, which sink and contaminate polyethylene terephthalate streams (e.g., polylactic acid, highly filled high density polyethylene, or highly filled polypropylene) during the float process. Polyethylene terephthalate streams are very sensitive to contamination, while polyethylene streams are generally more stable.

Accordingly, it is desirable to provide plastic packaging that is substantially free of virgin petroleum-based compounds, 100% sustainable, 100% recyclable, has a long shelf life, and can minimize or eliminate contamination during recycling.

Disclosure of Invention

The present invention relates to recyclable articles made of sustainable materials. The article has a shelf life of at least two years and is substantially free of virgin petroleum-based compounds.

In one aspect, the article comprises a container consisting of: at least about 10 wt.%, preferably at least about 25 wt.%, more preferably at least about 50 wt.%, even more preferably at least about 75 wt.% (e.g., at least about 90 wt.% or about 100 wt.%) of a High Density Polyethylene (HDPE) (having a biobased content of at least about 95%, preferably at least about 97%, more preferably at least about 99%, e.g., about 100%) based on the total weight of the container; and a polymer selected from the group consisting of post-consumer recycled polyethylene (PCR-PE), post-industrial recycled polyethylene (PIR-PE), regrind polyethylene, and mixtures thereof. The container has a density of less than about 1 g/mL.

The article of this aspect of the invention further comprises a lid. In some embodiments, the cap is comprised of a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; and mixtures thereof. In an alternative embodiment, the cap is comprised of a polymer selected from the group consisting of: a Linear Low Density Polyethylene (LLDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled LLDPE; LLDPE which is recycled after industrial production; a High Density Polyethylene (HDPE) having a biobased content of at least about 95%, preferably at least about 97%, more preferably at least about 99%, for example about 100%; HDPE recycled after consumption; HDPE recycled after industry; a Low Density Polyethylene (LDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; LDPE recycled after consumption; LDPE which is recycled after industry; and mixtures thereof. The cap has a density of less than about 1 g/mL.

Still further, the article of this aspect of the invention comprises a label consisting of an ink (e.g., a soy-based ink, a plant-based ink, or a mixture thereof) and a substrate comprising a polymer selected from the group consisting of: a polyethylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); paper materials; and mixtures thereof. In an alternative embodiment, the substrate comprises a polymer selected from the group consisting of: polyethylene terephthalate having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene terephthalate (PCR-PET); post-industrial recycled polyethylene terephthalate (PIR-PET); polyesters of furan dicarboxylic acid having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polyesters of furan dicarboxylic acid which are recycled after consumption; polyesters of furan dicarboxylic acid which are recycled after industry; reground polyesters of furan dicarboxylic acid; paper materials; and mixtures thereof. In other alternative embodiments, the substrate comprises a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; paper materials; and mixtures thereof. When the label is comprised of polyethylene or polypropylene, it has a density of less than about 1 g/mL. When the label is comprised of polyethylene terephthalate, a polyester of furan dicarboxylic acid, or a mixture thereof, it has a density greater than about 1 g/mL.

In another aspect, the article comprises a container consisting of: at least about 10 wt.%, preferably at least about 25 wt.%, more preferably at least about 50 wt.%, even more preferably at least about 75 wt.% (e.g., at least about 90 wt.% or about 100 wt.%) of a polyethylene terephthalate (PET) or a polyester of furan dicarboxylic acid (e.g., poly-ethylene 2, 5-furandicarboxylate (PEF)) composition having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, e.g., about 100%, based on the total weight of the container. In embodiments where the container comprises PET having a biobased content of at least about 90%, the container further comprises a polymer selected from the group consisting of: post-consumer recycled polyethylene terephthalate (PCR-PET); post-industrial recycled polyethylene terephthalate (PIR-PET); reground polyethylene terephthalate; and mixtures thereof. In embodiments where the container comprises a polyester of furan dicarboxylic acid having a biobased content of at least about 90%, the container further comprises a polymer selected from the group consisting of: post-consumer recycled polyesters of furan dicarboxylic acid, post-industrial recycled polyesters of furan dicarboxylic acid, reground polyesters of furan dicarboxylic acid, and mixtures thereof. The container has a density greater than about 1 g/mL.

Still further, the article of this aspect of the invention comprises a label consisting of an ink (e.g., a soy-based ink, a plant-based ink, or a mixture thereof) and a substrate comprising a polymer selected from the group consisting of: polyethylene terephthalate having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene terephthalate (PET); PET recycled after industry; reground PET; polyesters of furan dicarboxylic acid having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polyesters of furan dicarboxylic acid which are recycled after consumption; polyesters of furan dicarboxylic acid which are recycled after industry; reground polyesters of furan dicarboxylic acid; paper materials; and mixtures thereof; and ink (e.g., soy-based ink, plant-based ink, or mixtures thereof). In an alternative embodiment, the substrate comprises a polymer selected from the group consisting of: a polyethylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); paper materials; and mixtures thereof. In other alternative embodiments, the substrate comprises a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; paper materials; and mixtures thereof. When the label is comprised of polyethylene or polypropylene, it has a density of less than about 1 g/mL. When the label is comprised of polyethylene terephthalate, a polyester of furan dicarboxylic acid, or a mixture thereof, it has a density greater than about 1 g/mL.

In another aspect, the article comprises a container consisting of: at least about 10 wt%, preferably at least about 25 wt%, more preferably at least about 50 wt%, even more preferably at least about 75 wt% (e.g., at least about 90 wt% or about 100 wt%) of a polypropylene (PP) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, e.g., about 100%, based on the total weight of the container; and a polymer selected from the group consisting of post-consumer recycled polypropylene (PCR-PP), post-industrial recycled polypropylene (PIR-PP), regrind polypropylene, and mixtures thereof. The container has a density of less than about 1 g/mL.

The article of this aspect of the invention further comprises a lid. In some embodiments, the cap is comprised of a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; and mixtures thereof. In an alternative embodiment, the lid consists of: a Linear Low Density Polyethylene (LLDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled LLDPE; LLDPE which is recycled after industrial production; a High Density Polyethylene (HDPE) having a biobased content of at least about 95%, preferably at least about 97%, more preferably at least about 99%, for example about 100%; HDPE recycled after consumption; polyethylene HDPE which is recycled after industry; a Low Density Polyethylene (LDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; LDPE recycled after consumption; LDPE which is recycled after industry; and mixtures thereof. The cap has a density of less than about 1 g/mL.

Still further, the article of this aspect of the invention comprises a label. In some embodiments, the label consists of an ink and a substrate comprising a polymer selected from the group consisting of: a polyethylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polyethylene (PCR-PE) recycled after consumption and polyethylene (PIR-PE) recycled after industry; paper materials; and mixtures thereof; and ink (e.g., soy-based ink, plant-based ink, or mixtures thereof). In an alternative embodiment, the label consists of a substrate comprising a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polypropylene (PCR-PP) recycled after consumption and polypropylene (PIR-PP) recycled after industry; reground polypropylene; paper materials; and mixtures thereof. In other alternative embodiments, the substrate comprises a polymer selected from the group consisting of: polyethylene terephthalate having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene terephthalate (PCR-PET); post-industrial recycled polyethylene terephthalate (PIR-PET); polyesters of furan dicarboxylic acid having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polyesters of furan dicarboxylic acid which are recycled after consumption; polyesters of furan dicarboxylic acid which are recycled after industry; reground polyesters of furan dicarboxylic acid; paper materials; and mixtures thereof. When the label is comprised of polyethylene or polypropylene, it has a density of less than about 1 g/mL. When the label is comprised of polyethylene terephthalate, a polyester of furan dicarboxylic acid, or a mixture thereof, it has a density greater than about 1 g/mL.

Detailed Description

Sustainable articles comprising containers, lids, and labels that are substantially free of virgin petroleum-based compounds have now been developed. At least about 90 wt.%, preferably at least about 95 wt.%, more preferably at least about 97 wt.% of the article is derived from a combination of renewable (i.e., derived from renewable resources) materials along with recycled materials, reground materials, or mixtures thereof. The article has a shelf life of at least two years, is 100% sustainable, and can meet all end-of-life conditions for similar articles derived from virgin petroleum-based resources.

As used herein, "sustainable" refers to a material that has a life cycle assessment or life cycle profile that is improved by greater than 10% over the relevant virgin petroleum-based plastic materials that would otherwise have been used to make the article. As used herein, "Life Cycle Assessment (LCA)" or "Life Cycle profile (LCI)" refers to the investigation and evaluation of the environmental impact of a given product or service as a result of or necessitated by its presence. LCA or LCI may involve an "all-through" analysis, which refers to a full life cycle assessment or life cycle profile from the manufacturing ("beginning") to the use and processing ("end"). For example, High Density Polyethylene (HDPE) containers can be recycled into HDPE resin pellets, which are then used to form containers, films, or injection molded articles, for example, saving a significant amount of fossil-fuel energy. At the end of its life, the polyethylene can be disposed of, for example, by incineration. All inputs and outputs are considered for all phases of the life cycle. As used herein, the "end of life" (EoL) case refers to the treatment phase of an LCA or LCI. For example, polyethylene can be recycled, used for energy incineration (e.g., 1 kilogram of polyethylene produces as much energy as 1 kilogram of diesel), chemically converted to other products, and mechanically recycled. Alternatively, the LCA or LCI may involve a "raw-to-gate" analysis, which refers to the assessment of a portion of the product's life cycle from manufacture ("raw") to just before shipment (i.e., before shipment to a customer) as pellets. Alternatively, this second type of analysis is also referred to as "from end to end".

As used herein, "recyclable" refers to the ability of a part of an article (e.g., bottle, cap, label) to enter an existing recycle stream established for petroleum-derived resins (e.g., HDPE, PET, PP) or paper without compromising the recycled resin or paper output for remanufacturing the part.

The article of the present invention is advantageous because it has the same look and feel as similar articles made from virgin petroleum-based resources, performance characteristics similar to articles made from virgin petroleum-based resources (e.g., similar low and high loads), and can be handled in the same manner (e.g., by recycling the article), but the article of the present invention has improved sustainability over articles derived from virgin petroleum-based resources.

