BR112019013252A2 - carbohydrate-based polymeric materials - Google Patents

Abstract

these are articles that include carbohydrate-based polymeric materials and methods for forming such articles. such articles may exhibit enhanced sustainability, biodegradability, increased resistivity and / or several other beneficial characteristics. the carbohydrate-based polymeric material can be formed from one or more starches, a plasticizer (for example, glycerin) and water. the carbohydrate-based polymeric material can exhibit very low crystallinity characteristics, so as to be substantially amorphous (for example, with a crystallinity of at most 20%, at most 10%, less than 10% etc.). carbohydrate-based polymeric materials can be mixed with non-biodegradable plastics to make these plastic materials now biodegradable, can provide increased resistivity to the film or other article, can be mixed with a non-sustainable polymeric material (eg biope or similar) to increased sustainability (for example, as much as 90% or more) or similar.

Description

Invention Patent Descriptive Report for “CARBOHYDRATE POLYMERIC MATERIALS”.

[0001] This application claims the benefit of Application No. ² US 15 / 481,806 (21132.1) filed on April 7, 2017; US Order No. ² / 481,823 (21132.2) filed on April 7, 2017; Order No. ² US 15 / 691,588 (21132.7) filed on August 30, 2017; US Order No. ² / 836,555 (21132.4.1) filed on December 8, 2017; ² of US Application No. 62 / 610,615 (21132.9) filed on December 27 , 2017; US Order No. ² 62 / 610,618 (21132.12) filed on December 27, 2017; of US Application No. ² 62 / 440,399 (21132.10) filed on December 29, 2016 and US Application No. ² 62 / 442,432 (21132.11) filed on January 4, 2017 and US Application No. ² of 62 / 483,219 (21132.4 ), filed on April 7, 2017. The content of each of the aforementioned requests is incorporated into this document for reference in its entirety.

[0002] The contents of each of Order No. ² US 14 / 853,725 deposited on September 14, 2015 (21132.6); US Order No. ² / 853,780 filed on September 14, 2015 (21132.8); and Provisional Patent Application No. ² US 62 / 187,231 filed on June 30, 2015 is also incorporated in this document for reference in its entirety.

BACKGROUND [0003] Traditional plastics based on a petrochemical product are formulated to be strong, light and durable. However, these plastics are typically not biodegradable and, as a result, hundreds of millions of tons of plastics are left without landfills or floated in the ocean. In an attempt to reduce the amount of plastic waste, some articles typically produced using plastics based on petrochemicals are produced using biodegradable materials.

[0004] Plastics based on petrochemical product materials, such as large quantities of polyethylene and polypropylene, as well as numerous

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2/122 other plastics (polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, polycarbonate, nylon and the like) are typically not readily biodegradable. This is typically the case even for then called "ecological plastics" of such materials, which may come from sustainable or renewable sources, and not from petrochemical raw materials [0005] Although more recently there have been efforts to take such plastic materials more and more more degradable by adding UV and / or OXO additives (for example, such as PDQ-M, PDQ-H, BDA and OxoTerra ™ by Willow Ridge Plastics, 0X1014 by LifeLine, or organic additives (for example, such as Restore® from Enso, EcoPure® from Bio-Tec Environmental, ECM Masterbatch Pellets 1M from ECM Biofilms or BioSphere®), the use of such additives is generally frowned upon by industry associations (eg SPC, APR, FPA, and / or BPI) , once uqe or biodegradable and the rate of biodegradation is very very slow, and OXO additives usually simply initiate structural fragmentation or degradation that accelerates the physical deterioration of such plastic materials into small pieces of the underlying plastic material, instead of the actual desired conversion of the plastic back to natural materials such as carbon dioxide (CO2), water (H2O) and methane (CH4).

[0006] For example, such materials act simply to accelerate the breakdown of the macrostructure of the plastic article itself due to exposure to UV light (from exposure to the sun) and / or exposure to oxygen. Such special plastics may not degrade to any degree within a certain period of time (for example, 5 years, 3, years or 1 year), but they simply lose resistivity, crack and break into small pieces. The result is a pile or small pieces of polyethylene or other basic plastic material that results as a bottle, film or other article physically degrades with time due to the addition of UV and / or OXO additives, however the weight fraction of the polyethylene or other basic plastic material remains substantially the same, without actual biodegradation actually occurring. Degradation is

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3/122 simply physical, as the article becomes brittle, cracks and breaks into small pieces, leaving small fragments of polyethylene or other basic plastic material. The application of the term “biodegradable” to such plastic materials is sometimes a monomer, since the complete biodegradation of the material polymer, by itself, may not actually occur (for example, when substantial fractions of the plastic degrade in CO2 , CH4, H2O and the like).

[0007] Furthermore, most plastics used today are not formed from renewable or sustainable resources (for example, starting materials that can be renewed in approximately 100 years or less). The terms renewable and sustainable are used interchangeably in this document. Preferably, polyethylene (PE), polyethylene terephthalate (PET) and other typical plastics used in large quantities in bottles, bags and other packaging are produced from petroleum starting materials, which are not renewable or sustainable.

[0008] In an effort to increase sustainability, recently, there have been some efforts to develop processes to produce such plastic materials from materials from renewable sources, such as sugarcane, corn or other plant products, the materials being vegetables are sustainable. For example, such renewable materials can be used to produce ethanol, ethylene glycol or other chemical building block materials other than those that can be further reacted to produce monomers that can be polymerized. Such efforts have started to show some promise in special priced products in which such ecological plastic resins ”can be mixed with conventional resins based on petrochemicals (for example, to produce a bottle or other packaging in which a fraction (for example , 30%) of the materials is sustainable, in fact, some products can now be produced from 100% “ecological” plastic resins.

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4/122 [0009] Although blends of such “ecological materials” and conventional petrochemical plastics have started to become available, there are still practical difficulties in replacing the remaining conventional petrochemical plastic materials with all sustainable materials, in terms of processing challenges, cost and other considerations.

[0010] In addition, while reducing the use of conventional unsustainable plastic materials by replacing part of the material with sustainable plastic materials, the resulting plastic packaging is not biodegradable. For example, even a plastic packaging made from 100% environmentally friendly plastic or that includes a fraction of environmentally friendly PE or “environmentally friendly” PET is not biodegradable. This lack of biodegradability presents a huge ongoing problem. It would be a significant advance in the technique if biodegradable articles could be supplied. Increased resistivity is also desirable. It would be an additional step if such an article were formed entirely (or almost entirely) from sustainable materials.

[0011] In addition, recent efforts have been made to reduce the use of such plastic materials based on non-renewable petrochemical product. Some of these efforts have attempted to supply resins to produce plastic materials from renewable sources, such as sugarcane or other plant products. Although to a certain extent, such plastics from renewable sources are much more expensive to produce than their non-renewable petrochemical product equivalents.

[0012] In addition, plastic materials have particular characteristics of resistivity associated with them, depending on the particular material used in the formation of the plastic film or other material and on the physical characteristics of the film or other article by itself. For example, during the formation of a plastic film, the use of plastic resin material based on non-renewable petrochemical product can be reduced by forming a thinner film, however such reductions in the use of the material result in a weaker film .

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5/122 [0013] For example, although the document No ² of WO 2014/0190395 describes Leufgens film formation of a blend of polyethylene and a thermoplastic starch (particularly Cardia BL-F), such films are weaker than comparable films formed from polyethylene only and, due to the difficulties in processing blends that include conventional thermoplastic starches, the films produced in it are necessarily very thick (for example, 0.076 mm (3 mils)). Such very thick films can result in no real reduction in the use of plastic resin material based on petrochemical product, due to the fact that the formation of thin film is impossible in practical terms and / or because the inclusion of such thermoplastic starches weakens the general film, so that a space film is necessary to maintain a desired level of resistivity.

[0014] It is advantageous to provide films and associated manufacturing methods that can increase the resistivity for a film of any thickness, for example, by adjusting the manufacturing parameters used during manufacturing, when using a plastic material from a source renewable These methods allow a film to be produced at a certain thickness with increased resistivity or to produce the film with a smaller thickness, but with the same resistivity. Such methods at the same time would result in real reductions in the amount of plastic petrochemical material used, since a portion of them is replaced by a plastic material from a sustainable renewable source the overall thickness does not need to be increased.

[0015] Furthermore, although the replacement of a portion of the material with petrochemical starch or a starch-based material has shown some promise with regard to increased sustainability, a problem with the addition of such starch or starch-based materials the fact that the inclusion of a significant fraction of starch or a starch-based material in the plastic composition can result in a notable odor associated with the inclusion of such an article formed from a mixture. For example, the material can

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6/122 assume a slightly burnt starch odor, a popcorn odor or a caramelized corn-like odor. Although the odor may be pleasant, or even desirable, there is a preference for the presence of no odor, as would be the case for a plastic formed without the starch or starch-based material present (for example, formed from polyethylene or other polymeric resin, alone).

[0016] In light of the aforementioned, numerous problems remain to be addressed in the technique.

SUMMARY [0017] The present disclosure refers to several concepts that can be implemented in the manufacture of the article and / or manufacturing methods. In one embodiment, the disclosure refers to articles that exhibit increased resistivity and / or biodegradability. In some cases, articles may be produced from a mixture of one or more polymeric materials (for example, synthetic, for example, based on petrochemicals or other products) and one or more carbohydrate-based polymeric materials that have characteristics particulars of low crystallinity (i.e., are substantially amorphous), glass transition temperature, heat deflection temperature, vicat softening temperature or the like. In a particular example, the one or more carbohydrate-based polymeric materials may include one or more starch-based polymeric materials. For example, the carbohydrate-based polymeric material can be substantially amorphous, with a maximum crystallinity of 20%, it can have a Young's modulus of at least 1.0 GPa and / or it can have a transition temperature vitreous or heat deflection or vicat softening temperature from 70 ° C to 100 ° C. Other characteristics of carbohydrate-based materials will be described further in this document.

[0018] A process for producing an article may include providing one or more polymeric materials and one or more substantially amorphous carbohydrate-based polymeric materials. The one or more polymeric materials and the

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7/122 one or more carbohydrate-based polymeric materials can be mixed and heated. The resulting mixture can be extruded into a number of plastic products using plastic processing equipment, such as injection molders, blow molders, thermoformers, etc. A gas can be injected into the extruded mixture to form a film. Such films can be processed in a bag or other type of article. Other articles may be extruded plastic products, injection molded plastic products, blow molded plastic products, extruded or molten sheet or films, thermoformed plastic products and the like.

[0019] Articles may exhibit increased resistivity and / or biodegradability. For example, in one embodiment, mixing the substantially amorphous carbohydrate-based polymeric material with the other polymeric material provides biodegradability to the other polymeric material, even when the other polymeric material itself was not biodegradable on its own. For example, polyethylene is notoriously known as not being biodegradable on its own. The applicant has demonstrated the ability to provide biodegradability to plastic materials, such as polyethylene, the materials being non-biodegradable. Other examples of this may include, but are not limited to, polypropylene, other polyolefins, polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, nylon and polycarbonate. As an example, the quantity of the article that biodegrades in 5 years or in another determined period of time under simulated disposal conditions (for example, simulated landfill conditions) may be greater than an amount of the included carbohydrate-based polymeric material in the article. Such simulated disposal conditions may include simulated landfill conditions (for example, under any typical ASTM standard, such as, but without limitation D-5511 and / or D-5526), simulated industrial composite conditions (such as, ASTM D -5338) or simulated underwater conditions (such as ASTM D-6691). In other words, part of the otherwise non-biodegradable polymeric material now, somehow, if

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8/122 biodegraded, as well as the biodegradation of the carbohydrate-based material. For example, if the article is formed from a blend that includes 25% of the carbohydrate-based polymeric material, the amount of the article that biodegrades under such conditions is greater than 25% (that is, part of the other polymeric material also degrades , although such polymeric material may not degrade under similar conditions on its own).

[0020] Third party test results obtained by the Applicant show that such degradation can occur relatively quickly, for example, some in approximately 180 days (6 months), in approximately 1 year, in approximately 2 years or in approximately 3 years and not in 5 years. [0021] In addition to or alternatively to biodegradability, articles and methods may provide increased resistivity (for example, an increase in dart impact resistance or another resistivity characteristic of at least 5%) compared to the resistivity that the article would have if it were produced only from the other polymeric material, without the carbohydrate-based polymeric material.

[0022] Another aspect of the present disclosure refers to articles that are formed with renewable or sustainable ecological plastic materials and polymeric materials based on carbohydrate (for example, based on starch). For example, in one embodiment, the other polymeric material can also be a sustainable ecological polymeric material from sustainable sources (for example, plants, such as sugar cane, corn or the like). In one embodiment, the non-sustainable polymeric material can be processed into a polymer that otherwise exhibits similar if not identical characteristics to a polymer based on petrochemical products (for example, it can be ecological polyethylene, ecological polypropylene, polyethylene terephthalate (PET) or similar). Such an ecological polymer ”can have similar if not identical chemical and physical properties in comparison to the same polymer (for example, polyethylene) formed from petrochemical raw material. Polymeric material based on

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9/122 carbohydrate may provide biodegradable characteristics to the unsustainable polymeric material with which it is mixed or otherwise formed, and such unsustainable polymeric material may otherwise not exhibit such biodegradable characteristics (or such characteristics may be intensified, if the non-sustainable polymeric material has already exhibited some biodegradability).