The articles of the present invention are also advantageous in that any virgin polymer used in the manufacture of the articles is derived from renewable resources. As used herein, a "renewable resource" is a resource that is produced by a natural process and whose production rate is comparable to its consumption rate (e.g., within a 100 year time frame). The resources can be supplemented naturally or through agricultural techniques. Non-limiting examples of renewable resources include plants (e.g., sugarcane, sugar beet, corn, potato, citrus fruits, woody plants, lignocelluloses, hemicelluloses, cellulosic waste), animals, fish, bacteria, fungi, and forestry products. These resources may be naturally occurring, hybrid or genetically engineered organisms. The formation of natural resources such as crude oil, coal, natural gas and peat, which require more than 100 years, are not considered renewable resources. Because at least a portion of the articles of the present invention are derived from renewable resources that can sequester carbon dioxide, use of the articles can reduce global warming potential and reduce fossil fuel consumption. For example, some LCA or LCI studies on the resins from which the articles are derived have shown that about one ton of polyethylene made from virgin petroleum-based sources results in the emission of up to about 2.5 tons of carbon dioxide into the environment. Since sugar cane, for example, can absorb carbon dioxide during growth, one ton of polyethylene made from sugar cane can remove up to about 2.5 tons of carbon dioxide from the environment. Thus, using about one ton of polyethylene made from renewable resources (such as sugar cane) reduces the environmental carbon dioxide by up to about 5 tons compared to using one ton of polyethylene derived from petroleum-based resources.

Non-limiting examples of renewable polymers include: polymers produced directly by organisms, e.g. polyhydroxyalkanoates (e.g. poly (. beta. -hydroxyalkanoate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate, NODAX)^TM) And bacterial cellulose; polymers extracted from plants and biomass, such as polysaccharides and derivatives thereof (e.g., gums, cellulose esters, chitin, chitosan, starch, chemically modified starch), proteins (e.g., zein, whey, gluten, collagen), lipids, lignin, and natural rubber; and existing polymers and derivatives derived from monomers of natural origin, such as bio-polyethylene, bio-polypropylene, polytrimethylene terephthalate, polylactic acid, NYLON11, alkyd, succinic-based polyesters, and bio-polyethylene terephthalate.

The sustainable article of the present invention is also advantageous in that its properties can be adjusted by varying the amount of the biomaterials, recycled and regrind materials, or mixtures thereof used to form the container, lid, label, or by incorporating fillers. For example, decreasing recycled material while increasing the amount of biomaterial (e.g., homopolymer versus copolymer when making an equivalent comparison) tends to increase stress crack resistance, increase impact resistance, decrease opacity, and increase surface gloss. Increasing the amount of a particular type of recycled and/or reground material may improve some properties. For example, recycled materials with elastomeric content will increase impact resistance and reduce the cost of the article, depending on the exact grade. In contrast, recycled materials that do not contain elastomer content will tend to have slightly reduced impact resistance. Furthermore, because recycled materials tend to be already colored, the use of recycled materials rather than virgin materials often results in cost savings for the colorant masterbatch, particularly if the color of the recycled material is similar to the proposed color of the article.

The ability to adjust the composition of the sustainable article of the invention enables the incorporation of polymers having a density less than or greater than that of water, such that the overall composition has a density lower than that of water, such as when the article is not composed of polyethylene terephthalate. Thus, the sustainable articles of the present invention are easier to recycle in typical recycle streams than existing plastic packaging materials (which appear to be at least partially sustainable, e.g., those that include polylactic acid as part of the packaging), as contamination issues with polyethylene terephthalate streams during float separation can be avoided.

Even further, the article of the present invention is advantageous in that it can serve as a one-to-one replacement for similar articles (containing polymers derived in whole or in part from virgin petroleum-based materials) and can be prepared using existing manufacturing equipment, reactor conditions, and limiting parameters. Its use results in reduced environmental impact and less consumption of non-renewable resources. The reduced environmental impact occurs because the resource of the build material used to produce the article is replenished at a rate equal to or greater than its rate of consumption; because the use of materials derived from renewable sources generally results in a reduction of greenhouse gases, either due to the avoidance of atmospheric carbon dioxide, or because the construction raw materials are recycled (consumer or industrial) or reground within the plant to reduce the amount of virgin plastics used and the amount of used plastics discarded, for example, in landfills. Furthermore, the articles of the present invention do not result in the destruction of critical ecosystems or the loss of habitats for endangered species.

Sustainable, recyclable articles

The invention described herein relates to sustainable articles that have a shelf life of at least about two years, are 100% recyclable, and are substantially free of virgin petroleum-based materials (i.e., less than about 10 wt%, preferably less than about 5 wt%, more preferably less than about 3 wt% virgin petroleum-based materials based on the total weight of the article). As used herein, "virgin petroleum-based" refers to materials that are derived from petroleum sources (such as oil, natural gas, or coal) and that have not been recycled either industrially or through consumer waste streams.

The sustainable articles of the present invention comprise containers, caps, and labels, each component derived from renewable materials, recycled materials, regrind materials, or mixtures thereof. The container comprises at least about 90 wt.%, preferably at least about 95 wt.%, more preferably at least about 97 wt.% (e.g., about 100 wt.%) of a biopolymer, recycled polymer, reground polymer, or mixtures thereof. The lid comprises at least about 90 wt.%, preferably at least about 95 wt.%, more preferably at least about 97 wt.% (e.g., about 100 wt.%) of a biopolymer, recycled polymer, regrind polymer, or mixtures thereof. The label comprises at least about 90 wt.%, preferably at least about 95 wt.%, more preferably at least about 97 wt.% (e.g., about 100 wt.%) biopolymer, recycled polymer, reground polymer, or mixtures thereof.

Examples of renewable materials include bio-polyethylene, bio-polyethylene terephthalate, and bio-polypropylene. As used herein and unless otherwise specified, "polyethylene" encompasses High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), and Ultra Low Density Polyethylene (ULDPE). As used herein and unless otherwise specified, "polypropylene" encompasses homopolymer polypropylene, random copolymer polypropylene, and block copolymer polypropylene.

As used herein, "recycled" material encompasses post-consumer recycled (PCR) material, post-industrial recycled (PIR) material, and mixtures thereof. In some embodiments, the container and/or lid of the present invention consists of: the recycled high-density polyethylene, the recycled polyethylene terephthalate, the recycled polypropylene, the recycled LLDPE or the recycled LDPE, preferably the recycled high-density polyethylene, the recycled polyethylene terephthalate or the recycled polypropylene, and more preferably the recycled high-density polyethylene or the recycled polyethylene terephthalate. In some embodiments, the label is composed of high density polyethylene, polypropylene, or polyethylene terephthalate recycled from the container.

As used herein, "reground" material is thermoplastic waste, such as sprue, excess parison material, and off-spec parts from injection and blow molding and extrusion operations, which has been recovered by grinding or pelletizing.

As used herein, the prefix "biological" is used to refer to a material that has been derived from a renewable resource.

Biological high density polyethylene

In one aspect, the sustainable article of the present invention comprises a biohigh density polyethylene. Biopolyethylene is produced from the polymerization of bio-ethylene, which is formed from the dehydration of bio-ethanol. Bioethanol can be derived, for example, (i) from the fermentation of sugar from sugarcane, sugar beet or sorghum; (ii) saccharification of starch from corn, wheat or tapioca; and (iii) hydrolysis of the cellulosic material. U.S. patent application publication 2005/0272134, which is incorporated herein by reference, describes the fermentation of sugars to form alcohols and acids.

Suitable sugars for use in forming ethanol include monosaccharides, disaccharides, trisaccharides, and oligosaccharides. Sugars (such as sucrose, glucose, fructose and maltose) can be readily produced from renewable resources (such as sugar cane and sugar beets). As previously mentioned, sugars can also be derived (e.g., by enzymatic cleavage) from other agricultural products (i.e., renewable resources derived from land farming or animal feeding). For example, glucose can be produced on a commercial scale by enzymatic hydrolysis of corn starch. Other common crops that can be used as base starch for conversion to glucose include wheat, buckwheat, peru carrot, potato, barley, kudzu, tapioca, sorghum, sweet potato, yam, arrowroot, sago, and other similar starchy fruits, seeds, or tubers. Sugars produced from these renewable resources (e.g., corn starch produced from corn) can be used to produce alcohols such as propanol, ethanol, and methanol. For example, corn starch may be enzymatically hydrolyzed to produce glucose and/or other sugars. The resulting sugars can be converted to ethanol by fermentation.

Monofunctional alcohols such as ethanol and propanol may also be produced from fatty acids, fats (e.g., tallow), and oils (e.g., monoglycerides, diglycerides, triglycerides, and mixtures thereof). These fatty acids, fats and oils may be derived from renewable resources such as animals or plants. "fatty acid" refers to a straight chain monocarboxylic acid having a chain length of 12 to 30 carbon atoms. "monoglyceride", "diglyceride" and "triglyceride" refer to a plurality of mono-, di-and triesters containing (i) glycerol and (ii) the same or mixed fatty acid unsaturated double bonds, respectively. Non-limiting examples of fatty acids include oleic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. Non-limiting examples of monoglycerides include monoglycerides of any of the fatty acids described herein. Non-limiting examples of diglycerides include diglycerides of any of the fatty acids described herein. Non-limiting examples of triglycerides include triglycerides of any of the fatty acids described herein, such as tall oil, corn oil, soybean oil, sunflower oil, safflower oil, linseed oil, perilla oil, cottonseed oil, tung oil, peanut oil, oiticica oil, hemp seed oil, marine oil (e.g., alkali refined fish oil), dehydrated castor oil, and mixtures thereof. Alcohols can be produced from fatty acids by reduction of fatty acids by any method known in the art. Alcohols can be produced from fats and oils by first hydrolyzing the fats and oils to produce glycerol and fatty acids, and then reducing the fatty acids.

In a preferred embodiment, bio-ethylene is produced from sugar cane. The life cycle stages of ethylene production from sugar cane include (i) sugar cane tilling, (ii) sugar cane fermentation to form bioethanol, and (iii) bioethanol dehydration to form ethylene. Specifically, the sugar cane is washed and transported to the factory where the cane juice is extracted, leaving a filter cake (which serves as fertilizer) and bagasse (residual wood fibers of the stalks obtained after crushing). The bagasse is combusted to produce steam and electricity for powering the sugarcane plant, thereby reducing the use of petroleum-derived fuels. The sugarcane juice is fermented using yeast to form a solution of ethanol and water. Ethanol was distilled from water to produce about 95% pure bioethanol. Bioethanol is subjected to catalytic dehydration (e.g. with an alumina catalyst) to produce ethylene, which is subsequently polymerized to form polyethylene.

Advantageously, the life cycle assessment and profile of ethylene produced from sugar cane for global warming potential, non-biological depletion and fossil fuel consumption show in some aspects advantageous advantages over ethylene produced from petroleum feedstocks. For example, some studies have shown that about one ton of polyethylene made from virgin petroleum-based resources emits up to about 2.5 tons of environmentally generated carbon dioxide, as previously described. Thus, using up to about one ton of polyethylene from renewable resources (such as sugar cane) reduces the environmental carbon dioxide by up to about 5 tons compared to using one ton of polyethylene from petroleum-based resources.

Brasskem has demonstrated the production of High Density Polyethylene (HDPE) and Linear Low Density Polyethylene (LLDPE) using the Hostalen/Basell technology produced by HDPE and the sherilene/Basell technology produced by LLDPE. These catalysts (in some cases) allow the excellent processability of the bio-polyethylene and the resulting products have good consistency with existing resins made by other methods.

A. Container with a lid

The container of this aspect of the invention is comprised of at least about 10 wt.%, preferably at least about 25 wt.%, more preferably at least about 50 wt.%, even more preferably about 75 wt.% (e.g., at least about 90 wt.% or 100 wt.%) High Density Polyethylene (HDPE) having a biobased content of at least about 95%, preferably at least about 97%, more preferably at least about 99%, for example about 100%, based on the total weight of the container. As used herein, "biobased content" refers to the amount of biochar in a material, expressed as a weight (mass) percentage of total organic carbon in the product (see the biobased content evaluation section of the material).

The container further comprises a polymer selected from the group consisting of post-consumer recycled polyethylene (PCR-PE), post-industrial recycled polyethylene (PIR-PE), regrind polyethylene, and mixtures thereof. The recycled polyethylene is optionally present in an amount up to about 90 weight percent, preferably up to about 50 weight percent, more preferably up to about 25 weight percent, based on the total weight of the container. The regrind polyethylene is optionally present in an amount of up to about 75 weight percent, preferably up to about 50 weight percent, more preferably up to about 40 weight percent, based on the total weight of the container.

The container may comprise, for example, about 50 wt.% bio-HDPE, about 25 wt.% PCR-PE, and about 25 wt.% regrind PE; or if no recycled PE is available, about 65 wt.% bio-HDPE and about 35 wt.% reground PE may be included. The container has a density of less than about 1g/mL to facilitate separation during the recovery float process, as previously described.

B. Cover

In some embodiments, the cap of this aspect of the invention is comprised of a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; and mixtures thereof. In some embodiments, the cap is comprised of a polymer selected from the group consisting of: a Linear Low Density Polyethylene (LLDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled LLDPE; LLDPE which is recycled after industrial production; a High Density Polyethylene (HDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); and mixtures thereof. For example, the lid may consist of: (i) a polymer selected from the group consisting of: the bio-Linear Low Density Polyethylene (LLDPE) as described above; post-consumer recycled LLDPE; post-industrial recycled LLDPE, and mixtures thereof; or (ii) a polymer selected from: biohigh density polyethylene (HDPE) as described above; HDPE recycled after consumption; polyethylene HDPE which is recycled after industry; a Low Density Polyethylene (LDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; LDPE recycled after consumption; LDPE which is recycled after industry; and mixtures thereof.

The cover has a density of less than about 1g/mL to facilitate separation during the recycle float process, as previously described. For example, the cap may comprise a mixture of bio-polypropylene and recycled polypropylene; recycled polypropylene, free of bio-polypropylene; or bio-polypropylene, polypropylene that is not recycled.

C. Label (R)

The label of this aspect of the invention consists of a substrate comprising a polymer selected from the group consisting of: a polyethylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); paper materials; and mixtures thereof. The polyethylene may comprise LDPE, LLDPE or HDPE. In an alternative embodiment, the substrate comprises a polymer selected from the group consisting of: polyethylene terephthalate having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene terephthalate (PCR-PET); post-industrial recycled polyethylene terephthalate (PIR-PET); polyesters of furan dicarboxylic acid having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polyesters of furan dicarboxylic acid which are recycled after consumption; polyesters of furan dicarboxylic acid which are recycled after industry; reground polyesters of furan dicarboxylic acid; paper materials; and mixtures thereof. In other alternative embodiments, the substrate comprises a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; paper materials; and mixtures thereof.

The label also contains an ink, which may be solvent-based or water-based. In some embodiments, the ink is derived from a renewable resource, such as soy, a plant, or a mixture thereof. The ink may be cured using heat or ultraviolet radiation (UV). In some preferred embodiments, the ink is cured by UV, which results in a reduction in curing time and energy output. Non-limiting examples of inks include ECO-SURE!^TM(from Gans Ink)&Supply Co.) and solvent-basedAnd BioVu^TMInks (from EFI), they are derived entirely from renewable resources (e.g. corn).

The label may be secured to the container using an adhesive. In some preferred embodiments, the binder is a renewable binder, such as(by Berkshire Labels) which is fully biodegradable and compostable, complies with european standard EN13432, and is FDA approved, shrink-sleeved, or by melting the label onto the container during manufacture. Alternatively, the label may be molded directly into the plastic of the container.

The label may optionally include a layer. For example, when an outer layer consisting of polyethylene is provided on both sides of a layer consisting of ink/metallisation in a three-layer label, a metallisation effect results.

When the label is comprised of polyethylene or polypropylene, it has a density of less than about 1g/mL to facilitate separation during the recycle float process, as previously described. When the label is comprised of polyethylene terephthalate, a polyester of furan dicarboxylic acid, or a mixture thereof, it has a density greater than about 1 g/mL.

Bio-polyethylene terephthalate

In another aspect, the sustainable article of the present invention comprises bio-polyethylene terephthalate. Biopolyethylene terephthalate is produced by the polymerization of biopolyethylene glycol with biopolyterephthalic acid. Bioethanol can be derived from renewable resources through several suitable routes, such as described in WO2009/155086 and U.S. patent 4,536,584, each of which is incorporated herein by reference. Bio-terephthalic acid is obtainable from renewable alcohols via renewable p-xylene as described in international patent application publication WO2009/079213, the content of which is incorporated herein by reference.

In some embodiments, a regenerable alcohol (e.g., isobutanol) is dehydrated in a reactor over an acidic catalyst to form isobutene. Isobutene is recovered and reacted in a second reactor containing a catalyst known to aromatize aliphatic hydrocarbons under appropriately high heat and pressure conditions to form renewable para-xylene.

In another embodiment, a regenerable alcohol (e.g., isobutanol) is dehydrated and dimerized over an acid catalyst. The resulting diisobutylene is recovered and reacted in a second reactor to form renewable para-xylene.

In another embodiment, a renewable alcohol (e.g., isobutanol) containing up to 15 wt% water is dehydrated, or dehydrated and oligomerized, and the resulting oligomers are aromatized to form renewable p-xylene.

In another embodiment, dehydration of the renewable alcohols and aromatization of the resulting olefins occur in a single reactor using a single catalyst to form a mixture of renewable aromatics. The resulting renewable aromatic compound is purified, for example by distillation or crystallization, to yield a pure stream of individual renewable aromatic products. The pure xylenes from these reactions are oxidized to their corresponding phthalic acids and phthalates.

Renewable phthalic acids or phthalates can be produced by oxidation of p-xylene over a transition metal catalyst, optionally in the presence of one or more alcohols (see, e.g., ind.

Unless otherwise indicated, the polyethylene terephthalate used in the present invention can be replaced with a biological, recycled or reground polyester of furan dicarboxylic acid (FDCA), such as poly-ethylene-2, 5-furan dicarboxylate (PEF). FDCA can be produced from Hydroxymethylfurfural (HMF), which is a dehydrated sugar molecule. FDCA can also be produced from methoxymethylfurfural (MMF) derived from glucose and fructose. FDCA can be condensed with a bio-diol (e.g., bio-ethylene glycol) by any method known to those skilled in the art to form the desired polyester.

A. Container with a lid

The container of this aspect of the invention is comprised of at least about 10 wt.%, preferably at least about 25 wt.%, more preferably at least about 50 wt.%, even more preferably about 75 wt.% (e.g., at least about 90 wt.% or 100 wt.%) of polyethylene terephthalate (PET) or a polyester of furan dicarboxylic acid (e.g., poly-ethylene 2, 5-furandicarboxylate (PEF)) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%, based on the total weight of the container.

In embodiments where the container comprises PET having a biobased content of at least about 90%, the container further comprises a polymer selected from the group consisting of post-consumer recycled polyethylene terephthalate (PCR-PET), post-industrial recycled polyethylene terephthalate (PIR-PET), reground polyethylene terephthalate, and mixtures thereof. Recycled PET is optionally present in an amount up to about 90 weight percent, preferably up to about 50 weight percent, more preferably up to about 25 weight percent, based on the total weight of the container. The regrind PET is optionally present in an amount of up to about 75 weight percent, preferably up to about 50 weight percent, more preferably up to about 40 weight percent, based on the total weight of the container. The container may comprise, for example, about 30% by weight of bio-PET and about 70% by weight of PCR-PET.

In embodiments where the container comprises a polyester of furan dicarboxylic acid having a biobased content of at least about 90%, the container further comprises a polymer selected from the group consisting of post-consumer recycled polyesters of furan dicarboxylic acid, post-industrial recycled polyesters of furan dicarboxylic acid, regrind polyesters of furan dicarboxylic acid, and mixtures thereof. In these embodiments, the recycled polyester is optionally present in an amount of up to about 90 weight percent, preferably up to about 50 weight percent, more preferably up to about 25 weight percent, based on the total weight of the container. The regrind polyester is optionally present in an amount of up to about 75 weight percent, preferably up to about 50 weight percent, more preferably up to about 40 weight percent, based on the total weight of the container. The container may comprise, for example, about 30 wt.% of the biological PEF and about 70 wt.% of the PCR-PEF.