[0023] In addition to or alternatively to biodegradability, such articles may exhibit increased resistivity compared to articles similarly similar, but formed in the inclusion of carbohydrate-based polymeric material. For example, a modality refers to an article that includes one or more carbohydrate-based polymeric materials (for example, such as those described above), and one or more sustainable polymeric materials from a sustainable plant source, where a resistivity of the the article is at least 5% greater than the resistivity that the article would have if it were produced without the carbohydrate-based polymeric material. For example, the Applicant has found that the inclusion of such a carbohydrate-based polymeric material in the article (for example, as a mixture of the two polymeric materials) can provide increased resistivity, compared to what the unsustainable polymeric material alone would provide.

[0024] Another aspect of the present disclosure relates to methods for manipulating blowing ratios and / or matrix gaps used during filmmaking to increase resistivity of films produced from such mixtures of a polymeric material based on carbohydrate and another polymeric . In particular, the Applicant found that although the resistivity of most blown plastic films of various resin materials (for example, such as polyethylene and / or polypropylene) is not affected by changes in the blowing ratio, when polymeric materials based on renewable carbohydrates (for example, based on starch) that have particular amorphous characteristics, particular glass transition temperature characteristics, vicat softening temperature characteristics or

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10/122 heat deflection and / or particular characteristics of modulus of elasticity, as described in this document, are included in the blend of resin from which the film is blown, this resistivity, in fact, depends on the blowing ratio and / or span matrix and it is possible to blow extremely narrow gauge films. The Applicant did in fact blow films of thickness 0.0025 mm (0.1 mil) which has significant resistivity, and it is not believed that such a thin film blow was previously possible with any known resins or production methods.

[0025] The blowing ratio refers to the maximum diameter of the blown film divided by the diameter of the matrix of the film blowing apparatus. Typically, there is some increase in diameter as the molten resin material leaves the matrix and begins to travel upward through the “freezing line” towards the blown film bubble portion where the resin material is no longer melted, because it solidified. Solidification and crystallization typically occur in the freezing line, which is the location where opacity or a “frozen appearance” begins to be visible in the bubble blown film. The Applicant noted that during the use of such particular renewable carbohydrate-based polymeric materials, as described in this document, an increase in resistivity is obtainable, in addition to the resistivity achieved during the blowing of an otherwise similar plastic film (but without the polymeric material based on carbohydrates). Such an increase is obtained by selecting a high blowing ratio and / or a narrow die span. It is believed that this results in the alignment, orientation and / or stretching of the molecular structures of the carbohydrate-based polymeric material, which is homogeneously distributed throughout the mixture of resin from which the film is formed. Such alignment and orientation of the amorphous renewable carbohydrate-based polymeric material within the film is believed to be at least partly responsible for the observed increase in resistivity.

[0026] In other words, as described in this document,

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11/122 the particular renewable carbohydrate-based polymeric materials can be used in combination with the processing conditions described to enhance the resistivity of a given film, not to mention the sustainability benefits associated with replacing a portion of the other polymeric content of the film with renewable carbohydrate-based polymeric material.

[0027] In particular, typical films are blown at a blowing rate of about 1.5. The Applicant has found that by increasing the blowing ratio to at least 2.0, for example, from 2.2 to 2.8 (for example, about 2.5), when a polymeric material based on renewable carbohydrate, such as NuPlastiQ or Ecological Starch Resin “ESR”, available from the Applicant, is included in the resin blend from which the film is formed, there is a significant increase in the resistivity of the film at the higher blowing ratios. For example, a mixture of NuPlastiQ or ESR and a typical polymeric resin (for example, polyethylene and / or polypropylene) can exhibit resistivity characteristics at a blowing ratio of 1.5 that are substantially equal to the resistivity of a film that is, otherwise identical, but in fact, not to include NuPlastiQ or ESR.

[0028] Such a film (without NuPlastiQ or ESR) does not exhibit any significant increase in resistivity when the blowing ratio is increased and therefore there is no reason to manipulate this value during the blowing of such films. The Applicant has found that when NuPlastiQ or ESR is included in the resin blend, the resistivity is significantly increased when using a blowing ratio (for example, at least 2.0), as noted above.

[0029] In addition, NuPlastiQ or ESR does not suffer from many of the problems of alternative thermoplastic starch materials, which inhibits their use in forming relatively thin films (eg 0.051 mm (2 mil) or less, typically 0.038 mm (1.5 mil) or less, such as 0.003 mm (0.1 mil) to 0.038 mm (1.5 mil)). Such a combination of findings allowed the Applicant to form films with a certain thickness, which exhibited a

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12/122 increased resistivity compared to films formed from the same material, but without i NuPlastiQ or ESR (or compatibilizer - that is, formed from the other polymeric material, alone, such as polyethylene). Such finding also allows the production of films with the same resistivity, but with less thickness, when using NuPlastiQ or ESR in the mixture. Such results are surprising and advantageous, which allows the production of films that include a significant fraction of a renewable resin, while at the same time increasing the resistivity. This is achieved by manipulating the blowing ratio and / or the matrix span. In addition, applicants have found that increased resistivity is also possible by ensuring that a matrix gap used in the film blowing apparatus is relatively narrow. Again, narrow array spans are not practical in practical terms with many conventional thermoplastic starch blends, as evidenced by Leufgens (where the array span used was 1.6 to 1.8 mm). The present invention can employ matrix spans of 1,000 microns or less, more typically 500 microns or less. In this way, the blowing ratio and / or die span can be used according to the present methods to provide increased film resistivity.

[0030] As an example, a modality may refer to a method for providing increased resistivity to a blown plastic film, the method comprising blowing a plastic film with the use of a film blowing device, the film being it is blown from a mixture that includes a first polymeric material (for example, polyethylene, another polyolefin or another conventional polymeric material) and a renewable carbohydrate-based polymeric material. The renewable carbohydrate-based polymeric material may be substantially amorphous, with a crystallinity of at most 20%, may have a Young's modulus of at least 1.0 GPa and / or may have a glass transition temperature, vicat softening or heat deflection temperature from 70 ° C to 100 ° C. The film blowing apparatus can operate at a high blowing rate and / or narrow die span, for example, a ratio

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13/122 blowing of at least 2.0 during the blowing of the plastic film or the matrix gap can have a maximum of 500 microns. The high blowing ratio and / or narrow die span can provide the blown plastic film with increased resistivity (for example, compared to everything being equal, but at a lower blowing ratio and / or higher die span).

[0031] Another modality can refer to a method to increase the resistivity of a blown plastic film by manipulating the blowing ratio, the method comprising blowing a plastic film with the use of a film blowing device, being that the film is blown from a blend that includes a first polymeric material and a second polymeric material that comprises a renewable carbohydrate-based polymeric material. The renewable carbohydrate-based polymeric material can be substantially amorphous, which has a maximum crystallinity of 20%, can have a Young's modulus of at least 1 GPa, and can have a glass transition temperature, softening temperature vicat or heat deflection temperature from 70 ° C to 100 ° C. The method may additionally include manipulating (i.e., specifically selecting) a blowing ratio of the film blowing apparatus in order to select a high blowing ratio of at least 2.0 in order to increase the resistivity of the film (e.g. compared to everything being equal, but at a lower blowing rate). In addition or alternatively to the manipulation of the blowing ratio, methods may include manipulating (that is, selecting specifically) a matrix span of the film blowing apparatus in order to select a narrow matrix span of a maximum of 500 microns, of so that the narrow die span and / or high blowing ratio increase the resistivity of the film (for example, in comparison everything is the same, but in a larger die span and / or at a lower blowing ratio).

[0032] Another aspect of the present disclosure relates to methods for reducing a characteristic odor attributable to the inclusion of a starch-based polymeric material or other carbohydrate-based polymeric material, as well as

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14/122 articles that include reduced odor. The carbohydrate-based polymeric material described in this document, as well as other similar carbohydrate-based polymeric materials, exhibit a characteristic odor such as starch, popcorn, caramel or lightly burnt corn. Although not typically exaggerated, this odor is typically noticeable in some articles formed from mixtures of materials including the carbohydrate-based polymeric material, particularly, where the geometry of the finished article may be relatively “closed” (for example, as in a glass), or other confined structure where one is limited by the plastic material on two, three or more sides. Such a characteristic odor can tend to accumulate within a confined volume, so that it becomes noticeable to a consumer or other use (for example, if a user put their nose in such a glass and sniffed).

[0033] The Claimant wishes to remove or minimize such a characteristic odor, so that the odor is similar or identical to the odor (typically, odorless) that would be present if the article were instead formed from a standard polymeric material (for example, example, based on petrochemical product). For example, articles according to the present invention can be formed from a mixture of that standard "other polymeric material" and the carbohydrate-based polymeric material, as described above and throughout this document. The Applicant has found that the characteristic odor can be substantially removed or minimized by adding a very small fraction of an odor reducing agent, particularly an organic odor reducing agent.

[0034] Although some attempts may have been made previously by others to reduce the odor resulting from a dry grain material (DDG) from distillers, for example, as described in document No. ² W02009058426, such treatment required the addition of relatively high fractions of activated carbon or steam-activated anthracite materials. Although it may be effective to some extent, the concentration of such materials required is high, and the cost of such materials is prohibitive, so that commercial application

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15/122 of such modalities are not particularly viable. In addition, the addition of high fractions of dark colored materials of activated anthracite or activated carbon may be undesirable, given their tendency to act as a pigment under certain conditions, coloring the plastic material. This can be particularly problematic when you want a very clear film, light-colored article, or other similar article.

[0035] Thus, one embodiment of the present invention relates to a sustainable plastic material that includes the carbohydrate-based polymeric material, another polymeric material, as described above, but which also includes an odor reducing agent. In the absence of the odor reducing agent, the polymeric carbohydrate material provides a characteristic odor of burnt carbohydrate to the sustainable plastic material. In one embodiment, the odor reducing agent may be organic and comprise an aromatic compound (for example, including a benzene ring), such as a benzaldehyde compound, a benzyl ketone compound or another benzene derivative. In one embodiment, the organic odor reducing agent may comprise a lyophilized extract or other extract from a fruit or vegetable, such as vanillin. The organic odor reducing agent may, in fact, be extruded from such a fruit, vegetable or other plant or may comprise an aromatic compound typically found in such an extract, but which has been produced synthetically (for example, synthetic vanillin or another aromatic compound may be appropriate). Vanillin is an aromatic benzaldehyde compound also known as 4-hydroxy-3-methoxybenzaldehyde.

[0036] The Applicant has surprisingly found that very small fractions of such an aromatic odor-reducing agent are sufficient to remove substantially any characteristic odor otherwise attributable to the carbohydrate-based polymeric material included in the blend that forms the sustainable plastic material. For example, the weight ratio between an odor reducing agent and the carbohydrate-based polymeric material to substantially remove the odor is on the order of 1: 1000 or less of the reducing agent

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16/122 of odor. For example, as much as 100 ppm, 50 ppm, or even 20 ppm or less, is sufficient to remove any practical sign of the characteristic odor. [0037] This is particularly surprising, since so little of the odor reducing agent is needed to remove the odor. Due to the fact that so little is needed, and the odor typically appears not to have been replaced or disguised by any odor provided by the odor reducing agent, it is believed that the mechanism at work may not be a simple disguise of the characteristic carbohydrate odor . Although any of these mechanisms may not be fully understood, it is possible that there is a chemical interaction between such aromatic agents or other organic odor reducing agents and the characteristic odor compounds generated by heating the carbohydrate-based polymeric material during melting and formation of the thermoplastic mixture in the desired article.

[0038] The odor-reducing agent can be included as a carbohydrate-based polymeric material, for example, in a main batch thereof. Thus, one modality can refer to such a sustainable thermoplastic carbohydrate-based polymeric material that exhibits reduced odor that includes the organic odor reducing agent pre-mixed with the carbohydrate-based polymeric material. A weight ratio between the organic odor reducing agent and the carbohydrate-based polymeric material can be a maximum of 1: 1,000 (that is, at least 1,000 times more than the carbohydrate-based polymeric material compared to the amount odor reducing agent). In one embodiment, the ratio of the odor reducing agent to the carbohydrate-based polymeric material can be much more dilute, for example, such as 1: 50,000.

[0039] It will be apparent that the present disclosure also encompasses related methods, for example, methods to reduce a characteristic odor of a mixture of material that includes a carbohydrate-based polymeric material, for example, including a small fraction of an agent organic odor reducer inside the blend. When the carbohydrate-based polymeric material is supplied as a main batch, the

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17/122 odor can be supplied inside the main batch, already mixed with the polymeric material based on carbohydrate. Thus, when the main batch is then mixed with a polymeric resin material (for example, any of the numerous plastic resins, such as PE, PP, other polyolefins, polyesters, polystyrenes, PBAT, polycarbonate or others), the mixed material also then includes the odor reducing agent mixed in it.

SUMMARY OF EXEMPLIFICATIVE CONCEPTS TO BE CLAIMED [0040] 1. An article comprising: one or more substantially amorphous carbohydrate-based polymeric materials (for example, starch-based polymeric materials) that have a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, heat deflection temperature, vicat softening temperature, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR; and one or more polymeric materials based on polyolefin; the article having a dart drop impact value of at least about 140g per thousand (0.0254 mm) thickness.

[0041] 2. The article of claim 1, wherein the one or more starch-based polymeric materials are formed from one or more starches and one or more plasticizers.

[0042] 3. The article of claim 2, wherein the one or more starches comprise one or more of potato starch, corn starch, tapioca starch and the plasticizer comprises glycerin.

[0043] 4. The article of claim 1, wherein the one or more polymeric materials based on polyolefin comprises a polyethylene.

[0044] 5. The article of claim 1, the article being a pouch having a thickness of about 0.01 mm to about 0.1 mm and the pouch includes a cavity having a volume of about 1 I at about 100 I.

[0045] 6. The article of claim 1, wherein: the one or more polymeric starch-based materials comprise about 20% by weight at about

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40% by weight of the article; the one or more polymeric materials based on polyolefin comprise about 60% by weight to 80% by weight of the article; the article has a thickness of about 0.02 mm to about 0.051 mm; and the article has a dart drop impact value of about 265 g to about 330 g per thousand (0.0254mm) in thickness.

[0046] 7. The article of claim 1, which further comprises a compatibilizer present in an amount of at most 8% by weight of the article.

[0047] 8. An article comprising: a substantially amorphous polymer-based polymeric material (for example, starch-based polymeric materials) which has a crystallinity of less than 20%, less than 10%, a particular glass transition temperature , vicat softening temperature or heat deflection temperature, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR, formed from a mixture of starches that include a first quantity of a first starch and a second quantity a second starch; and a polyolefin-based polymeric material; the article having a dart drop impact value that is greater than: (i) a first dart drop impact value of a first article that includes the polyolefin-based polymer material and a first polymer-based material of starch formed from a single starch consisting of the first starch and (ii) a second dart drop impact value of a second article which includes the polyolefin-based polymeric material and a second formed starch-based polymeric material from a single starch consisting of the second starch.

[0048] 9. The article of claim 8, wherein the polymeric starch-based material is formed from one or more plasticizers.

[0049] 10. The article of claim 8, wherein the first starch comprises or is derived from one of potato starch, corn starch or tapioca starch; and the second starch comprises or is derived from a starch other than potato starch, corn starch or tapioca starch.

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19/122 [0050] 11.0 The article of claim 8, wherein the polymeric starch-based material is present in an amount of about 20% by weight to about 30% by weight of the article and the polyolefin-based polymeric material it is present in an amount of about 65% by weight to about 75% by weight of the article.

[0051] 12. The article of claim 11, wherein the first starch comprises from about 10% by weight to about 50% by weight of the mixture of starches from which the polymeric starch-based material is formed, and the second starch comprises from about 50% to 90% of the mixture of starches from which the polymeric starch-based material is formed.

[0052] 13. The article of claim 12, wherein: the mixture of starches from which the polymeric starch-based material is formed includes a third starch; the third starch comprises from about 10% by weight to about 35% by weight of the mixture of starches from which the polymeric starch-based material is formed; and the dart drop impact value of the article is greater than a third dart drop impact value of a third article that includes the polyolefin-based polymeric material and a third starch-based polymeric material formed from a second starch which consists of the third starch.

[0053] 14. The article of claim 8, wherein the article has a stretching stress value in the machine direction that is greater than a stretching stress value in the machine direction of an additional article formed at from the polyolefin-based polymeric material which is free from starch-based polymeric materials.

[0054] 15. The article of claim 9, which further comprises a compatibilizer present in an amount of at most 8% by weight of the article.

[0055] 16. A process that comprises: supplying one or more polymeric materials based on petrochemical product; supply one or more substantially amorphous carbohydrate-based polymeric materials (eg

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20/122 (starch-based polymeric materials) which has a crystallinity of less than 20%, less than 10%, the particular glass transition temperature, vicat softening temperature or heat deflection temperature, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR; mixing the one or more polymeric materials based on petrochemical product and the one or more polymeric materials based on carbohydrate to produce a mixture of materials; heating the material mixture to a temperature in the range of about 120 ° C to about 180 ° C; and produce a film using the mix of materials, the film having a dart drop impact value of about 250 g to about 350 g per thousand (0.0254mm) thick.

[0056] 17. The process of claim 16, wherein the production of the film using the mixture of materials includes: extruding the mixture of materials to produce an extruded object; and inject a gas into the extruded object.

[0057] 18. The process of claim 16, wherein: the one or more carbohydrate-based polymeric materials are formed from a first starch and a second starch; and the film has a dart drop impact value that is greater than: (i) a first dart drop impact value of a first article that includes one or more petrochemical-based polymeric materials and a first material polymer-based carbohydrate formed from a single starch consisting of the first starch and (ii) a second dart drop impact value from a second article that includes the one or more petrochemical product-based polymeric materials and a second carbohydrate-based polymeric material formed from a single starch consisting of the second starch.

[0058] 19. The process of claim 16 wherein: the mixing of materials further comprises one or more compatibilizers; and the mixture of materials includes: from about 10% by weight to about 40% by weight of the one or more carbohydrate-based polymeric materials, from about 60% by weight to about 89% by weight of the one or more polymer based materials

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21/122 of petrochemical product; and from about 1% by weight to a maximum of 8% by weight of the one or more compatibilizers.

[0059] 20. The process of claim 16, the article including a film having a thickness of about 0.02 mm to about 0.051 mm.

[0060] 1. An article comprising:

[0061] polymeric content comprising:

[0062] a substantially amorphous carbohydrate-based polymeric material (e.g., starch-based polymeric material) that has a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, vicat softening temperature or temperature heat deflection, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR, formed from at least one first starch; and [0063] another polymeric material;

[0064] in which an amount of polymeric content that biodegrades after 91 days is greater than an amount of starch-based polymeric material based on the results of a potential biomethane test conducted at a temperature of about 52 ° C with use of an inoculum that has about 55% water by weight and about 45% by weight organic solids.

[0065] 2. The article of claim 1, in which substantially all polymeric material based on starch biodegrades after 91 days, as measured according to the potential biomethane test conducted at a temperature of about 52 ° C using of an inoculum that has about 55% water by weight and about 45% by weight organic solids.

[0066] 3. The article of claim 1, wherein the article further comprises a biodegradation enhancing additive present in an amount of about 0.5% by weight to about 2.5% by weight.

[0067] 4. The article of claim 1, the article being substantially free of a biodegradation enhancing additive.

[0068] 5. The article of claim 4, the article having a

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22/122 amount of biodegradation of the article after 91 days which is about 5% to about 60% greater than an amount of the starch-based polymeric material based on the results of the potential biomethane test conducted at a temperature of about 52 ° C using an inoculum that has about 55% water by weight and about 45% by weight organic solids.

[0069] 6. The article of claim 1, wherein the polymeric starch-based material is formed from materials including one or more plasticizers.

[0070] 7. The article of claim 1, wherein the polymeric starch-based material is formed from the first starch and a second starch, the first starch comprising or derived from one of potato starch, starch corn or tapioca starch; and the second starch comprises or is derived from a starch among potato starch, corn starch or tapioca starch.

[0071] 8. The article of claim 7, wherein a first amount of the first starch comprises from about 10% by weight to about 50% by weight of a mixture of starches from which the polymeric starch-based material is formed, and a second amount of the second starch comprises from about 50% by weight to about 90% by weight of a mixture of starches from which the polymeric starch-based material is formed.

[0072] 9. The article of claim 1 which further comprises a compatibilizer present in an amount of up to 8% by weight of the article. [0073] 10. An article comprising:

[0074] polymeric content comprising:

[0075] one or more substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) that have a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, vicat softening temperature or heat deflection temperature, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR, formed at

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12/23 from one or more carbohydrates; and [0076] one or more polymeric materials based on petrochemical product;

[0077] in an amount of the polymeric content that biodegrades after 91 days is greater than an amount of one or more carbohydrate-based polymeric materials based on the results of a potential biomethane test conducted at a temperature of about 40 ° C at about 50 ° C and using an inoculum that has from about 50% by weight water to about 60% by weight water and from about 40% by weight of organic solids to about 50% by weight of solids organic.

[0078] 11.0 The article of claim 10 wherein the article comprises from about 20% by weight to about 40% by weight of the one or more carbohydrate-based polymeric materials and from about 65% by weight to about 85% by weight of one or more polymeric materials based on petrochemical product. [0079] 12. The article of claim 11 wherein the amount of the polymeric content that biodegrades after 91 days is from about 30% to about 50% based on the results of the potential biomethane test conducted at a temperature of about 52 ° C. ° C with the use of an inoculum that has about 55% by weight water and about 45% by weight of organic solids.

[0080] 13. The article of claim 10 wherein the amount of the polymeric content that biodegrades after 62 days is from about 25% to about 35% based on the results of the potential biomethane test conducted at a temperature of about 52 ° C with the use of an inoculum that has about 55% by weight water and about 45% by weight of organic solids.

[0081] 14. The article of claim 10 wherein the one or more petrochemical product-based polymeric materials include a first petrochemical product-based polymeric material and a second petrochemical product-based polymeric material, the second polymeric material based on petrochemical product it is compostable according to the ASTM D-6400 standard. [0082] 15. A process comprising:

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24/122 supply one or more polymeric materials based on petrochemical product; [0083] providing one or more substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) that have a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, softening temperature vicat or heat deflection temperature, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR, formed from one or more carbohydrates;

[0084] mixing the one or more polymeric materials based on petrochemical product and the one or more polymeric materials based on carbohydrate to produce a mixture of materials;

[0085] heat the mixture of materials to a temperature included in a range of about 120 ° C to about 180 ° C;

[0086] produce a film using the mixture of materials, in which: [0087] the film includes polymer content comprised of one or more polymeric materials based on petrochemical product and one or more polymeric materials based on carbohydrate; and [0088] an amount of the polymeric content that biodegrades after 91 days is greater than an amount of the one or more carbohydrate-based polymeric materials based on the results of a potential biomethane test conducted at a temperature of about 52 ° C with the use of an inoculum that has about 55% water by weight and about 45% by weight organic solids. [0089] 16. The process of claim 15 in which:

[0090] o one or more carbohydrate-based polymeric materials are formed from a first starch and a second starch; and [0091] substantially all one or more polymeric materials based on biodegraded carbohydrate after 91 days based on the results of a potential biomethane test conducted at a temperature of about 52 ° C using an inoculum that has about 55 wt% water and about 45 wt% organic solids.

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25/122 [0092] 17. The process of claim 15 wherein the mixing of materials includes:

[0093] up to 8% by weight of one or more compatibilizers;

[0094] from about 10% by weight to about 40% by weight of the one or more carbohydrate-based polymeric materials; and [0095] from about 60% by weight to about 90% by weight of the one or more petrochemical product-based polymeric materials.

[0096] 18. The process of claim 15 which further comprises producing a film pouch.

[0097] 19. The process of claim 15 wherein the pouch has a thickness of about 0.02 mm to about 0.051 mm and the pouch includes a cavity that has a volume of about 5 I to about 20 I.

[0098] 20. The process of claim 15 wherein:

[0099] the material mixture is heated in a plurality of chambers of an extruder;

[00100] a first chamber of the extruder is defined at a first temperature; and [00101] a second chamber of the extruder is set at a second temperature that is different from the first temperature.

[00102] 21. An article comprising:

[00103] polymeric content comprising:

[00104] a substantially amorphous carbohydrate-based polymeric material (e.g., starch-based polymeric materials) which has a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, vicat softening temperature or temperature heat deflection, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR, formed from at least one first starch; and [00105] a synthetic polymeric material;

[00106] in which an amount of polymeric content that biodegrades after

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26/122 about 1 year under simulated landfill conditions, simulated compost conditions or simulated underwater conditions is greater than an amount of polymeric material based on starch.

[00107] 22. The article according to claim 21 wherein at least 25% of the synthetic polymeric material biodegrades in approximately 3 years.

[00108] 23. The article of claim 21, wherein the polymeric starch-based material is formed from the first starch and a second starch, the first starch comprising or derived from one of potato starch, starch corn or tapioca starch; and the second starch comprises or is derived from a starch among potato starch, corn starch or tapioca starch.

[00109] 24. The article of claim 23, wherein a first amount of the first starch comprises from about 10% by weight to about 50% by weight of a mixture of starches from which the polymeric starch-based material is formed, and a second amount of the second starch comprises from about 50% by weight to about 90% by weight of a mixture of starches from which the polymeric starch-based material is formed.

[00110] 25. The article according to claim 21 which further comprises a compatibilizer.

[00111] 1. An article comprising:

[00112] a substantially amorphous carbohydrate-based polymeric material (e.g., starch-based polymeric materials) that has a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, vicat softening temperature or temperature heat deflection, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR configured to provide other materials of the article with biodegradability; and [00113] a non-sustainable polymeric material from a sustainable plant source;

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27/122 [00114] in which an amount of the article that biodegrades in 5 years under simulated landfill conditions is greater than an amount of the carbohydrate-based polymeric material.

[00115] 2.0 article according to 1 wherein the carbohydrate-based polymeric material comprises a starch-based polymeric material.

[00116] 3. The article according to 1, in which the non-sustainable polymeric material comprises one or more among polyethylene, polypropylene or polyethylene terephthalate formed from sustainable plant sources.

[00117] 4. The article according to 3, in which the non-sustainable polymeric material is formed from one or more among sugarcane or corn. [00118] 5.0 article according to 2, in which the polymeric material based on starch is formed from one or more starches comprising one or more among potato starch, corn starch or tapioca starch.

[00119] 6.0 article according to 5, in which the polymeric material based on starch is formed from two or more starches, the first starch comprising one or more of potato starch, corn starch or tapioca starch and a second starch comprising one or more of the potato starch, corn starch or tapioca starch.