The container has a density greater than about 1 g/mL.

B. Cover

In some embodiments, the cap of this aspect of the invention is comprised of a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; and mixtures thereof. In some embodiments, the cap is comprised of a polymer selected from the group consisting of: a Linear Low Density Polyethylene (LLDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled LLDPE; LLDPE which is recycled after industrial production; a High Density Polyethylene (HDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); and mixtures thereof. For example, the lid may consist of: (i) a polymer selected from the group consisting of: the bio-Linear Low Density Polyethylene (LLDPE) as described above; post-consumer recycled LLDPE; post-industrial recycled LLDPE, and mixtures thereof; or (ii) a polymer selected from: biohigh density polyethylene (HDPE) as described above; HDPE recycled after consumption; HDPE recycled after industry; a Low Density Polyethylene (LDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; LDPE recycled after consumption; post-industrial recycled LDPE, and mixtures thereof.

C. Label (R)

The label of this aspect of the invention consists of a substrate comprising a polymer selected from the group consisting of: polyethylene terephthalate having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene terephthalate (PET); PET recycled after industry; reground PET; polyesters of furan dicarboxylic acid having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polyesters of furan dicarboxylic acid which are recycled after consumption; polyesters of furan dicarboxylic acid which are recycled after industry; reground polyesters of furan dicarboxylic acid; paper or mixtures thereof. In some alternative embodiments, the label consists of a substrate comprising a polymer selected from the group consisting of: a polyethylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); paper materials; and mixtures thereof. In other alternative embodiments, the substrate comprises a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; paper materials; and mixtures thereof.

The label also contains an ink, which may be solvent-based or water-based, as previously described. In some embodiments, the ink is derived from a renewable resource, such as soy, a plant, or a mixture thereof. The ink may be cured using heat or ultraviolet radiation (UV). In some preferred embodiments, the ink is cured by UV, which results in a reduction in curing time and energy output. Non-limiting examples of inks include ECO-SURE!^TM(from Gans Ink)&Supply Co.) and solvent-basedAnd BioVu^TMInks (from EFI), they are derived entirely from renewable resources (e.g. corn).

The label may be secured to the container using an adhesive. In some embodiments, the binder is a renewable binder, such as(by Berkshire Labels) which is fully biodegradable and compostable, complies with european standard EN13432, and is FDA approved, shrink-sleeved, or by melting the label onto the container during manufacture. Alternatively, the label may be molded directly into the plastic of the container.

The label may optionally include a layer, as previously described.

When the label is comprised of polyethylene or polypropylene, it has a density of less than about 1 g/mL. When the label is comprised of polyethylene terephthalate, a polyester of furan dicarboxylic acid, or a mixture thereof, it has a density greater than about 1 g/mL.

Biological polypropylene

In yet another aspect, the sustainable article of the present invention comprises a bio-polypropylene. The biological polypropylene is produced by polymerizing propylene formed by dehydrating propanol. The renewable resources used to obtain propanol are as described previously. Propanol may also be derived from bio-ethylene. In this route, bio-ethylene is converted to propionaldehyde by hydroformylation using carbon monoxide and hydrogen in the presence of a catalyst (cobalt octacarbonyl or rhodium complex). Propionaldehyde is hydrogenated in the presence of a catalyst (e.g., sodium borohydride and lithium aluminum hydride) to produce propan-1-ol, which can be dehydrated in an acid catalyzed reaction to produce propylene, as described in U.S. patent application publication 2007/0219521, the contents of which are incorporated herein by reference.

A. Container with a lid

The container of this aspect of the invention is comprised of at least about 10 wt.%, preferably at least about 25 wt.%, more preferably at least about 50 wt.%, even more preferably at least about 75 wt.% (e.g., at least about 90 wt.% or about 100 wt.%) polypropylene (PP) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%, based on the total weight of the container.

The container further comprises a polymer selected from the group consisting of post-consumer recycled polypropylene (PCR-PP), post-industrial recycled polypropylene (PIR-PP), regrind polypropylene, and mixtures thereof. The recycled polypropylene is optionally present in an amount up to about 90 wt%, preferably up to about 50 wt%, more preferably up to about 25 wt%, based on the total weight of the container. The regrind polypropylene is optionally present in an amount of up to about 75 weight percent, preferably up to about 50 weight percent, more preferably up to about 40 weight percent, based on the total weight of the container.

The container has a density of less than about 1g/mL to facilitate separation during the float process of a typical recovery system, as previously described. For example, the container can comprise about 50 wt.% biological PP, about 25 wt.% PCR-PP, and about 25 wt.% regrind PP; or if there is no recycled PP available, about 60 wt.% bio-PP and about 40 wt.% reground PP may be included.

B. Cover

In some embodiments, the cap of this aspect of the invention is comprised of a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polypropylene (PCR-PP); polypropylene (PIR-PP) which is recycled after industry; and mixtures thereof. In some embodiments, the cap is comprised of a polymer selected from the group consisting of: a Linear Low Density Polyethylene (LLDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled LLDPE; LLDPE which is recycled after industrial production; a High Density Polyethylene (HDPE) having a biobased content of at least about 95%, preferably at least about 97%, more preferably at least about 99%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); and mixtures thereof. For example, the lid may consist of: (i) a polymer selected from the group consisting of: the bio-Linear Low Density Polyethylene (LLDPE) as described above; post-consumer recycled LLDPE; post-industrial recycled LLDPE, and mixtures thereof; or (ii) a polymer selected from: biohigh density polyethylene (HDPE) as described above; HDPE recycled after consumption; HDPE recycled after industry; a Low Density Polyethylene (LDPE) having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; LDPE recycled after consumption; LDPE which is recycled after industry; and mixtures thereof.

C. Label (R)

The label of this aspect of the invention consists of a substrate comprising a polymer selected from the group consisting of: a polyethylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene (PCR-PE); post-industrial recycled polyethylene (PIR-PE); paper materials; and mixtures thereof. In an alternative embodiment, the label consists of a substrate comprising a polymer selected from the group consisting of: polypropylene having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polypropylene (PCR-PP) recycled after consumption and polypropylene (PIR-PP) recycled after industry; reground polypropylene; paper materials; and mixtures thereof. In other alternative embodiments, the substrate comprises a polymer selected from the group consisting of: polyethylene terephthalate having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; post-consumer recycled polyethylene terephthalate (PCR-PET); post-industrial recycled polyethylene terephthalate (PIR-PET); polyesters of furan dicarboxylic acid having a biobased content of at least about 90%, preferably at least about 93%, more preferably at least about 95%, for example about 100%; polyesters of furan dicarboxylic acid which are recycled after consumption; polyesters of furan dicarboxylic acid which are recycled after industry; reground polyesters of furan dicarboxylic acid; paper materials; and mixtures thereof.

The label also contains an ink, which may be solvent-based or water-based, as previously described. In some embodiments, the ink is derived from a renewable resource, such as soy, a plant, or a mixture thereof. The ink may be cured using heat or ultraviolet radiation (UV). In some preferred embodiments, byUV cures the ink, which results in a reduction in cure time and energy output. Non-limiting examples of inks include ECO-SURE!^TM(from Gans Ink)&Supply Co.) and solvent-basedAnd BioVu^TMInks (from EFI), they are derived entirely from renewable resources (e.g. corn).

The label may optionally include a layer, as previously described.

Evaluation of the biobased content of materials

As used herein, "biobased content" refers to the biocarbon content in a material, which is the weight (mass) percentage of all organic carbon in the product. For example, polyethylene contains two carbon atoms in its structural unit. If the ethylene is derived from a renewable resource, the homopolymer of polyethylene theoretically has a biobased content of 100% because all carbon atoms are derived from a renewable resource. Copolymers of polyethylene may also theoretically have a biobased content of 100% if each of the ethylene and comonomer is derived from renewable resources. In embodiments where the comonomer is not derived from renewable resources, the HDPE will typically only include from about 1 wt% to about 2 wt% of the non-renewable comonomer, resulting in the HDPE having a biobased content of somewhat less than 100% in theory. As another example, polyethylene terephthalate contains ten carbon atoms in its structural units (i.e., two from ethylene glycol monomers and eight from terephthalic acid monomers). If the ethylene glycol moiety is derived from renewable resources, but the terephthalic acid is derived from a petroleum-based source, the theoretical bio-based content of the polyethylene terephthalate is 20%.

A suitable method for evaluating materials derived from renewable resources is by the method of ASTM D6866, which allows the biobased content of materials to be determined by accelerator mass spectrometry, liquid scintillation counting, and isotope mass spectrometry using radioactive carbon analysis. When atmospheric nitrogen is struck by neutrons produced by ultraviolet light, it loses a proton and forms carbon with a molecular weight of 14, which is radioactive. This is¹⁴C is immediately oxidized to carbon dioxide, which provides a small, but measurable, portion of atmospheric carbon. Atmospheric carbon dioxide is circulated through green plants to produce organic molecules in a process known as photosynthesis. The cycle ends when the green plants or other forms of life metabolize organic molecules to produce carbon dioxide, which causes the release of carbon dioxide back to the atmosphere. Virtually all forms of life on earth rely on such green plants to produce organic molecules to produce chemical energy that promotes growth and reproduction. Thus existing in the atmosphere¹⁴C becomes part of all life forms and their biological products. These renewable based organic molecules biodegrade into carbon dioxide, which does not contribute to global warming because no net increase in carbon is released into the atmosphere. In contrast, fossil fuel-based carbon does not have the labeled radioactive carbon ratio of atmospheric carbon dioxide. See WO2009/155086, incorporated herein by reference.

The ASTM D6866 patent application derived from "biobased content" is built on the same concept as radiocarbon dating, but without the use of an age equation. The analysis is performed by obtaining an unknown sampleRadioactive carbon of (C)¹⁴C) Is compared to the amount of radioactive carbon in modern reference standards. This ratio is reported as a percentage, in units of "pMC" (modern carbon percentage). If the material being analyzed is a mixture of modern radiocarbon and fossil carbon (which does not contain radiocarbon), the resulting pMC value is directly related to the amount of biomass material present in the sample.