[00120] 7. The article according to 6, in which:

[00121] an amount of the first starch comprises from about 50% to about 90% by weight relative to a combined weight of the first starch and the second starch and an amount of the second starch comprises from about 10% to about 50% % by weight with respect to a combined weight of the first starch and the second starch; and [00122] an amount of the carbohydrate-based polymeric material comprises from about 10% to about 40% by weight of a combined weight of the carbohydrate-based polymeric material and the unsustainable polymeric material, and an amount of the polymeric material unsustainable comprises from about 60% to about 90% by weight of the combined weight of the carbohydrate-based polymeric material and the non-polymeric material

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12/28 sustainable.

[00123] 8. The article according to 7, in which the resistivity of the article is at least about 5% higher than the resistivity that the article would have had it been produced only from the unsustainable polymeric material, without the polymeric material at carbohydrate base.

[00124] 9. The article according to 1, in which at least 90% of the polymeric content of the article comes from sustainable sources.

[00125] 10. The article according to 1, the article comprising a film.

[00126] 11.0 article according to 1, the article comprising at least one of a bottle or a leaf.

[00127] 12. An article comprising:

one or more substantially amorphous carbohydrate-based polymeric materials (for example, starch-based polymeric materials) which has a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, vicat softening temperature or heat deflection, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR configured to provide other materials of the article with biodegradability; and one or more sustainable polymeric materials from a sustainable plant source;

[00128] in which the resistivity of the article is at least about 5% higher than the resistivity that the article would have had it been produced only from the unsustainable polymeric material, without the carbohydrate-based polymeric material.

[00129] 13. The article according to 12, the article comprising a film and has a resistance to the impact of the fall of the dart of at least about 100 g per thousand (0.0254mm) of thickness.

[00130] 14. The article according to 12, in which the non-sustainable polymeric material comprises one or more among polyethylene, polypropylene or

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29/122 polyethylene terephthalate formed from sustainable plant sources.

[00131] 15.0 article according to 14, in which the unsustainable polymeric material is formed from one or more among sugarcane or corn. [00132] 16. The article according to 12 wherein the carbohydrate-based polymeric material comprises a starch-based polymeric material.

[00133] 17. The article according to 16, wherein the polymeric starch-based material is formed from one or more starches comprising one or more of potato starch, corn starch or tapioca starch.

[00134] 18. The article according to 17, in which the polymeric material based on starch is formed from two or more starches, the first starch comprising one or more of potato starch, corn starch or starch of tapioca and a second starch which comprises one or more other among potato starch, corn starch or tapioca starch.

[00135] 19. The article according to 18, in which:

[00136] an amount of the first starch comprises from about 50% to about 90% by weight with respect to a combined weight of the first starch and the second starch and an amount of the second starch comprises from about 10% to about 50% % by weight with respect to a combined weight of the first starch and the second starch; and [00137] an amount of the carbohydrate-based polymeric material comprises from about 10% to about 40% by weight of a combined weight of the carbohydrate-based polymeric material and the unsustainable polymeric material, and an amount of the polymeric material unsustainable comprises from about 60% to about 90% by weight of the combined weight of the carbohydrate-based polymeric material and the non-sustainable polymeric material.

[00138] 20. The article according to 12, in which the resistivity of the article is at least 10% greater than the resistivity that the article would have had it been produced only from the unsustainable polymeric material, without the polymeric material based on carbohydrate.

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30/122 [00139] 21. The article according to 12, in which at least 90% of the polymeric content of the article comes from sustainable sources.

[00140] 22. The article according to 12, the article comprising a film.

[00141] 23. The article according to 12, the article comprising at least one of a bottle or a leaf.

[00142] 1. A method for providing biodegradability to a plastic material that, by itself, is not biodegradable otherwise, the method comprising:

provide a plastic material that, on its own, is not biodegradable on its own;

[00143] providing one or more substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) that have a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, softening temperature vicat or heat deflection temperature, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR, the one or more carbohydrate-based polymeric material being selected for its ability to provide biodegradability to the plastic material that, by itself, it is not biodegradable on its own; and [00144] merge the carbohydrate-based polymeric material with the plastic material.

[00145] 2. The method of claim 1, wherein the one or more carbohydrate-based polymeric materials comprise one or more starch-based polymeric materials.

[00146] 3. The method of claim 2, wherein the one or more starch-based polymeric materials are formed from one or more starches and one or more plasticizers.

[00147] 4. The method of claim 3, wherein the one or more starches comprises one or more of potato starch, corn starch or starch.

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12/31 tapioca and the plasticizer comprises glycerin.

[00148] 5. The method of claim 3, characterized by the fact that the polymeric starch-based material is formed from a mixture of at least two different starches.

[00149] 6. The method of claim 5, wherein the two different starches from which the polymeric starch-based material is formed include (i) one of potato starch, corn starch or tapioca starch and (ii ) another among potato starch, corn starch or tapioca starch, where (ii) is selected to be different from (i).

[00150] 7. The method of claim 6, wherein the two different starches from which the polymeric starch-based material is formed are selected from one of the rows in the table below:

Starch 1 Starch 2 Potato Corn Potato Tapioca Corn Tapioca

[00151] 8. The method of claim 1, wherein the plastic material comprises a polyolefin.

[00152] 9. The method of claim 1, wherein the plastic material comprises polyethylene.

[00153] 10. The method of claim 9, wherein the plastic material comprises a polyethylene film, the film being formed from a mixture of the polymeric material based on carbohydrate and polyethylene.

[00154] 11.0 The method of claim 1, wherein the plastic material comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride or polycarbonate.

[00155] 12. The method of claim 1, wherein the mixture of 5% by weight or more among the carbohydrate-based polymeric material with the material

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32/122 plastic is enough to make the plastic material biodegradable.

[00156] 13. The method of claim 1, wherein mixing the carbohydrate-based polymeric material with the plastic material includes at least 5% by weight of the carbohydrate-based polymeric material.

[00157] 14. The method of claim 1, wherein mixing the carbohydrate-based polymeric material with the plastic material includes from 5% to 50% by weight of the carbohydrate-based polymeric material.

[00158] 15. The method of claim 1, wherein mixing the carbohydrate-based polymeric material with the plastic material includes from 10% to 50% by weight of the carbohydrate-based polymeric material.

[00159] 16. The method of claim 1, wherein mixing the carbohydrate-based polymeric material with the plastic material includes from 20% to 40% by weight of the carbohydrate-based polymeric material.

[00160] 17. The method of claim 1, wherein mixing the carbohydrate-based polymeric material with the plastic material additionally includes a compatibilizer.

[00161] 18. The method of claim 17, wherein the compatibilizer comprises at most 10% by weight of the blend.

[00162] 19. A method for providing biodegradability to a plastic material that, by itself, is not biodegradable otherwise, the method comprising:

provide a plastic material that, on its own, is not biodegradable on its own;

[00163] providing one or more substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) which have a crystallinity of less than 20%, less than 10%, a particular glass transition temperature, softening temperature vicat or heat deflection temperature, particular characteristics of Young's modulus and / or other physical characteristics of NuPlastiQ or ESR, the one or more carbohydrate-based polymeric material being selected for its

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33/122 ability to provide biodegradability to plastic material, which by itself is not biodegradable on its own; and [00164] mixing the carbohydrate-based polymeric material with the plastic material, where the carbohydrate-based polymeric material makes the plastic material biodegradable.

[00165] 1. A method for providing increased resistivity to a blown plastic film, the method comprising:

[00166] blowing a plastic film with a film blowing apparatus, the film being blown from a mixture that includes a first polymeric material and a renewable polymeric material based on starch, the polymeric material being renewable based on starch is (i) substantially amorphous, with a maximum crystallinity of 20%, (ii) has a Young's modulus of at least 1.0 GPa and / or (iii) has a glass transition temperature, softening temperature vicat or heat deflection temperature from 70 ° C to 100 ° C;

[00167] where:

[00168] (A) the film blowing apparatus operates at a high blowing rate of at least 2.0 during the blowing of the plastic film, the high blowing ratio providing the blown plastic film with increased resistivity; and / or [00169] (B) a matrix span of the film blowing apparatus is selected to be a matrix span of a maximum of 500 microns, with the narrow matrix span providing the blown plastic film with increased resistivity .

[00170] 2. The method of claim 1, wherein the first polymeric material comprises a polyolefin.

[00171] 3. The method of claim 1, wherein the first polymeric material comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride or polycarbonate.

[00172] 4. The method of claim 1, wherein the first material

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34/122 polymeric comprises at least one of polyethylene or polypropylene.

[00173] 5. The method of claim 1, wherein the blown plastic film has a thickness of 0.1 mil (0.0025mm) to 10 mil (0.2540mm).

[00174] 6. The method of claim 1, wherein the blowing ratio is

2.2 to 2.8.

[00175] 7. The method of claim 1, wherein the blowing ratio is about 2.5.

[00176] 8. The method of claim 1, wherein the renewable polymeric starch-based material is formed from a mixture of at least two different starches.

[00177] 9. A method to increase the resistivity of a blown plastic film, manipulating a blowing ratio, the method comprising:

[00178] blowing a plastic film with a film blowing apparatus, the film being blown from a mixture that includes a first polymeric material and a second polymeric material that comprises a renewable starch-based polymeric material, the material being renewable polymer based on starch is (i) substantially amorphous, with a maximum crystallinity of 20%, (ii) has a Young's modulus of at least 1.0 GPa, and (iii) has a glass transition temperature , vicat softening temperature or heat deflection temperature from 70 ° C to 100 ° C;

[00179] manipulate a blowing ratio of the film blowing apparatus in order to select a high blowing ratio of at least 2.0, in order to increase the resistivity of the blown plastic film.

[00180] 10. The method of claim 9, wherein the resistivity is increased by at least 1% by selecting the high blowing ratio.

[00181] 11.0 The method of claim 9, wherein the resistivity is increased by at least 10% by selecting the high blowing ratio.

[00182] 12. The method of claim 9, wherein the blowing ratio is

2.2 to 2.8.

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35/122 [00183] 13. The method of claim 9, wherein the blowing ratio is about 2.5.

[00184] 14. The method of claim 9, wherein the blown plastic film has a thickness of 0.1 mil (0.0025 mm) to 10 mil (0.254 mm).

[00185] 15. A method to increase the resistivity of a blown plastic film by manipulating the blowing ratio and a matrix gap, the method comprising:

[00186] blowing a plastic film with a film blowing apparatus, the film being blown from a mixture that includes a first polymeric material and a second polymeric material that comprises a renewable starch-based polymeric material, the material being renewable polymer based on starch is (i) substantially amorphous, with a maximum crystallinity of 20%, (ii) has a Young's modulus of at least 1.0 GPa, and / or (iii) has a temperature of glass transition, vicat softening temperature or heat deflection temperature from 70 ° C to 100 ° C;

[00187] manipulating a matrix span of the film blowing apparatus in order to select a narrow matrix span of a maximum of 500 microns; and [00188] manipulating the blowing ratio to be at least 2.0 during the blowing of the plastic film, the high blowing ratio and / or narrow die span providing the blown plastic film with resistivity increased ..

[00189] 16. The method of claim 15, wherein the blowing ratio is at least 2.0.

[00190] 17. The method of claim 15, wherein the blowing ratio is 2.2 to 2.8.

[00191] 18. The method of claim 15, wherein the blowing ratio is about 2.5.

[00192] 19. The method of claim 15, wherein the matrix span is of

250 microns to 500 microns.

[00193] 20. The method of claim 15, wherein the plastic film

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36/122 blown has a thickness of 0.1 mil (0.0025mm) to 10 mil (0.254 mm).

[00194] 1. A sustainable plastic material that exhibits a reduced odor comprising:

[00195] a polymeric resin;

[00196] an organic odor reducing agent; and [00197] a carbohydrate-based polymeric material, in which in the absence of the organic odor reducing agent, the carbohydrate-based polymeric material provides a characteristic odor of burnt carbohydrate to the sustainable plastic material.

[00198] 2. The material of claim 1, wherein the organic odor reducing agent comprises a lyophilized powder.

[00199] 3. The material of claim 1, wherein the organic odor reducing agent comprises a vanilla extract.

[00200] 4. The material of claim 1, wherein the organic odor reducing agent comprises vanillin.

[00201] 5. The material of claim 1, wherein the organic odor reducing agent has the following chemical structure:

OH [00202] 6. The material of claim 1, wherein the organic odor reducing agent essentially consists of 4-hydroxy-3-methoxybenzaldehyde.

[00203] 7. The material of claim 1, wherein the organic odor reducing agent comprises at most 1% of the plastic material.

[00204] 8. The material of claim 1, wherein the organic odor reducing agent comprises at most 0.1% of the plastic material.

[00205] 9. The material of claim 1, wherein the organic odor reducing agent comprises at most 0.01% of the plastic material.

[00206] 10. The material of claim 1, wherein the reducing agent

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37/122 organic odor comprises, at most, 1,000 ppm of the plastic material.

[00207] 11.0 material of claim 1, wherein the organic odor reducing agent comprises a maximum of 100 ppm of the plastic material.

[00208] 12. The material of claim 1, wherein the organic odor reducing agent comprises a maximum of 50 ppm of the plastic material.

[00209] 13. The material of claim 1, wherein the organic odor reducing agent comprises a maximum of 20 ppm of the plastic material.