The modern benchmark standard used in the radiocarbon dating is the nist (national institute of Standards and technology) standard, with a known radiocarbon content, corresponding to approximately the year 1950 of a metric. The notary 1950 was chosen because it represented the time before thermonuclear weapons testing, which introduced large amounts of excess radioactive carbon into the atmosphere with each explosion (the term "carbon explosion"). The benchmark for the metric 1950 is denoted 100 pMC.

Tests have shown that the radioactive carbon content in the atmosphere peaks in 1963, reaching nearly twice the normal level, due to the effect of a "carbon explosion" before the end of the thermonuclear weapons test. Its distribution in the atmosphere has been evaluated since its emergence and has shown values of more than 100pMC for plants and animals since the year 1950 of the official document. The distribution of carbon explosions has gradually declined with time, with current values approaching 107.5 pMC. Thus, new biomass materials such as maize may result in radioactive carbon labelling close to 107.5 pMC.

Petroleum-based carbon does not have the labeled radioactive carbon ratio of atmospheric carbon dioxide. Research has noted that fossil fuels and petrochemicals have less than about 1pMC, typically less than about 0.1pMC, for example less than about 0.03 pMC. However, compounds that are fully derived from renewable resources have at least about 95% modern carbon (pMC), preferably at least about 99pMC, for example about 100 pMC.

Combining fossil carbon with modern carbon into one material will reduce modern pMC values. A contemporary biomass material of 107.5pMC and a petroleum derivative of 0pMC were mixed and the measured pMC value of the material would reflect the ratio of the two components. 100% of the current soybean-derived material showed a radioactive carbon measurement close to 107.5 pMC. If such a material is diluted with 50% of a petroleum derivative, the measurement is close to 54 pMC.

One 100% biobased content result was from 107.5pMC, while the 0% result was equivalent to 0 pMC. In this regard, a sample measuring 99pMC would provide 93% equivalent biobased content results.

Evaluation of the materials described herein was performed according to ASTM D6866, particularly according to method B. The mean values quoted in this report cover the absolute range of 6% (plus and minus 3% on either side of the bio-based content value) to account for changes in the end component radiocarbon label. It is assumed that all materials are fossil, provided or in an initial state during the day, and that the desired result is the amount of biological components "present" in the material, not the amount of biological material "used" in the manufacturing process.

Other techniques for assessing bio-based content of materials are described in U.S. patent publications 3,885,155, 4,427,884, 4,973,841, 5,438,194 and 5,661,299, WO2009/155086, each of which is incorporated herein by reference.

Examples

The container of the sustainable article of any aspect (preferably when comprised of polypropylene) may further comprise impact modifier in an amount of from about 2 wt% to about 20 wt%, preferably from about 5 wt% to about 10 wt%. Impact modifiers generally comprise LDPE in an amount of about 5 to about 10 weight percent, olefinic elastomers in an amount of about 5 to about 15 weight percent, styrenic elastomers in an amount of about 2 to about 10 weight percent, or mixtures thereof. Examples of impact modifiers include Dow AFFINITY^TM(i.e., polyolefin elastomer), Exxon Mobil VISTA MAX^TM(i.e., polypropylene-based elastomers) and GLS-derived(i.e., based on styrenes)Block copolymers/elastomers) in which the saturation level of the olefin portion may vary. The impact modifier may be derived in whole or in part from oil, in whole or in part from renewable resources, or in whole or in part from recycled materials.

The cap of the sustainable article of any aspect can optionally comprise up to 70 wt%, preferably up to about 30 wt%, more preferably up to about 40 wt%, even more preferably up to about 50 wt% of regrind polypropylene, regrind polyethylene, or mixtures thereof (based on the total weight of the cap). In some embodiments, the amount of regrind polymer may be from about 5 wt.% to about 75 wt.%, preferably from about 25 wt.% to about 50 wt.%, based on the total weight of the cap. Incorporating regrind material in the cap can reduce the cost of the resulting article and prevent material waste within the plant, further increasing plant sustainability.

Additionally or alternatively, the cover of the sustainable article of any aspect can optionally comprise an elastomer derived from recycled materials, such as from waste diapers, that contain a quantity of the elastomer. The presence of an elastomer in the cap may improve, for example, the stress crack resistance and drop impact resistance of the cap. The elastomer may be present in the cap in an amount of about 0.1 wt% to about 60 wt%, preferably about 0.1 wt% to about 40 wt%, more preferably about 0.1 wt% to about 20 wt%, depending on the exact performance requirements. The elastomer may also be derived in whole or in part from oil, in whole or in part from renewable resources, or in whole or in part from recycled materials.

In aspects in which the container, cap, and label are not comprised of polyethylene terephthalate, at least one of the container, cap, or label can optionally comprise less than about 70 weight percent of biodegradable polymer based on the total weight of the container, cap, or label, so long as the resulting container, cap, or label has a density of less than 1 g/mL. The biodegradable polymer can be embedded (e.g., by physical blending) into the polymer matrix of the renewable, recyclable, or reground material to prevent exposure of the biodegradable polymer to the articleThe surface of the component, preventing its biodegradation and/or deterioration. Non-limiting examples of biodegradable polymers include: aliphatic polyesters such as polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), and copolymers thereof; aliphatic-aromatic polyesters, e.g. from BASF(i.e., aliphatic-aromatic copolyesters based on terephthalic acid, adipic acid, and 1, 4-butanediol), derived from DuPont(i.e., an aromatic copolyester having a high terephthalic acid content); polyhydroxyalkanoates (PHAs), and copolymers thereof; a thermoplastic starch (TPS) material; cellulose; and mixtures thereof. In some embodiments, the biodegradable polymer further comprises an inorganic salt (such as calcium carbonate sulfate), talc, clay (e.g., nanoclay), aluminum hydroxide, CaSiO₃Glass fibers, crystalline silica (e.g., quartz, novacite, crystallolite), magnesium hydroxide, mica, sodium sulfate, lithopone, magnesium carbonate, iron oxide, or mixtures thereof.

At least one of the container, cap, or label of the sustainable article of any aspect can optionally comprise a colorant masterbatch. As used herein, "colorant masterbatch" refers to a mixture of pigments dispersed in a carrier material at a high concentration. The colorant masterbatch is used to impart color to the final product. In some embodiments, the carrier is a bio-based plastic or a petroleum-based plastic, while in alternative embodiments, the carrier is a bio-based oil or a petroleum-based oil. The colorant masterbatch may be derived in whole or in part from petroleum resources, in whole or in part from renewable resources, or in whole or in part from recycled resources. Non-limiting examples of carriers include polyethylene of biological or oil origin (e.g., LLDPE, LDPE, HDPE), oils of biological origin (e.g., olive oil, rapeseed oil, peanut oil), oils of petroleum origin, reclaimed oils, polyethylene terephthalate of biological or petroleum origin, polypropylene, and mixtures thereof. Pigments that may be derived from carriers of renewable or non-renewable resources may include, for example, inorganic pigments, organic pigments, polymeric resins, or mixtures thereof. Non-limiting examples of pigments include titanium dioxide (e.g., rutile, anatase), copper phthalocyanine, antimony oxide, zinc oxide, calcium carbonate, fumed silica, phthalocyanines (e.g., phthalocyanine blue), ultramarine blue, cobalt blue, monoazo pigments, diazo pigments, acid dyes, basic dyes, quinacridones, and mixtures thereof. In some embodiments, the colorant masterbatch may further include one or more additives, which may be derived from renewable or non-renewable resources. Non-limiting examples of additives include slip agents, UV absorbers, nucleating agents, UV stabilizers, heat stabilizers, clarifying agents, fillers, whitening agents, processing aids, fragrances, flavoring agents, and mixtures thereof.

In some embodiments, color can be imparted to the container, lid, or label of any aspect of the sustainable article by employing direct compounding (i.e., in-line compounding). In these examples, a twin screw compounder is placed at the beginning of an injection, blow or film line and additives (such as pigments) are blended into the resin just prior to article formation.

At least one of the container or cap of the sustainable article of any aspect can further comprise from about 1 wt% to about 50 wt%, preferably from about 3 wt% to about 30 wt%, more preferably from about 5 wt% to about 15 wt%, of a filler, based on the total weight of the container, cap, or label. Non-limiting examples of fillers include starch, renewable fibers (e.g., hemp, flax, coconut, wood, paper, bamboo, grass), inorganic materials (e.g., calcium carbonate, mica, talc), gases (e.g., high pressure gas), blowing agents, microspheres, biodegradable polymers (e.g., PLA, PHA, TPS), renewable but non-biodegradable polymers (e.g., cellulose acetate particles, polyamide-11, alkyd resins), and mixtures thereof.

Of the sustainable article of any of the preceding aspectsOne or more of the container, lid, and label may exhibit a single layer or multiple layers. When the component of the sustainable article exhibits multiple layers, the component can include 2, 3, 4,5, 6, 7,8, 9, or 10 layers. Preferably, the plurality of layers is a bilayer, trilayer, quadruple or quintuple. In some embodiments, the multilayer is a bilayer having a weight ratio of outer layer to inner layer of from about 99:1 to about 1:99, preferably from about 10:90 to about 30:70, for example, about 20: 80. In some embodiments, the multilayer is a trilayer with a weight ratio of outer layer to intermediate layer and inner layer of about 1:98:1 to about 30:40:30, for example, about 5:90:5, 10:80:10, or 20:60: 20. In some embodiments where the component of the article has at least three layers, the recycled material, one or more biodegradable polymers (e.g., PLA, PHA, TPS, cellulose), or mixtures thereof comprise the intermediate layer. The intermediate layer consisting of recycled material, biodegradable polymer, or mixtures thereof may further comprise inorganic salts (such as calcium carbonate calcium sulfate), talc, clays (e.g., nanoclays), aluminum hydroxide, CaSiO₃Glass fibers, crystalline silica (e.g., quartz, novacite, crystallolite), magnesium hydroxide, mica, sodium sulfate, lithopone, magnesium carbonate, iron oxide, or mixtures thereof. The multilayer component having an intermediate layer of a material or biodegradable polymer that can be recycled, for example, by injection techniques (e.g., co-injection), stretch blow molding processes, or extrusion blow molding processes, as described herein. In some embodiments, the multi-layer component of the sustainable article comprises a barrier layer of a gas (e.g., oxygen, nitrogen, carbon dioxide, helium). The barrier layer may be bio-based or petroleum-based and consists of, for example, ethyl vinyl alcohol copolymer (EVOH).