[00210] 14. The material of claim 1, wherein the organic odor reducing agent is present in a relative ratio of the carbohydrate-based polymeric material from 1: 1,000 to 1: 100,000.

[00211] 15. The material of claim 1, wherein the organic odor reducing agent is present in a relative ratio of the carbohydrate-based polymeric material from 1: 25,000 to 1: 75,000.

[00212] 16. The material of claim 1, wherein the organic odor reducing agent comprises a fruit extract.

[00213] 17. The material of claim 16, wherein the organic odor reducing agent comprises a lyophilized organic fruit extract selected from extracts of vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, passion fruit, raspberry or a combination thereof.

[00214] 18. The material of claim 16, wherein the lyophilized organic fruit extract is present in the plastic material in a ratio of at most 1: 1,000 to the carbohydrate-based polymeric material.

[00215] 19. The material of claim 1, wherein the carbohydrate-based polymeric material is a starch-based polymeric material.

[00216] 20. A polymeric material based on sustainable thermoplastic carbohydrate that exhibits reduced odor comprising:

[00217] an organic odor reducing agent; and [00218] a polymeric carbohydrate material;

[00219] in which a weight ratio between the organic odor reducing agent and the carbohydrate-based polymeric material is at most 1: 1,000

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38/122 so that there is at least 1,000 times more carbohydrate-based polymeric material than the organic odor reducing agent.

[00220] 21. The material of claim 20, which further comprises a thermoplastic polymeric resin mixed with the polymeric material based on sustainable thermoplastic carbohydrate, wherein by hot mixing of the polymeric material based on sustainable thermoplastic carbohydrate with the thermoplastic polymeric resin , an odor of burnt carbohydrate is present, however for the presence of the organic odor reducing agent.

[00221] 22. The material of claim 21, wherein the thermoplastic polymeric resin comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride or polycarbonate.

[00222] 23. The material of claim 22, in either the mixture of the carbohydrate-based polymeric material with the thermoplastic polymeric resin includes from 5% to 50% by weight of the carbohydrate-based polymeric material.

[00223] 1. A process that comprises:

[00224] supplying one or more other polymeric materials (for example, polymeric materials based on petrochemical product);

[00225] supply one or more polymeric materials based on carbohydrate;

[00226] mixing one or more other polymeric materials and one or more carbohydrate-based polymeric materials to produce a mixture;

[00227] heat the mixture to a temperature in the range of about 120 ° C to 180 ° C; and [00228] producing a film using the mixture, the film having a thickness of about 1 to about 6 microns and a dart drop impact value of about 40 g to about 100 g.

[00229] 1. A process that comprises:

[00230] supply one or more polymeric materials based on

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39/122 carbohydrate;

[00231] providing one or more other polymeric materials (for example, including PBAT or bioPE);

[00232] mixing one or more other polymeric materials and one or more carbohydrate-based polymeric materials to produce a mixture;

[00233] heat the mixture to a temperature in the range of about 120 ° C to 180 ° C; and [00234] producing a film using the mixture, the film having a thickness of about 10 to about 100 microns and a dart drop impact value of about 200 g to about 600 g.

[00235] These and other advantages and features of the present invention will be more fully evident from the description and attached claims below or can be learned by practicing the invention as presented hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS [00236] In order for the manner in which the advantages and objects mentioned above of the invention are achieved, a more particular description of the invention briefly described above will be provided by reference to specific modalities thereof which are illustrated in the accompanying drawings. The understanding that these drawings portray only typical modalities of the invention and, therefore, are not considered as limiting the scope of the same, the invention will be described and explained with specificity additional details through the use of the attached drawings in which:

[00237] Figure 1 illustrates a flow diagram of an exemplary process for forming an article in accordance with the present disclosure.

[00238] Figure 1A illustrates a flow diagram of an exemplary process for increasing the resistivity of a blown plastic film by manipulating the blowing ratio.

[00239] Figure 1B illustrates a flow diagram of an exemplary process for including an odor reducing agent in the mix of materials

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40/122 including carbohydrate-based polymeric material and other polymeric material. [00240] Figure 1C illustrates a flow diagram of an exemplary process for forming a carbohydrate-based polymeric material that includes an odor reducing agent that neutralizes a characteristic odor of the carbohydrate-based polymeric material and then using the polymeric material based on carbohydrate with odor reducing agent to produce an article.

[00241] Figure 2A illustrates components of an exemplary manufacturing system for producing articles in accordance with the present disclosure.

[00242] Figure 2B illustrates a schematic foreground view of the film blowing apparatus of Figure 2A, which shows the matrix, the matrix gap, the blown film bubble that has a high blowing ratio and the freezing line of the bubble.

[00243] Figure 20 illustrates a schematic cross-sectional view in the foreground through a portion of the matrix of Figure 2B, showing the narrow matrix span.

[00244] Figure 3 shows data on modulus of elasticity and elongation at break for various black chemical plastics that are typically not biodegradable or compostable (identified standard plastics) as well as various plastics that are more "environmentally friendly" in one or more aspects.

[00245] Figure 4 shows X-ray diffraction patterns for a NuPlastiQ carbohydrate-based polymeric material or “ESR” commercially available from BiologiQ compared to that of the blend of native corn starch and native potato starch used to form NuPlastiQ or ESR. [00246] Figure 5 shows resistance to dart impact for films of different thicknesses based on the percentage of carbohydrate-based polymeric material in the film.

[00247] Figure 6 shows resistance to dart impact for films of different thicknesses (from about 0.0025 mm (0.1 mil) to 0.0508 mm (2

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41/122 thousand)) formed from a mixture of 25% of carbohydrate-based polymeric material, about 5% of compatibilizer and about 70% of PE, compared to 100% of PE film and it also shows , the comparison for existing production, transport and potato exchanges.

[00248] Figure 7 shows resistance to the impact of the dart for films of different thicknesses for various merged films including NuPlastiQ or ESR, as well as comparative files formed from virgin or recycled materials.

[00249] Figures 8A to 8B show the percentage of biodegradation measured over 349 days according to the test conducted according to the ASTM D-5511 standard for three samples formed according to the present disclosure.

[00250] Figure 9 shows the percentage of biodegradation measured over 843 days according to the test conducted according to the ASTM D-5526 standard for potato bags produced with 25% NuPlastiQ or ESR, 70% PE, and 5% of compatibilizer under simulated landfill conditions.

[00251] Figures 10A to 10B show the percentage of biodegradation measured over 370 days according to the test conducted according to the ASTM D-5338 standard for several samples produced according to the present disclosure, as well as comparative controls.

[00252] Figure 11 shows the percentage of biodegradation measured over 205 days according to ASTM D-6691, which means stimulating underwater conditions, for several samples produced according to the present disclosure, as well as comparative controls.

[00253] Figure 12A shows resistance to the impact of the dart for films produced with a mixture of polymeric material based on NuPlastiQ or ESR carbohydrate and a bio-polyethylene or ecological PE. The dart's impact resistance is shown as a percentage function of NuPlastiQ or ESR, for films of various thicknesses.

[00254] Figure 12B shows data similar to FIG. 12A, however

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42/122 shows resistance to dart impact as a function of film thickness, for blends that include varying percentages of NuPlastiQ or ESR. [00255] Figure 13 shows resistance to the impact of the dart for films formed from a mixture that includes 25% NuPlastiQ or ESR material, in which the balance is a compatibilizer and polyethylene in a blowing ratio of 2.5, compared to dart impact resistance for films formed entirely from polyethylene, polyethylene films do not exhibit resistivity dependence on the blowing ratio.

DETAILED DESCRIPTION

I. DEFINITIONS [00256] All publications, patents and patent applications cited earlier or later in this document are incorporated by reference in their entirety as well if each individual publication, patent or patent application was specifically or individually indicated for be incorporated as a reference.

[00257] The term "that comprises" that is synonymous with "that includes", "that contains" or "characterized by", is inclusive or is open and does not exclude elements or steps of additional methods not recited.

[00258] The term "essentially consists of" limits the scope of a claim to the specified materials or steps and to those that do not materially affect the basic and innovative feature (or basic and innovative features) of the claimed invention.

[00259] The term "consisting of", as used herein, excludes any element, step, or ingredient not specified in the claim.

[00260] The terms one, one, o, “a” and similar referents used in the context of describing innovative features (especially in the context of the following claims) should be interpreted as encompassing both the singular and the plural, unless otherwise indicated. otherwise in this document or clearly contraindicated by the context. Thus, for

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43/122 example, reference to a "starch" may include one, two or more starches.

[00261] The film, as used in this document, refers to a thin continuous article that includes one or more polymeric materials that can be used to separate areas or volumes, to retain items in order to act as a barrier and / or as a printable surface.

[00262] Bag, as used in this document, refers to a container made from a relatively thin flexible film that can be used to contain and / or transport goods.

[00263] “Bottle, as used in this document, refers to a container that can be produced from the plastics disclosed in this document, typically with a thickness greater than a film and that typically includes a relatively narrow neck adjacent to an opening. Such bottles can be used to hold a wide variety of products (for example, drinks, personal care products, such as shampoo, conditioner, lotion, soap, cleansers and the like).

[00264] Unless otherwise stated, all percentages, ratios, parts and quantities used and described in this document are by weight.

[00265] Numbers, percentages, ratios or other values stated in this document may include this value, as well as other values that are about or approximately the declared value, as will be observed by a person of ordinary skill in the art. Therefore, a declared value must be interpreted broadly enough to encompass values that are at least close enough to the declared value in order to perform a desired function or obtain a desired result and / or values that round off the declared value. The declared values include at least the variation to be expected in a typical manufacturing process and can include values that are within 25%, 15%, 10%, within 5%, within 1% etc. of a declared value. In addition, the terms "substantially", "similarly", "about" or "approximately", as used in the

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44/122 present document represent a quantity or declare proximity to the declared quantity or state that still performs a desired function or obtains the desired result. For example, the term "substantially" "about" or "approximately" may refer to an amount that is within 25%, 15%, 10%, 5% or 1% of a declared amount or value.

[00266] Some tracks are revealed in this document. Additional ranges can be defined between any values disclosed in this document as being exemplary of a particular parameter. All of these tracks are covered and are within the scope of the present disclosure. In addition, the recitation of ranges of values in this document is intended to serve as a short method of referring individually to each separate value covered by the range. Unless otherwise indicated in this document, each individual value is incorporated into the specification as if it were individually recited in this document.

[00267] All numbers that express quantities of ingredients, constituents, conditions and so on used in the specification and claims must be understood as being modified in all instances by the term "about". In addition to the numerical ranges and parameters that present the broad scope of the invention are approximations, the numerical values presented in the specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors that necessarily result from the standard deviation found in the respective test measurements.

[00268] The phrase 'free from' or similar phrases, as used in this document, means that the composition comprises 0% of the declared component, that is, the component was not intentionally added to the composition. However, it will be appreciated that such components may be formed incidentally under appropriate circumstances, may be present incidentally within another component included, for example, as an incidental contaminant or the like.

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45/122 [00269] The phrase "substantially free of" or similar phrases, as used herein, means that the composition preferably comprises 0% of the declared component, however, it will be noted that very small concentrations may possibly be present, for example, through incidental formation, incidental contamination or even by intentional addition. Such components may be present if they are present in quantities less than less than 1%, less than 0.5%, less than 0.25%, less than 0.1%, less than 0.05%, less than 0, 01%, less than 0.005%, less than 0.001%, or less than 0.0001%.

II. INTRODUCTION [00270] The present disclosure refers, among other things, to articles that are formed from mixtures that include a non-sustainable polymer material based on carbohydrate or renewable, in combination with another polymer material. In addition to increased sustainability, such articles may exhibit increased biodegradability and / or resistivity. Articles can be formed by mixing one or more polymeric carbohydrate materials and one or more other polymeric materials (for example, sustainable polymeric version based on a petrochemical or ecological product of such plastic resin), heating the mixture and forming a article from it, for example, by means of extrusion, injection molding, blow molding, blow forming or the like. In various embodiments, carbohydrate-based polymeric materials can include polymeric starch-based materials that are substantially amorphous and / or exhibit other specific characteristics with respect to the glass transition temperature, heat deflection temperature, vicat softening temperature, modulus Young, low crystallinity and the like, as described in this document.

[00271] The articles described in this document can be produced in the form of any conceivable structure, including, but not limited to bottles, boxes, other containers, glasses, plates, utensils, leaves,

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46/122 films, bags and the like. Then, films for bags and film wrappers (for example, to wrap around or on top of a product) can be easily produced using a blown film equipment. Other processes that can be used for article forming may include, but are not limited to, injection molding, blow molding, thermoforming and other plastic manufacturing processes.

[00272] Examples of suitable polymeric materials based on starch or carbohydrate based for use in the formation of such articles are available from BiologiQ, under the trade name NuPlastiQ or ESR (“Ecological Starch Resin”). Specific examples include, but are not limited to, GS-270, GS-300 and GS-330. The specific characteristics of such NuPlastiQ or ESR materials will be described in more detail in this document. Other starch-based or carbohydrate-based polymeric materials that exhibit similar properties may also be suitable for use, so NuPlastiQ or ESR available from BiologiQ is just a non-limiting example of a carbohydrate-based or polymer-based material of adequate starch.