Characterization of containers, caps and labels

Each component of the article of the invention has a shelf life of at least about two years. Astm d792 may be employed to determine the density of a container, lid or label of the present invention.

A. Container with a lid

Containers having a shelf life of at least two years can be characterized by at least one of the following convenient properties: its Water Vapor Transmission Rate (WVTR), Environmental Stress Cracking (ESC), and longitudinal bearing.

The water vapor transmission rate is the steady state rate of water vapor permeation through the membrane under specified conditions of temperature and relative humidity, and can be determined using ASTM 1249-06. The containers of the present invention comprised of HDPE have less than about 0.3 grams per 100 square inches per 1 day (g/100 in) at about 38 ℃ and about 90% relative humidity²Daily), preferably less than about 0.2g/100in²A day, more preferably less than about 0.1g/100in²WVTR/day. The containers of the present invention comprised of PP have less than about 0.6g/100in at about 38 ℃ and about 90% relative humidity²A day, preferably less than about 0.4g/100in²A day, more preferably less than about 0.2g/100in²WVTR/day. The container composed of PET has less than about 2.5g/100in at about 38 ℃ and about 90% relative humidity²A day, preferably less than about 1.25g/100in²A day, more preferably less than about 0.625g/100in²WVTR/day.

Environmental Stress Cracking (ESC) is the premature onset of cracking and embrittlement of plastics due to the simultaneous effects of stress, strain and contact with a specific chemical environment. One method of determining ESC is by employing ASTM D-2561. The container of the present invention can withstand a load of 4.5 kg at 60 ℃ for 15 days, preferably 30 days, when subjected to ASTM D-2561.

Alternatively, the ESC can be determined according to the following procedure. The container to be tested is filled with a liquid to a target filling level and optionally a closure is mounted on the container. If the closure is a screw type closure, it is tightened to a specified torque. The test vessel was conditioned for four hours at 50 ℃. + -. 1.5 ℃. The screw cap was then re-torqued to the original specified torque level and the leaking sample was discarded. It is placed in an upright position at the adjusted temperature of the container and a weight of 4.5 to 5.0 kg is placed on top of it. The containers were inspected daily for thirty days for signs of stress cracking or for signs of leakage that might indicate stress cracking. The container of the present invention can withstand a load of 4.5 to 5.0 kilograms for about thirty days, with the first fifteen days being most critical.

Longitudinal compression testing provides information about the mechanical compression properties (e.g., compression yield load, deflection under compression yield load, compression load at break, apparent compression stiffness) of blown thermoplastic containers. When an empty open-ended vented container is subjected to ASTM D-2659 pressure-longitudinal test at a speed of 50mm/min, the peak compressive strength force (at a deflection of no more than about 5 mm) is not less than about 50N, preferably not less than about 100N, more preferably not less than about 230N. Furthermore, when the containers of the present invention are tested for filling with water at a temperature between 28 ℃ and 42 ℃ and subjected to the ASTM D-2659 longitudinal compression test using a speed of 12.5mm/min, the compressive strength peak force (at deflection of no more than about 5 mm) is no less than about 150N, preferably no less than about 250N, more preferably no less than about 300N. The longitudinal pressure bearing test was conducted in a room maintained at room temperature.

Additionally or alternatively, a construction material comprising HDPE, PET or PP; and the polymers used to produce the containers of the present invention as described above preferably have a heat distortion temperature or Vicat softening point as specified below, and/or can withstand stresses applied according to the full notch creep test as specified below.

Heat Distortion Temperature (HDT) is the temperature at which the test material deflects when loaded at a 3-point bend at a specified maximum external fiber stress. The heat distortion temperature can be determined using the standard procedure outlined in ISO75, where method A uses an external fiber stress of 1.80MPa and method B uses an external fiber stress of 0.45 MPa. The HDPE container construction feedstock of the present invention has an HDT according to method a of at least about 40 ℃, preferably at least about 45 ℃, more preferably at least about 50 ℃, and an HDT according to method B of at least about 73 ℃, preferably at least about 80 ℃, more preferably at least about 90 ℃. The starting material of construction of the PET container of the present invention has an HDT according to method A of at least about 61.1 deg.C, preferably at least about 63 deg.C, more preferably at least about 65 deg.C, and an HDT according to method B of at least about 66.2 deg.C, preferably at least about 68 deg.C, more preferably at least about 70 deg.C. The construction stock for the PP container of the present invention has an HDT according to method a of at least about 57 ℃, preferably at least about 65 ℃, more preferably at least about 70 ℃, and an HDT according to method B of at least about 75 ℃, preferably at least about 90 ℃, more preferably at least about 100 ℃.

The Vicat softening point is the softening point of a defined material which has no definite melting point, but can still be measured for those materials which do have a melting point. The value is the temperature at which the material is penetrated to a depth of 1 mm by a plain end needle having a square mm circular or square cross-section. The Vicat softening point can be determined using the standard procedure outlined in ISO306, with a load of 10N and a heating rate of 50 ℃ per hour for test method A50 and a load of 50N and a heating rate of 50 ℃ per hour for test method B50. The HDPE container construction stock of the present invention has a Vicat softening temperature of at least about 112 ℃, preferably at least about 125 ℃, more preferably at least about 130 ℃ according to test method a50, and a Vicat softening temperature of at least about 75 ℃, preferably at least about 77 ℃, more preferably at least about 80 ℃ according to test method B50. The construction stock for the PET containers of the present invention has a Vicat softening temperature of at least about 79 ℃, preferably at least about 85 ℃, more preferably at least about 90 ℃ according to test method a50, and a Vicat softening temperature of at least about 75 ℃, preferably at least about 77 ℃, more preferably at least about 80 ℃ according to test method B50. The construction stock for the PP container of the present invention has a Vicat softening temperature of at least about 125 c, preferably at least about 154 c, more preferably at least about 175 c, according to test method a50, and a Vicat softening temperature of at least about 75 c, preferably at least about 85 c, more preferably at least about 95 c, according to test method B50.

The Full Notch Creep Test (FNCT) is an accelerated test used to evaluate the resistance of polymers to slow crack growth in selected environments. The HDPE or PP container construction stock of the present invention can withstand at least about 4 hours, preferably at least about 18 hours, more preferably at least about 50 hours, even more preferably about 100 hours at room temperature and with an applied stress of about 4.4MPa when subjected to FNCT as described in ISO 16770.

B. Cover

Lids having a shelf life of at least two years may be characterized by at least one of the following convenient properties: its hinge life (if the lid design includes a hinge), stress crack resistance, drop impact resistance, modulus change upon immersion in water, and Vicat softening point. Hinge life is the ability of a hinge to withstand being opened multiple times by a person or machine. If the hinge life of the lid is tested manually, the lid of the present invention can withstand being opened by a person at least about 150 times, preferably at least about 200 times, and more preferably at least about 300 times, at room temperature. If the hinge life of the lid is tested by machine, it can withstand being opened by machine at least about 1500 times, preferably at least about 1700 times, more preferably at least about 2000 times, at room temperature. In some of these embodiments, the cover is comprised of polypropylene. After each test, the hinge region was examined for breakage. The lid of the present invention shows no breakage when placed in a cold environment (e.g., below about 5 ℃).

The stress crack resistance of the cap can be determined by the ESC method described previously. For example, the cap of the present invention can withstand a 4.5 kilogram load at about 50 ℃ for about fifteen days, preferably about thirty days. Alternatively, the caps of the present invention can withstand cracking in soak stress crack resistance (ISCR) and exhibit no discoloration in about 15 days, preferably about 30 days, according to ASTM D-5419.

Drop impact resistance is the ability of the lid to withstand a drop. To determine the drop impact resistance, containers of the desired configuration without damage were filled with tap water to the nominal filling capacity and left without lid at 23 ± 2 ℃ for 24 hours to reach the standardized temperature. The container is capped and dropped from a specified height. The lid of the present invention (when fitted on a water-filled container) can withstand both a side panel or horizontal drop and an inverted drop from a height of about 1.2 m. The lid of the present invention (when fitted on a water-filled container) can withstand a drop from a vertical bottom of about 1.5m height.

Additionally or alternatively, the construction raw materials constituting PP, LLDPE, HDPE and LDPE caps as described above for producing the caps of the invention preferably have a modulus change or Vicat softening point on immersion in water as specified below.

The change in modulus upon immersion in water was tested using ASTM D-638, which measures the modulus of plastics. The modulus before and after two weeks of soaking in the product at room temperature and 45 ℃ was compared. The construction materials comprising the caps of the present invention exhibit negligible change in modulus upon immersion in water, with a decrease in modulus of less than about 1%.

The construction stock constituting the lid of the present invention exhibits a Vicat softening point of at least about 75 c, preferably at least about 125 c, according to ISO306 test method a50 as previously described. For example, the construction stock comprising the caps of the present invention may exhibit a Vicat softening point of from about 75 ℃ to about 175 ℃, preferably from about 125 ℃ to about 154 ℃. The caps of the present invention exhibit a Vicat softening point of at least about 50 ℃ to about 95 ℃, preferably about 75 ℃ to about 85 ℃, according to ISO306 test method B50 as previously described.

C. Label (R)

Labels having a shelf life of at least two years can be characterized by at least one of the following convenient properties: its chemical resistance, product resistance, shrinkage, friction test and wipe test. The chemical resistance of the label was determined by a soak squeeze test that assesses the adhesion of the label to the container during simulated shower or bath use, the resistance of the label to delamination, and the resistance of the label to product or water. The test results were determined from the label performance after immersing the container filled with the diluted soap solution in a soap solution bath (i.e., 5 grams/liter) diluted at 38 ℃ for one hour and squeezing the container 10, 50, and 100 times. The labels of the present invention do not exhibit changes (e.g., changes in crease, blister, bubble, drop-off ink, printed ink color in the label) after multiple squeezes.