[00273] In one embodiment, the "other" polymeric material included in the blend (different from the carbohydrate-based polymeric material) can be a non-sustainable polymeric material, for example, formed from a plant or other renewable sources (for example , bacterial products). In this way, all or substantially all (for example, 90% or more, 95% or more, 97% or more, 98% or more, 99% or more) the polymer content of the article can be formed from polymers from sustainable vegetable or renewable sources. This characteristic is particularly advantageous, from a sustainability perspective. As described in this document, a small fraction of a compatibilizer may be present in addition to the polymer content, in order to increase compatibility between the "other" polymeric resin material and the carbohydrate-based polymeric material. In some modalities, such a compatibilizer may be the only component that is not

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47/122 from or derived from sustainable sources. In other modalities, such compatibilizer can be sustainable, so that 100% of the article can potentially come from a sustainable source.

[00274] In addition to the desirable sustainability characteristics, the carbohydrate-based polymeric material can be configured to supply the material with which it is mixed (ecological non-sustainable polymeric material, such as ecological PE (or biopolyethylene), ecological PP or BioPET ) with biodegradability. In other words, even when the ecological unsustainable polymeric material, by itself, is not biodegradable on its own, its inclusion in the article, which also includes the carbohydrate-based polymeric material, can in fact make it biodegradable. Such a result is also very advantageous.

[00275] Furthermore, many articles (for example, particularly thin films) do not have particularly good resistivity when formed from conventional plastic materials (for example, polymeric materials based on petrochemicals), so that the increased resistivity in a certain thickness is desirable. Due to the fact that ecological plastics "exhibit physical characteristics that are similar to those equivalent to their conventional petrochemical product base, such ecological plastic materials" also do not have a particularly satisfactory resistivity, and a means to increase resistivity, without increasing the thickness of the article, it is desirable. When mixed with carbohydrate-based polymeric materials as described in this document, such results of increased resistivity are obtainable. For example, although a polyethylene film (for example, or biopolyethylene (ecological PE) or metallocene petrochemical based PE) may have a dart impact resistance of around 150 g for a 0.025 mm (1 mil ) of thickness, it will be advantageous if the resistivity can be increased, without increasing the thickness of the film. The present embodiments can provide such increased resistivity. For example, by mixing

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48/122 with a carbohydrate-based polymeric material, as described in this document, resistivity can increase by at least 5%. The typical results of some modalities can result in increases of resistivity of 20% or even more.

[00276] Articles can be produced by mixing the carbohydrate-based polymeric material with the unsustainable polymeric material, heating the mixture and molding (for example, injection molding) the mixture, extruding the mixture by blowing the mixture, blowing the mixture, thermoforming the mixture or the like. Various other plastic manufacturing processes will become apparent to those skilled in the art in light of the present disclosure.

[00277] With respect to biodegradability, methods and articles can provide biodegradability to a plastic material that, by itself, is not biodegradable, otherwise, mixing such plastic material with the polymeric materials based on carbohydrate (for example , based on starch) which has specific characteristics, including low crystallinity, as described in this document. Such modalities are particularly beneficial in that they allow numerous plastic items that are discarded to be readily biodegraded in a landfill or similar environment, rather than continuing to exist in the stable polymeric state indefinitely.

[00278] In addition, the Applicant has noted that the biodegradation of such articles does not occur readily when the articles are stored in typical storage and typical environments (for example, stored in a residence, office, warehouse or the like), however this biodegradation generally begins to occur only when the article is placed in an environment that simulates or is that of a landfill or compost condition or other typical disposal conditions. For example, such conditions often include (i) a temperature that is raised to a degree above normal ambient temperatures for “use” or “storage” (ii) exposure to high humidity levels and (iii) exposure to particular classes

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49/122 of microbes indigent to landfills or similar compounds and disposal environments. The high temperature and humidity will not cause such items to degrade unless the necessary microorganisms are also present. The combination of such conditions causes articles formed from such a mixture of materials to begin to biodegrade. Third-party testing as described in this document confirms that not only is the polymeric carbohydrate material that biodegrades, but also the plastic material that is not otherwise biodegradable, it is also biodegraded.

[00279] Although the mechanisms by which such biodegradation is made possible by mixing with the carbohydrate-based polymeric material may not be fully understood, it is believed that the mixture of the two plastic materials together, perhaps combined with particular characteristics of the polymeric material to carbohydrate-based in some way breaks the hygroscopic barrier associated with non-biodegradable plastic materials, which allows microbes that biodegrade the carbohydrate-based polymeric material not only biodegrade the carbohydrate-based polymeric material, but also biodegrade the adjacent plastic molecules too. Carbon bonds are broken and biodegradation is shaped based on third-party tests that capture and measure carbon dioxide and which is effluent. Such results are surprising, unexpected and particularly advantageous.

[00280] Another aspect of the present disclosure relates to methods for providing increased resistivity to a blown plastic film, in at least some modalities by manipulating blow rate and or matrix gap. Such methods may include blowing a plastic film with a film blowing apparatus, the film being blown from a mixture that includes a polymeric material (eg polyethylene or the like) and renewable carbohydrate-based polymeric materials (eg , based on starch) described in this document, and the renewable polymeric material based on carbohydrate is substantially amorphous, for example, which has a

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50/122 crystallinity of a maximum of 20% and / or includes other particular characteristics. For example, the renewable carbohydrate-based polymeric material can have a Young's modulus of at least 1.0 GPa and / or it can have a glass transition temperature, vicat softening temperature or heat deflection temperature of 70 ° C to 100 ° C. The film blowing apparatus is specifically operated at a high blowing ratio of at least 2.0 during the blowing of the plastic film and / or with a narrow die span (for example, maximum 500 microns). Such characteristics, during the use of the carbohydrate-based polymeric material, were found by the Applicant to provide surprisingly increased resistivity to the plastic film, in comparison to the resistivity that is provided in a more typical lower blow ratio (for example, 1.5) or go from a wider matrix. Such a comparison that shows increased resistivity can be with the same material, while only the change or the blowing ratio or the matrix gap. Such increased resistivity can also be exhibited in comparison to the resistivity that is provided during the blowing of the film with the use of the "other" polymeric material (eg polyethylene) alone, without NuPlastiQ or ESR or other renewable carbohydrate polymeric material which has particular characteristics, as identified in this document. During PE blowing alone, the blowing ratio and the matrix span do not significantly affect resistivity.

[00281] Such methods may include a step of specifically selecting the high blowing ratio and / or narrow die span in order to provide increased resistivity to the resulting blown film, in return for any other purpose for which the reason may possibly be manipulated blow (for example, to perhaps manipulate the flat width of the resulting film).

[00282] For example, the Applicant found that during the blowing of the film from the "other" polymeric material, such as polyethylene, only, there is no significant effect on resistivity since the blowing ratio is manipulated.

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51/122

In addition, the Applicant has found that during the addition of a renewable carbohydrate-based polymeric material, such as NuPlastiQ or ESR, to the blend from which the film is blown, there is no significant decrease in resistivity for such a merged film, in comparison to 100% polyethylene film or other polymeric material, when proportioned in the same blowing ratio typical of 1.5 typically used in blowing films. The Applicant thought further and further noted that increases in resistivity can, in fact, be achieved during the blowing of a blended film that includes a renewable carbohydrate-based polymeric material, such as NuPlastiQ or ESR by increasing the blowing ratio, for example, at least 2.0, preferably from 2.2 to 2.8 (for example, 2.5).

[00283] Although it is not completely understood why resistivity increases at higher blowing ratios, when there is no effect on resistivity with films formed from the "other" polymeric material only, it is believed that there may be some type of orientation of alignment, stretching or ordered arrangement of amorphous structures or other structures of the mixture molecules when the blowing ratio is increased, which results in increased resistivity. In any case, although perhaps not fully understood, the Applicant observed and measured the increased resistivity under the conditions and methods described in this document.

[00284] Articles can be produced by mixing the renewable carbohydrate-based polymeric material with the other polymeric material (for example, a polyolefin, such as polyethylene, or another plastic), heating the mixture and feeding the molten mixture to a film blowing apparatus, which is specifically operated at a high blowing ratio and / or narrow die span, in which the selection (or selections) is made specifically for the purpose of providing increased resistivity to the resulting film. Blown films can be further processed in a wide variety of possible structures, including, but not limited to, plastic bags,

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52/122 film wrappers and the like.

[00285] Another aspect of the present disclosure relates to modalities in which a characteristic burnt carbohydrate odor resulting during typical heating and molding or other form of the plastic material is neutralized by including a very small fraction of an odor reducing agent, preferably , an organic odor reducing agent. In one embodiment, the odor reducing agent may be included with the carbohydrate-based polymeric material (for example, as part of a major batch of the carbohydrate-based polymeric material).

[00286] In one embodiment, the polymeric material based on carbohydrate can be present in fractions much higher than the odor reducing agent. For example, the carbohydrate-based polymeric material can be at least 1,000 times, 10,000 times, or 50,000 times more complete than the odor reducing agent. Even in very small concentrations (for example, 1 part odor reducing agent to 50,000 parts of carbohydrate-based polymeric material), effective control (ie substantially complete removal) of popcorn, caramelized corn or slightly burnt starch odor odor can be achieved. It is surprising that such a small fraction of the odor reducing agent is sufficient to obtain such results.

[00287] A main batch that includes the odor control agent and the carbohydrate-based polymeric material can be mixed with almost any conceivable polymeric resin material and used to produce a desired plastic article. For example, articles can be produced by mixing the carbohydrate-based polymeric material (including an odor reducing agent) with the polymeric resin, heating the mixture and molding (for example, injection molding) the mixture, extruding the mixing, blow molding of the mixture, blow forming of the mixture (e.g. forming a blown film), thermoforming the mixture or the like. The aforementioned list of plastic manufacturing processes is evidently not exhaustive and several other plastic manufacturing processes will become evident

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53/122 for people skilled in the art.

[00288] A small fraction of an odor reducing agent can be included within the carbohydrate-based polymeric material, introduced with a polymeric resin with which the carbohydrate-based polymeric material is mixed or otherwise introduced into the blend . In one embodiment, a major batch of the carbohydrate-based polymeric material can be provided with the odor reducing agent already included in it. In another embodiment, the odor-reducing agent can be added separately from the carbohydrate-based polymeric material and / or separated from a polymeric resin that is included in the blend from which an article is to be formed. In addition to NuPlastiQ or ESR available from BiologiQ, it will be apparent that other carbohydrate-based or starch-based polymeric materials may also benefit from the addition of a small fraction of an odor reducing agent as described in this document.

III. EXEMPLIFICATIVE ARTICLES AND METHODS [00289] Figure 1 illustrates an exemplary basic process 100 according to the present invention. It will be apparent from the disclosure that various specifications can be added, such as the inclusion of an odor reducing agent, provided that the "other" polymeric material comprises a sustainable resin in its own right (for example, ecological PE, bioPET or similar) or specific selections during the blowing of a film, with respect to the blowing ratio and / or matrix span. In 102, process 100 may include providing one or more "other" polymeric materials, for example, typically, though not necessarily, non-biodegradable materials (for example, including but not limited to polyethylene, polypropylene, other polyolefins, polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, nylon or polycarbonate). In 104, process 100 may include providing one or more carbohydrate-based polymeric materials, which are substantially amorphous, exhibiting a maximum crystallinity of 20% (for example, more typically less than 10%). Other features may be alternative or

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54/122 additionally present (for example, Young's modulus of 1.0 GPa or greater, glass transition temperature, vicat softening temperature or heat deflection temperature of at least 70 ° C, at least 80 ° C or 80 ° C to 100 ° C). The one or more carbohydrate-based polymeric materials can include starch-based polymeric materials. The carbohydrate-based polymeric materials and the other polymeric material can be supplied in a desired form, such as pellets, powders, pollution, slurry and / or liquids. In specific modalities, the materials can be in the form of pellets. The method additionally includes mixing the other polymeric material with the carbohydrate-based polymeric material.

[00290] Such blends can be formed in the manufacture of a desired article through any conceivable process. An example of this is an extrusion process. For example, an extruder can be fed with the other polymeric material and the carbohydrate-based polymeric material (for example, in one or more feeders thereof). The extruder can be fed with different materials can be fed in the same chamber, in different chambers, at approximately the same time (for example, through the same feeder), or at different times (for example, through different feeders, where one is inserted in the extruder next to the screw before the other), etc. It will be evident that there may be many other possibilities.

[00291] In some cases, the other polymeric material may include a polyolefin. For example, such plastic or polymeric materials may include, but are not limited to, polyethylene, polypropylene, polyethylene terephthalate, other polyolefins, polyester, polystyrene, ABS, polyvinyl chloride, nylon, polycarbonates and the like. Such plastic material can come from sustainable petrochemical sources, or from sustainable sources then called "ecological" (for example, ecological PE, bioPET and the like).