Product resistance is the resistance of the label to its intended product. To test product compatibility, the product is dropped onto the printed side of the label at about 20 to 24 ℃. After about 24 hours, the product was wiped off the label surface using a soft paper towel and the label was inspected for ink bleed, surface discoloration and inter-foil blocking. No change in parameters was shown for each examination of the tags of the present invention.

Shrinkage is the loss of label size. The labels of the present invention exhibit less than about 0.2%, preferably less than about 0.1% shrinkage 24 hours after their manufacture.

The rub test measures the level of friction of the label surface to determine slippage of the product on the packaging line conveyor. In this test, the label is wrapped around a 200g steel block and pulled across the rubber mat at a rate of 150mm/min for at least 15 mm. The labels of the present invention remain unchanged when subjected to the rub test.

The rub test ensures that the label design is not rubbed or scratched off during manufacture or use. In this test, the printed side of the label is folded inwards and placed between the thumb and forefinger. The label was gently pushed back and forth between the fingers for ten cycles. The labels of the present invention remain unchanged after the rub test.

Method of producing a composite material

A. Container with a lid

Blow molding may be used to produce the containers of the present invention. Blow molding is a manufacturing process for forming hollow plastic parts from thermoplastic materials. The blow molding process begins by melting a thermoplastic and forming it into a parison or preform. The parison is a tubular plastic part with a hole at one end through which compressed air can pass. A pressurized gas (typically air) is used to expand the parison or hot preform and force it against the mold cavity. The pressure is maintained until the plastic cools. After the plastic has cooled and hardened, the mold is opened and the part ejected.

There are three main types of blow molding: extrusion blow molding, injection blow molding and injection stretch blow molding. In extrusion blow molding, a molten plastic tube is extruded into a mold cavity and inflated with compressed air. One end of the cartridge is clamped closed. The plastic part is removed from the mold after it has cooled. Extrusion blow molding can be used to produce the HDPE and PP containers of the present invention. These containers may be single-layered or multi-layered.

Injection Blow Molding (IBM) comprises three steps: injection molding, blow molding, and ejection. First, molten polymer is fed into a manifold where it is injected through a nozzle into a hollow heated preform mold. The preform mold forms the outer shape of the resulting container and is clamped around a mandrel (core rod) that forms the inner shape of the preform. The preform consists of a fully formed bottle/jar neck finish with a thick polymer tube attached, which will form the body. The preform mold is opened and the core rod is rotated and sandwiched into the hollow cooling blow mold. The core rod opens and allows compressed air to enter the preform, which expands it to the finished shape. After the cooling period, the blow mold is opened and the mandrel is rotated to the ejection position. And stripping the finished product from the core rod and performing a crack and leak test. Injection blow molding and other blow molding processes described herein are used to form parts of articles embedded with biodegradable polymers. Injection blow molding can be used to produce containers comprising blends of biodegradable polymers.

Injection Stretch Blow Molding (ISBM) is a process for producing plastic containers from preforms or parisons that are stretched in the hoop and axial directions as the preforms are blown into their desired container shape. In the ISBM process, plastic is first molded into a "preform" using an injection molding process. These preforms are produced with the neck of the container, including the threads. The preforms are packaged and, after cooling, fed to a reheated stretch blow molding machine. The preform is heated above its glass transition temperature and then blown into a container using a high pressure air blow mold using a metal blow mold. Typically, the preform is stretched with a core rod as part of the process. Injection stretch blow molding can be used to produce the HDPE, PET, and PP containers of the present invention.

B. Cover

Injection molding may be used to form the caps of the present invention. Injection molding is a manufacturing process for producing parts from thermoplastic materials, thermoset plastic materials, or mixtures thereof. In an injection molding process, polymeric material is fed into a barrel, mixed, formed into a melt and forced into a three-dimensional mold cavity where it solidifies into the configuration of the mold cavity by cooling, heating and/or chemical reaction. Injection molding can be used to make single layer or multilayer caps.

C. Label (R)

Film extrusion may be used to form the labels of the present invention. In film extrusion, a thermoplastic material is melted and formed into a continuous profile. In some embodiments, a multilayer film is coextruded. Film extrusion and coextrusion can be carried out by any method known to those skilled in the art.

Examples of the invention

The compositions shown in the following examples illustrate specific embodiments of the components of the articles of the present invention and are not intended to be limiting thereof. Other modifications can be made by the skilled person without departing from the spirit and scope of the invention.

The components shown in the following examples were prepared by conventional formulation and mixing methods, examples of which are described above. All exemplified amounts are listed in weight percent and, unless otherwise indicated, do not include secondary materials such as diluents, preservatives, colored solutions, image components, botanicals, and the like.

Example 1

The following examples represent suitable compositions for forming the bio-high density polyethylene containers of the present invention.

SGF4950 of 1 BRASKEM

101-150 of 2 KW/PCA

3 has 50% by weight TiO₂White master batch of (2) for TiO₂And LLDPE carrier resins

4 pearls containing TiO₂White masterbatch of mica and LLDPE carrier

5 white masterbatch containing calcium carbonate (73.6 wt%), titanium dioxide (6.4 wt%) and LLDPE carrier resin (20.0 wt%)

6 Pearl containing TiO₂White masterbatch of mica and LLDPE carrier

7 white masterbatch containing calcium carbonate (62 wt%), titanium dioxide (17 wt%) and LLDPE carrier resin (21 wt%)

Any of the colorant masterbatches and fillers previously described herein or known to those skilled in the art can be substituted for the colorant masterbatches and fillers in the above table.

Example 2

The following examples represent suitable compositions for forming the biopolyethylene terephthalate container of the present invention using a liquid colorant master batch.

LNO c rPET of 1 PHOENIX TECHNOLOGIES, rPET of EVERGREEN, CT-1500 of CLEANTECH, or NPL of PHOENIX TECHNOLOGIES

The following examples represent suitable compositions for forming the biopolyethylene terephthalate container of the present invention using opaque liquid colorant masterbatches.

The following examples represent suitable compositions for forming the biopolyethylene terephthalate containers of the present invention using a translucent solid colorant masterbatch.

The following examples represent suitable compositions for forming the biopolyethylene terephthalate container of the present invention using opaque solid colorant masterbatches.

Any of the colorant masterbatches and fillers previously described herein or known to those skilled in the art may be substituted for the colorant masterbatches and fillers in the tables above.

Example 3

The following examples represent suitable compositions for forming the bio-polypropylene container of the present invention.

1 BRASKEM development stage

2 WM054 by WELLMAK

3 may be any reground PP described herein or known to those skilled in the art

OM51687650 of 4 CLARIANT

Of 5 OMYAF-FL

MD6932 of 6 KRATON

In some embodiments where the polypropylene container is multi-layered, the outer layer is comprised of polypropylene and the inner layer is comprised of polyethylene. Any of the colorant masterbatches and fillers previously described herein or known to those skilled in the art may be substituted for the colorant masterbatches, fillers and impact modifiers in the above table.

Example 4

The following examples represent suitable compositions for forming the caps of the present invention. The cap of the present invention may be characterized by the methods and specifications previously described.

1 BRASKEM development stage

2 WM054 by WELLMAK

SGE7252 of 3 BRASKEM

4 ENVISION LDPE PCR

5 ENVISION HDPE PCR

OM51687650 of 6 CLARIANT

Any of the colorant masterbatches described herein or known to those skilled in the art can be substituted for the colorant masterbatches in the above table.

Example 5

The following examples represent suitable compositions for forming the polyethylene and polypropylene labels of the present invention. In some preferred examples, the ink is derived from a renewable resource, as previously described herein.

1 BRASKEM development stage

101-150 of 2 KW/PCA

3 BRASKEM development stage

WM054 of 4 WELLMAK

Example 6

The following examples represent suitable compositions for forming the polyethylene terephthalate labels of the present invention. In some preferred examples, the ink is derived from a renewable resource, as previously described herein.

The tags of the present invention may be characterized by the methods and specifications previously described.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, the disclosed dimension "40 mm" is intended to mean "about 40 mm".

All documents cited in the detailed description are, in relevant part, incorporated herein by reference. The citation of any document is not to be construed as an admission that it is prior art with respect to the present invention. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A sustainable, recyclable, two-year shelf life article substantially free of virgin petroleum-based compounds, the article comprising:

(a) a container, the container comprising:

(i) at least 10 wt% of a High Density Polyethylene (HDPE) having a biobased content of at least 95%; and

(ii) a polymer selected from the group consisting of post-consumer recycled polyethylene (PCR-PE), post-industrial recycled polyethylene (PIR-PE), regrind polyethylene, and mixtures thereof;

(b) a lid, the lid comprising:

(i) a polymer selected from the group consisting of polypropylene having a biobased content of at least 90%, post-consumer recycled polypropylene (PCR-PP), post-industrial recycled polypropylene (PIR-PP), and mixtures thereof; or

(ii) A polymer selected from the group consisting of Linear Low Density Polyethylene (LLDPE) having a biobased content of at least 90%, post-consumer recycled LLDPE, post-industrial recycled LLDPE, High Density Polyethylene (HDPE) having a biobased content of at least 95%, post-consumer recycled HDPE, post-industrial recycled HDPE, Low Density Polyethylene (LDPE) having a biobased content of at least 90%, post-consumer recycled LDPE, post-industrial recycled LDPE; and mixtures thereof; and

(c) a label comprising an ink and a substrate, the substrate comprising:

(i) a polymer selected from the group consisting of polyethylene having a biobased content of at least 90%, post-consumer recycled polyethylene (PCR-PE), post-industrial recycled polyethylene (PIR-PE), paper, and mixtures thereof; or

(ii) A polymer selected from the group consisting of polyethylene terephthalate having a biobased content of at least 90%, post-consumer recycled polyethylene terephthalate (PET), post-industrial recycled PET, regrind PET, polyesters of furan dicarboxylic acid having a biobased content of at least 90%, post-consumer recycled polyesters of furan dicarboxylic acid, post-industrial recycled polyesters of furan dicarboxylic acid, regrind polyesters of furan dicarboxylic acid, paper, and mixtures thereof; or

(iii) A polymer selected from the group consisting of polypropylene having a biobased content of at least 90%, post-consumer recycled polypropylene (PCR-PP), post-industrial recycled polypropylene (PIR-PP), paper, and mixtures thereof;

wherein the container, the lid, the label comprising PE, and the label comprising PP each exhibit a density of less than 1g/mL, and the label comprising PET, a polyester of furan dicarboxylic acid, or a mixture thereof exhibits a density of greater than 1 g/mL.

2. The article of claim 1, wherein the container meets at least one of the following convenience properties:

(i) exhibit less than 0.3 grams per 100 square inches per 1 day (g/100 in) as determined according to ASTM1249-06²Water vapor transmission rate per day (WVTR);

(ii) (ii) withstands a 4.5 kilogram load at 60 ℃ for at least 15 days according to the Environmental Stress Cracking (ESC) method ASTM D-2561; and

(iii) exhibits a peak force of void compressive strength of no less than 50N at a deflection of no more than 5mm when empty, uncapped and vented and tested at a speed of 50 mm/min; or when tested at a speed of 12.5mm/min and filled with water at a temperature of 28 ℃ to 42 ℃ when subjected to a longitudinal compression test ASTM D-2659, exhibits a peak force of filling compression strength of not less than 150N at a deflection of not more than 5 mm.

3. The article of claim 1, wherein the HDPE and the polymer comprising the container satisfy at least one of the following convenience properties:

(i) exhibits a Heat Distortion Temperature (HDT) of at least 40 ℃ according to method a of ISO75 and at least 73 ℃ according to method B of ISO 75; or a Vicat softening point according to ISO306, method A50 of at least 112 ℃, and method B50 of at least 75 ℃; and

(ii) an applied stress of 4.4MPa is withstood according to Full Notch Creep Test (FNCT) method ISO16770 for at least 4 hours.

4. A sustainable, recyclable, two-year shelf life article substantially free of virgin petroleum-based compounds, the article comprising:

(a) a container, the container comprising:

(i) at least 10% by weight of a polyester of polyethylene terephthalate (PET) or furan dicarboxylic acid, each having a biobased content of at least 90% based on the total weight of the container; and

(ii) a polymer selected from the group consisting of post-consumer recycled polyethylene terephthalate (PCR-PET), post-industrial recycled polyethylene terephthalate (PIR-PET), reground polyethylene terephthalate, and mixtures thereof; or a polymer selected from the group consisting of post-consumer recycled polyesters of furan dicarboxylic acid, post-industrial recycled polyesters of furan dicarboxylic acid, reground polyesters of furan dicarboxylic acid, and mixtures thereof;

with the proviso that (i) and (ii) are both PET or both are polyesters of furandicarboxylic acid;

(b) a lid, the lid comprising:

(c) a label comprising an ink and a substrate, the substrate comprising:

wherein the cap, the label comprising PE, and the label comprising PP each exhibit a density of less than 1g/mL, and the container and the label comprising PET, a polyester of furan dicarboxylic acid, or a mixture thereof each exhibit a density of greater than 1 g/mL.

5. The article of claim 4, wherein the container meets at least one of the following convenience properties:

(i) exhibit less than 2.5 grams per 100 square inches per 1 day (g/100 in) as determined by ASTM1249-06²Water vapor transmission rate per day (WVTR);

6. The article of claim 4 wherein the polyester of PET or furan dicarboxylic acid and the polymer comprising the container exhibit a Heat Distortion Temperature (HDT) of at least 61.1 ℃ according to ISO75, method A, and at least 66.2 ℃ according to ISO75, method B; or a Vicat softening point according to ISO306, method A50 of at least 79 ℃ and method B50 of at least 75 ℃.

7. A sustainable, recyclable, two-year shelf life article substantially free of virgin petroleum-based compounds, the article comprising:

(a) a container, the container comprising:

(i) at least 10 wt% of polypropylene (PP) having a biobased content of at least 90%, based on the total weight of the container; and

(ii) a polymer selected from the group consisting of post-consumer recycled polypropylene (PCR-PP), post-industrial recycled polypropylene (PIR-PP), regrind polypropylene, and mixtures thereof;

(b) a lid, the lid comprising:

(ii) A polymer selected from the group consisting of Linear Low Density Polyethylene (LLDPE) having a biobased content of at least 90%, post-consumer recycled LLDPE, post-industrial recycled LLDPE, High Density Polyethylene (HDPE) having a biobased content of at least 95%, post-consumer recycled HDPE, post-industrial recycled HDPE, Low Density Polyethylene (LDPE) having a biobased content of at least 90%, post-consumer recycled LDPE, post-industrial recycled LDPE, and mixtures thereof; and

(c) a label comprising an ink and a substrate, the substrate comprising:

8. The article of claim 7, wherein the container meets at least one of the following convenience properties:

(i) exhibits less than 0.6 grams per 100 square inches per 1 day (g/100 in) as determined by ASTM1249-06²Water vapor transmission rate per day (WVTR);

9. The article of claim 7, wherein the PP and the polymer comprising the container satisfy at least one of the following convenience properties:

(i) exhibits a Heat Distortion Temperature (HDT) of at least 57 ℃ according to method a of ISO75 and at least 75 ℃ according to method B of ISO 75; or a Vicat softening point according to ISO306, method A50 of at least 125 ℃, and method B50 of at least 75 ℃; and

10. The article of any one of claims 1,4, and 7, wherein the biobased content of the HDPE is at least 97%.

11. The article of any one of claims 1,4, and 7, wherein the biobased content of the PP, LLDPE, LDPE, PE, PET, or furandicarboxylic acid is at least 93%.

12. The article of claim 7, wherein the container further comprises 2 to 20 weight percent of an impact modifier, based on the total weight of the container.

13. The article of any one of claims 1,4, and 7, wherein the cap further comprises up to 75 wt.% of regrind polypropylene, regrind polyethylene, or mixtures thereof, based on the total weight of the cap.

14. The article of any one of claims 1,4, and 7, wherein the PCR-PP, PIR-PP, or mixture thereof of the cap further comprises 0.1 wt% to 60 wt% elastomer, based on the total weight of the cap.

15. The article of any one of claims 1,4, and 7, wherein the ink is soy-based, plant-based, or a mixture thereof.

16. The article of any one of claims 1,4, and 7, wherein the label further comprises an adhesive.

17. The article of claim 1 or 7, wherein the container, the cap, the label comprising PE, the label comprising PP, or a mixture thereof further comprises less than 70% by weight of a biodegradable polymer based on the total weight of the container, cap, or label.

18. The article of claim 17, wherein the biodegradable polymer is selected from the group consisting of polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), aliphatic-aromatic copolyesters based on terephthalic acid, aromatic copolyesters with high terephthalic acid content, Polyhydroxyalkanoates (PHA), thermoplastic starch (TPS), cellulose, and mixtures thereof.

19. The article of any one of claims 1,4, and 7, wherein the container, lid, label, or mixture thereof further comprises a colorant masterbatch.

20. The article of claim 19, wherein the colorant masterbatch comprises a carrier selected from a bio-based plastic, a petroleum-based plastic, a bio-based oil, a petroleum-based oil, or mixtures thereof.

21. The article of claim 19, wherein the colorant masterbatch comprises a pigment selected from the group consisting of inorganic pigments, organic pigments, polymeric resins, and mixtures thereof.

22. The article of claim 19, wherein the colorant masterbatch comprises an additive.

23. The article of any one of claims 1,4, and 7, wherein the container, lid, or combination thereof optionally comprises from 1 wt% to 50 wt% of a filler selected from the group consisting of starch, fiber, inorganic material, blowing agent, microspheres, biodegradable polymers, renewable but non-biodegradable polymers, and mixtures thereof, based on the total weight of the container or lid.

24. The article of claim 23, wherein the filler is calcium carbonate.

25. The article of any one of claims 1,4, and 7, wherein the container, lid, label, or mixture thereof comprises a single layer or multiple layers.

26. The article of claim 25, wherein the multilayer is a bilayer, a trilayer, a quadruple layer or a quintuple layer.

27. The article of claim 26, wherein the bi-layer has a weight ratio of the outer layer to the inner layer of from 99:1 to 1: 99.

28. The article of claim 27, wherein the ratio of the outer layer to the inner layer is from 10:90 to 30: 70.

29. The article of claim 26, wherein the three layers have a weight ratio of outer layer to intermediate layer to inner layer of 20:60: 20.

30. The article of claim 26, wherein the intermediate layer comprises a biodegradable polymer.

31. The article of claim 30, wherein the biodegradable polymer is selected from the group consisting of polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), aliphatic-aromatic copolyesters based on terephthalic acid, aromatic copolyesters with high terephthalic acid content, Polyhydroxyalkanoates (PHA), thermoplastic starch (TPS), cellulose, and mixtures thereof.

32. The article of claim 25, wherein the multilayer comprises a barrier layer.

33. The article of any one of claims 1,4, and 7, wherein the cover satisfies at least one of the following convenience properties:

(i) withstand being opened at least 150 times by a person or at least 1500 times by a machine;

(ii) bearing a load of 4.5 kg at 50 ℃ for 15 days; and

(iii) subject to side panel drops, horizontal drops and inverted drops from a height of at least 1.2m, and vertical bottoms from a height of at least 1.5 m.

34. The article of any one of claims 1,4, and 7, wherein the polymer comprising the cap satisfies at least one of the following convenience properties:

(i) exhibits a modulus decrease of less than 1% when soaked in water according to ASTM D-638; and

(ii) exhibits a Vicat softening point according to ISO306 method A50 of at least 75 ℃; or a Vicat softening point of at least 50 ℃ according to ISO306 method B50.

35. The article of any one of claims 1,4 and 7, wherein the label meets at least one of the following convenience properties:

(i) shows no change after immersing the article in a 38 ℃ water bath for one hour and pressing the article 100 times;

(ii) shows no change after dropping the product on it at 20 to 24 ℃ and then wiping off the product after 24 hours; and

(iii) exhibiting less than 2% shrinkage 24 hours after its manufacture.