[00292] In some cases, the "other" polymeric material may, in itself, be

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55/122 only, sustainable, for example, a sustainable polyolefin. For example, such sustainable polymeric materials may include, but are not limited to, an ecological polyethylene (bioPE), an ecological polypropylene (bioPP), a bioPET or other plastic material that can be formed from sustainable plant sources. As a non-limiting example, ecological PE can be derived from ethanol which can be formed from sugar cane, other crops of sugar (for example, sugar beet) or a grain (for example, corn, wheat or similar). Ecological PE (sometimes also called “bioPE”) has a chemical structure similar to PE formed from a petrochemical raw material, but in which ethanol, or the ethylene monomer used in polymerization is derived from sustainable sources and not a petrochemical raw material. Ecological PP "can be similarly formed from propylene which can be derived from propanol (or perhaps isopropanol) derived from sugar cane, another crop of sugar or grains (for example, corn) Another example of an ecological unsustainable polymeric material is bioPET, for example, in which the monomers used in the formation of poly (ethylene terephthalate) (for example, typically ethylene glycol and terephthalic acid) can be similarly derived from plant sources, such as sugar cane, another crop of sugar or grains. PET is the most common thermoplastic resin in the polyester family. Another polyester that can be formed similarly of sustainable plant sources is adipate terephthalate polybutyrate (bioPBAT). PBAT can be formed as a copolyester of adipic acid, 1,4 butanediol and dimethyl terephthalate. One or more of these starting materials can be derived from sustainable plant sources. Another polymeric resin material that can be used is poly (lactic acid). PLA is typically produced from lactic acid monomers and / or lactide esters, as will be seen by those skilled in the art. One or more materials for PLA production can be derived from sustainable plant sources. Other sufficient "ecological" polymers that are familiar to people skilled in the art that can be used include PBS (succinate

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56/122 of polybutylene) or PCL (polycaprolactone).

[00293] People skilled in the art will be familiar with processes for synthesizing such polymers. One or more of the components used to manufacture such polymers can be derived from a suitable renewable plant or other renewable biological source (for example, generation of bacteria). Ecological PE is available from Braskem, bioPET is available from Coca Cola ^{TMe and} is used in the same Plant Bottle ™ and probably also from other plastic manufacturers. Although PE, PP, PET and PBAT are examples of ecological bioplastics that can be formed from materials derived from sustainable plant sources, it will be noted that several other ecological plastics may also be suitable for use, as long as they can be formed at least in part from sustainable materials (eg plant sources). In addition, although sugar cane, another crop of sugar, corn, wheat and other grains may be non-limiting examples of plant materials from which such ecological polymeric materials can be derived, it will be noted that several other plants and materials also can be used properly.

[00294] Polymeric carbohydrate-based materials can be formed from a plurality of materials (e.g., a mixture) including one or more starches. For example, the one or more starches can be produced from one or more plants, such as a corn starch, tapioca starch, cassava starch, wheat starch, potato starch, rice starch, sorghum starch and the like. In some embodiments, a mixture of different types of starches can be used, and the Applicant has found that it results in a synergistic increase in resistivity. A plasticizer is also present within the mixture of components from which carbohydrate-based polymeric materials are formed. Water can also be used in the formation of the carbohydrate-based polymeric material, although only a small to negligible dosage amount of water is present in the finished carbohydrate-based polymeric material.

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57/122 [00295] It will be noted that in some embodiments, then, the entire polymeric content (or substantially all of the polymeric content) of the article can be derived from plant materials. Although the ecological polymeric material ”typically employs polymerizable monomers or other small molecule polymerizable components that can be derived from ethanol (or the like) formed from a desired plant material, the carbohydrate-based (or carbon-based) polymeric material starch) can be formed from starch (and glycerin or another plasticizer), instead of processing such starch or other plant materials to form smaller polymerizable monomers. Thus, the molecular weight of the starch (or starches) used to produce the polymeric starch-based material can be much greater than the molecular weight of the relatively small molecular monomers produced for use in the manufacture of the ecological non-sustainable polymeric material. For example, monomers from a sustainable plant source or other polymerizable components used in the production of ecological non-sustainable polymeric material can typically be less than about 500 Daltons, less than 400 Daltons, less than 300 Daltons, less than 200 Daltons, or less than 100 Daltons, although the molecular weight of starch (or starches) used in the manufacture of polymeric starch-based material typically can be significantly greater, often greater than 500 Daltons, often measured in thousands, tens of thousands or even more (for example, more than 500 Daltons, at least 1,000 Daltons, at least 10,000 Daltons, at least 25,000 Daltons, at least 40,000 Daltons or similar). In other words, the starch materials (for example, native starches) used in the formation of the starch-based material are typically more complex molecules than the monomers or other polymerizable components used in the production of the ecological non-sustainable polymeric material. For example, corn starch can have a molecular weight of about 693 Daltons. Potato starch can have a molecular weight that can vary widely, for example, from about 20,000 Daltons to about 400 million Daltons (for example,

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58/122 example, amylose can range from about 20,000 Daltons to about 2 million Daltons, whereas amylopectin can range from about 65,000 Daltons to about 400 million Daltons). Tapioca starch can have a molecular weight ranging from about 40,000 Daltons to about 340,000 Daltons. The glycerin used in the formation of the polymeric material based on starch can also be derived from sustainable sources. Glycerin has, of course, a molecular weight of 92 Daltons.

[00296] Turning to the characteristics of the carbohydrate-based polymeric material, the one or more carbohydrate-based polymeric materials can be formed, in large part, by starch. For example, at least 65%, at least 70%, at least 75%, or at least 80% by weight of the carbohydrate-based polymeric material can be attributable to one or more starches. In one embodiment, 65% to 90% by weight of the polymeric material based on polymeric carbohydrate can be attributed to one or more starches. In addition to the negligible water content, the balance of the finished carbohydrate-based polymeric material can be attributed to the plasticizer (eg glycerin). The percentages above may represent a percentage of starch in relation to the starting materials from which the carbohydrate-based polymeric material is formed or that fraction of the finished carbohydrate-based polymeric material that is derived from the plasticizer assigned to it (for example, by minus 65% of the carbohydrate-based polymeric material can be attributed to starch (or starches) (formed from it) as a starting material). Although part of the water can be used in the formation of the carbohydrate-based polymeric material, substantially, the balance of the carbohydrate-based polymeric material can be attributed to glycerin, or another plasticizer. Very little residual water (for example, less than 2%, typically, not more than about 1%) can be present in the finished carbohydrate-based polymeric material.

[00297] For example, materials from which the one or more carbohydrate-based polymeric materials are formed can include at least 12%,

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59/122 at least 15%, at least 18%, at least 20%, at least 22%, at most 35%, at most 32%, at most 30%, at most 28% or at most 25% by weight a plasticizer. Such percentages may represent that fraction of the finished carbohydrate-based polymeric material that is derived from or attributable to the plasticizer (for example, at least 12% of the carbohydrate-based polymeric material can be attributed to the plasticizer (or formed from it) ) as a starting material).

[00298] Exemplary plasticizers include, but are not limited to, glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, hydrogen bonding that forms organic compounds that do not have a hydroxyl group, sugar alcohol anhydrides, animal proteins, vegetable proteins , aliphatic acids, phthalate esters, esters related to dimethyl esters and diethylsuccinate ester and related esters, glycerol triacetate, glycerol mono and diacetates, glycerol mono, di, and tripropionates, butanoates, tearates, esters of lactic acid, esters of citric acid adipic acid esters, stearic acid esters, oleic acid esters, other acid esters or combinations thereof. Glycerin may be preferred.

[00299] The finished carbohydrate-based polymeric material may include a maximum of 5%, a maximum of 4%, a maximum of 3%, a maximum of 2%, a maximum of 1.5%, a maximum of 1.4%, a maximum of 1.3%, maximum 1.2%, maximum 1.1%, or maximum 1% water weight. The NuPlastiQ or ESR materials available from BiologiQ are examples of such finished carbohydrate-based polymeric materials, however, it will be noted that other materials available on another occasion (for example, in the future) can also be used for use.

[00300] In some embodiments, mixtures of different starches can be used in the formation of the carbohydrate-based polymeric material. It has been found that the use of such a mixture of different starches (for example, from different) is surprisingly associated with a synergistic increase in resistivity in articles that include such polymeric materials to

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60/122 carbohydrate base. In such a mixture of starches, a starch may be present in the mixture in an amount of at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15 %, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at most 95%, at most 90%, at most 85%, at most 80%, at most 75 %, maximum 70%, maximum 65%, maximum 60%, maximum 55%, maximum 50%, or 10% to 50% by weight, based on the combined weight of the plurality of starches. Some exemplary non-limiting mixtures may include 90% of a first starch and 10% of a second starch or 30% of a first starch and 70% of a second starch or 50% of a first starch and 50% of a second starch. Mixtures of more than two starches (for example, using 3 or 4 different starches) can also be used.

[00301] Examples of suitable carbohydrate-based polymeric materials (for example, starch-based) for use in forming films and other articles are available from BiologiQ, located in Idaho Falls, Idaho, under the trade name NuPlastiQ or ESR (“Ecological Amifo Resin”). Specific examples include, but are not limited to, GS-270, GS-300 and GS330. NuPlastiQ or ESR can be formed as a pellet. The physical characteristics for GS-270 and GS-300 are shown in Table 1 below.

TABLE 1

PROPERTY TEST METHOD GS-270 RATIO GS-300 RATIO Density ASTM D-792 1.40 g / cm ³ 1.42 g / cm ³ THERMAL PROPERTIES Flow rate Cast Material 200 ° C / 5kg ASTM D-1238 1.98 g / 10 min 1.95 g / 10 min Range Temperature ASTM D-3418 166 to 180 ° C 166 to 180 ° C

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PROPERTY TEST METHOD GS-270 RATIO GS-300 RATIO Fusion Glass Transition Temperature ASTM D-3418 81 to 100 ° C 81 to 100 ° C MECHANICAL PROPERTIES Yield Tensile Strength ASTM D-638 > 30 MPa > 14 MPa Tensile strength at break ASTM D-638 > 30 MPa > 14 MPa Young's Module ASTM D-638 1.5 GPa 1.5 GPa Elongation at Break ASTM D-638 <10% <10% Impact Resistance (Dart) ASTM D-5628 3.5 kg 4.5 kg ADDITIONAL PROPERTIES Water content ASTM D-6980 <1.5%, or <1% <1.5%, or <1%

[00302] The characteristics shown above for GS-270 and GS-300 are exemplary of other NuPlastiQ or ESR products available from BiologiQ, although the values may vary in some way. For example, NuPlastiQ or ESR products from BiologiQ can generally have a glass transition temperature, vicat softening temperature or heat deflection temperature that is at least 70 ° C, at least 75 ° C, at least 80 ° C, up to 200 ° C, up to 150 ° C, up to 125 ° C, up to 110 ° C, or in a range of about 70 ° C to about 100 ° C, or from 80 ° C to 100 ° C. Those skilled in the art will note that the glass transition temperature, vicat softening temperature and heat deflection temperature can indicate a degree of crystallinity. The values for merging the temperature range, density, Young's modulus and water content can be identical or similar to those in Table 1. Some characteristics may similarly vary in some way (for example, ± 25% or ± 10%) from the values shown for GS-270 and GS-300. NuPlastiQ or ESR has a

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62/122 amorphous structure (for example, more amorphous than typical raw starch). For example, typical raw starch powder has a largely crystalline structure (for example, greater than 50%), whereas NuPlastiQ or ESR has a large amorphous structure (for example, less than 10% crystallinity) . Any suitable standard can be used to measure glass transition temperature, heat deflection temperature, vicat softening temperature or any other physical characteristic. As an example, the glass transition temperature can be determined according to ASTM D-3418, heat deflection temperature by ASTM D-648 and vicat softening temperature by ASTM D-1525.

[00303] NuPlastiQ or ESR has a low water content, as described. As NuPlastiQ or ESR absorb moisture, they exhibit plastic behavior and become flexible. When removed from a humid environment, the material dries and becomes rigid again (for example, exhibiting less than about 1% water content again). The moisture present in NuPlastiQ or ESR (for example, in pelletized form) can be released as value during processing, such as that shown in Figure 1. As a result, films or other articles produced from a polymeric material to starch-based, such as NuPlastiQ or ESR mixed with a non-biodegradable plastic material, may exhibit an even lower water content, since the non-biodegradable plastic material will typically not include water content or a negligible water content, and water in NuPlastiQ or ESR it can typically be released during the manufacture of a desired article.

[00304] The low water content in the carbohydrate-based polymeric material can be important, since the significant water content can result in incompatibility with the non-biodegradable plastic material, particularly if the article requires the formation of a thin film. For example, as the water vaporizes, this can result in empty spaces within the film or other article, as well as other problems. During the blow and a film

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63/122 fine, the carbohydrate-based polymeric material used may preferably include at most about 1% water.

[00305] Low water content is not achieved in the NuPlastiQ or ESR material by means of esterification, as in some conventional TPS materials that may include relatively low water content. Such esterification can be expensive and complex to perform. The same can be said about etherification. In addition, NuPlastiQ or ESR materials that are exemplified by the carbohydrate-based polymer materials used in this document also typically do not typically include any identifiable starch, or identifiable glycerin, as such, since the NuPlastiQ or ESR or other starting materials carbohydrate-based polymeric material were chemically reacted and / or altered. The X-ray diffraction patterns of exemplary carbohydrate-based polymeric materials, as described below (for example, and shown in Figure 4) evidence such a chemical change, which shows that the finished polymeric material can be substantially starchless in such native identifiable form. In other words, the carbohydrate-based polymeric material is simply not recognized as a mixture that includes starch and glycerin. It is believed that the low water content obtainable in the carbohydrate-based polymeric material is, at least partially, due to the chemical alteration of the starch and plasticizers in a thermoplastic polymer, which does not retain water, as would native starch or thermoplastic starches. conventional.

[00306] Turning to Figure 1, processing at relatively high temperatures can result in some release of volatilized glycerin (for example, visible as smoke). If necessary (for example, when stored pellets may have absorbed additional water), pellet drying can be done simply by introducing hot dry air, for example, at 60 ° C for 1 to 4 hours, which is sufficient to eliminate the absorbed water. Pellets should be dried to less than about 1%

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64/122 moisture content before processing, particularly if a film is formed. NuPlastiQ or ESR pellets can simply be stored in a container sealed with a desiccant in a dry location, away from heat to minimize water absorption and prevent unwanted degradation.

[00307] In addition to NuPlastiQ or ESR being thermoplastic, NuPlastiQ or ESR can also be thixotropic, which means that the material is solid at room temperature, but flows like a liquid when heat, pressure and / or frictional movement are applied. Advantageously, NuPlastiQ or ESR pellets can also be used as pellets based on a petrochemical product (any non-biodegradable plastic resin pellets) in standard plastic production processes. NuPlastiQ or ESR materials and products produced from them can exhibit gas barrier characteristics. Products (eg films) produced using such NuPlastiQ or ESR pellets exhibit oxygen gas barrier characteristics (for example, see examples of the Applicant's previous deposits, already incorporated by reference). NuPlastiQ or ESR materials can be non-toxic and edible, produced using raw materials that are all edible. NuPlastiQ or ESR and products produced from them can be water resistant, but soluble in water. For example, NuPlastiQ or ESR can resist expansion under warmer conditions to the point where pellets (for example, 3 to 4 mm in size) may not completely dissolve in boiling water within 5 minutes, however a pellet will dissolve in your mouth in approximately 10 minutes. NuPlastiQ or ESR can be stable, in that they cannot exhibit any significant retrogradation, even if left in relatively high humidity conditions, where the characteristic is different from many other thermoplastic starch materials. Of course, products with NuPlastiQ or ESR can also exhibit such characteristics. If NuPlastiQ or ESR is stored in humid conditions, excess water absorbed

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65/122 can simply be evaporated, and when the water content is at most about 1%, it can be used in the formation of a film or other article.

[00308] NuPlastiQ or ESR material is also not typically subjected to biodegradation under typical storage conditions, even in relatively humid conditions, as other conditions of a landfill, compost or similar disposal environment containing the micro - particular necessary organisms are not present. Of course, when such conditions are present, not only is NuPlastiQ or biodegraded ESR, but otherwise, non-biodegradable plastic materials mixed with them also biodegrade surprisingly. Evidence of such surprising results is also included in the examples section, included in this document.

[00309] NuPlastiQ or ESR may have competing prices, as they are manufactured at a cost that competes with traditional polyethylene plastic resins. NuPlastiQ or ESR can be mixed with other polymers, including, but not limited to PE, PP, PET, polyester, polystyrene, acrylonitrile butadiene styrene (ABS), polyvinyl chloride, nylon and others. Although the non-biodegradable polymers above can become biodegradable by mixing with NuPlastiQ or ESR, it will be noted that NuPlastiQ or ESR can also be mixed with polymers that are already biodegradable and / or compostable, such as lactic polyacid (PLA), poly (adipate -butylene co-terephthalate) (PBAT), polybutylene succinate (PBS), polycaprolactone (PCL), polyhydroxyalkanoates (PHA), other starches then called thermoplastics, as well as several others. PBS, PCL and PHA are polyesters. EcoFLEX ™ is another example of a plastic material with which the NuPlastiQ material or the carbohydrate-based polymeric ESR can be mixed. For example, the present methods are not limited to mixing the carbohydrate-based polymeric material (eg NuPlastiQ or ESR) with only a non-biodegradable plastic material, as it will be noted that biodegradable plastics

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66/122 (other than NuPlastiQ or ESR) can also be incorporated into the mix, if desired.

[00310] As an additional explanation, PLA is compostable, which means that it can degrade under high temperature conditions (ie, composting conditions), but it is technically not “biodegradable”. Some of the materials listed above, such as PBS, PCL and PHA can be both biodegradable and compostable. EcoFLEX ™ is certified as compostable. The FTC ecological guidelines stipulate that it cannot be unqualified that a plastic is “degradable” unless it degrades in a “short period of time” (more recently defined as 5 years) “after common disposal”.

[00311] In some embodiments, NuPlastiQ or ESR could be supplied in a main batch formulation that can include the carbohydrate-based polymeric material as described above and an amount of one or more compatibilizers. The main batch may also include or more non-biodegradable plastic materials. Such main batch formulation pellets can be mixed with pellets of the non-biodegradable plastic material at the time of processing. Any conceivable reasons can be used in mixing such different pellets, depending on the desired percentage of NuPlastiQ or ESR and / or compatibilizer and / or non-biodegradable plastic material in the finished article.

[00312] NuPlastiQ or ESR includes a very low water content. For example, although raw starch (for example, used in ESR formation) can typically include about 13% water by weight, NuPlastiQ or ESR pellets available from BiologiQ include about 1% water. NuPlastiQ or ESR materials are biodegradable and, as described in this document, not only NuPlastiQ or ESR starch-based material is biodegradable, but when mixed with other polymers such as PE, PP, PET, polyester, polystyrene, ABS, polyvinyl chloride, non-biodegradable nylon and other non-biodegradable plastic materials, the material

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67/122 mixture becomes completely biodegradable. Such results are very surprising and particularly advantageous. The examples in this document provide evidence of such surprising results. Typical thermoplastic starch materials do not claim or exhibit such characteristics when mixed with other plastic materials.

[00313] The NuPlastiQ or ESR material may exhibit some elasticity, although its elasticity may be less than many other polymers (for example, particularly ecological sustainable polymers ”that mimic their petrochemical-based polymer equivalents). Films and other articles can be formed from mixtures of NuPlastiQ or ESR and any other desirable polymer (or polymer), which provides elasticity results that exhibit increased resistivity, at a given article thickness compared to the other polymer, alone . Although films are described and often used in the examples in this document, when resistivity is often of great importance, it will be evident that increased resistivity can also be provided in articles other than films (for example, bottles, sheets, boxes, cups, plates, utensils or other forms). Table 2 below shows values of elongation at break and modulus of elasticity for various standard plastic materials (“SP”), various “environmentally friendly” plastic materials and NuPlastiQ or ESR, for comparison. By "environmentally friendly", the material can have one or more desirable characteristics in environmental terms, such as being derived at least partially from a sustainable material, being compostable and / or being biodegradable. NuPlastiQ or ESR in Table 2 had a tensile strength of 40 MPa.

TABLE 2

MATERIAL ECOLOGICALLY CORRECT OR STANDARD PLASTIC Elongation at Break Modulus of elasticity Eco Flex EP 700% 0.10 GPa

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MATERIAL ECOLOGICALLY CORRECT OR STANDARD PLASTIC Elongation at Break Modulus of elasticity C1200 NuPlastiQ or ESR EP 100% 1.5 GPa HDPE SP 650% 0.80 GPa LDPE SP 550% 0.40 GPa PBS EP 450% 0.50 GPa PCL EP 600% 0.20 GPa PHA EP 300% 3.40 GPa PLA EP 150% 3.50 GPa PET SP 200% 2.50 GPa PP SP 500% 1.75 GPa ABS SP 25% 2.00 GPa nylon SP 100% 3.00 GPa

[00314] Figure 3 shows similar data as shown in Table 2, in the form of a graph. Of course, some of the products listed in the Table and shown in Figure 3 that are listed as standard plastics have ecological equivalents that can be derived from sustainable sources, such as, but not limited to, BioPET, ecological PP ”, ecological PE and bioPBAT. PLA is compostable, which means that it can degrade under high temperature conditions (ie, composting conditions), but it is technically not “biodegradable”. The other exemplary materials listed above, such as EcoFlex, PBS, PCL, PHA can be both biodegradable and compostable. The FTC ecological guidelines stipulate that it cannot be unqualified that a plastic is “degradable” unless it degrades in a “short period of time” (more recently defined as 5 years) “after common disposal”.

[00315] NuPlastiQ or ESR materials described as suitable for use in this document as polymeric material based on

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69/122 carbohydrates (for example, based on starch) are substantially amorphous. For example, raw starch powder (for example, as used in the production of eNuPlastiQ or ESR and various other thermoplastic starch materials) has an approximately 50% crystalline structure. The NuPlastiQ or ESR materials available from BiologiQ are different from many other commercially available thermoplastic starch (TPS) materials in crystallinity versus amorphous characteristics. For example, pages 62 and 63 of “Thermoplastic Starch Composites and Blends” a 'PhD thesis by Kris Frost (September 2010) declares the conclusion of gelatinization in TPS is of particular interest during processing and any subsequent trend towards retrogradation to form type V amylose crystals ”. Freezing continues “[the] loss of gelatinization involves loss of granular and crystalline structures by heating with water and often including other plasticizers or modifying polymers. Retrogradation is due to the rewinding of helical amylose coils. The broken starch molecules during gelatinization will slowly rewind in their helical dispositions or new helical conformations known as type V, which causes TPS films to quickly become brittle and lose optical clarity ”. Thus, conventional TPS tends to re-form a crystalline structure after the gelatinization process used to produce TPS from raw starch. In contrast, the NuPlastiQ or ESR material available from BiologiQ does not return to a largely crystalline structure. In addition, it can maintain a stable, relatively high degree of optical clarity, so as to be useful in forming relatively optically clear films (for example, particularly sandwiching NuPlastiQ or ESR containing layers between polyethylene or other layers of polyolefin ).

[00316] In contrast to typical TPS materials, NuPlastiQ or ESR materials which are suitable examples of polymeric starch-based materials for use in forming articles described in this application have an amorphous microstructure, and physical characteristics, as shown in

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Table 1. The difference in molecular structure between conventional TPS and NuPlastiQ or ESR materials is evidenced by NuPlastiQ or ESR materials, as described in this document, being much less crystalline than conventional starch-based thermoplastic materials, as shown by diffraction X-ray, shown in Figure 4, compared to the diffraction pattern results for NuPlastiQ or ESR material available from BiologiQ (sample 1) compared to a mix of raw native corn starch and raw native potato starch, a from which NuPlastiQ or ESR in Figure 4 was formed. The diffraction pattern of NuPlastiQ or ESR, as seen in Figure 4, is much less crystalline (for example, less than about 10% crystallinity) than that of native starch blending (about 50% crystallinity). The difference in the diffraction pattern shows that a chemical change occurred in the material, due to the processing of native starches in NuPlastiQ or ESR. For example, although there is a prominent diffraction peak between 20 to 25 ° with native starch, no peak is displayed on NuPlastiQ or ESR. Native starch additionally shows a high peak at about 45 ° (at an intensity of 0.5 to 0.6), with the peak being highly reduced in NuPlastiQ or ESR (only about 0.25 to 0.3). Across most of the spectrum, diffraction intensities are higher for native starches than for NuPlastiQ or ESR, with the exception of about 18 ° to about 22 °, as shown. The high diffraction intensity observed over the entire broad spectrum indicates greater crystallinity of native starches compared to NuPlastiQ or ESR. There are also numerous other differences, as shown.

[00317] As an example, the polymeric material based on carbohydrate (for example, based on starch) used in the production of films, according to the present disclosure, may have a crystallinity of less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, less than about 8%, less than about 6%, less than about 5%, or less than about 3%.

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Any suitable mechanism test to determine crystallinity can be used, for example, including, but not limited to, FTIR analysis, X-ray diffraction methods and symmetric transmission reflection techniques. Various suitable test methods will be apparent to those skilled in the art.

[00318] In addition to the differences in the microstructure of the finished NuPlastiQ or ESR compared to the starting materials, films, bottles, sheets, disposable utensils, plates, cups or other articles produced from a blend including the carbohydrate-based polymeric material are different from articles which are otherwise similar, but formed using conventional TPS and starch powder or non-biodegradable plastic materials only. For example, articles formed by mixing carbohydrate-based polymeric materials, such as NuPlastiQ or ESR, as described in this document with a non-biodegradable plastic material, do not have “sea island” features that are common during mixture of conventional TPS materials with polymeric materials, such as polyethylene. The properties of the different films can be observed by comparing the physical properties of films, as shown in Table 11 of Example 5 of Patent Application ² US 15 / 481,806 of the Applicant, already incorporated by reference. In particular, this Table compares the physical properties of films produced by mixing polymeric materials based on carbohydrates, as contemplated in this document with non-biodegradable polyethylene versus a conventional TPS mixed with PE (Cardia BL-F). In addition to the differences in properties in Table 11 of Example 5 of Applicant Patent No. US15 / 481,806, the film based on conventional TPS materials, such as Cardia BL-F, mixed with PE is neither biodegradable nor compostable.

[00319] As described in this document, the mixture of polymeric materials based on carbohydrates, as described in this document with a non-biodegradable plastic material, results not only in

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72/122 biodegradability of the carbohydrate-based material with the actual biodegradability of the non-biodegradable plastic material (even when the non-biodegradable plastic material alone is not biodegradable). Such results do not occur when mixing with typical TPS materials. Such differences in biodegradability clearly illustrate that there are structural and / or significant differences in the results films and in other articles, since the entire composite structure (that is, the film or another structure) is not capable of being biodegraded, as shown by the various examples to follow.

[00320] Without theoretical limitation, it is believed that polymeric resins based on carbohydrates can reduce the crystallinity of the mixed products, interrupting the crystallinity and / or hygroscopic barrier characteristics of polyethylene or other non-biodegradable plastic material in a way that allows water and bacteria degrade the dispositions and bonds of plastic molecules, otherwise non-biodegradable from the mixture next to the polymeric resin material based on carbohydrate. In other words, the long chains of polyethylene polymer or other non-biodegradable plastic material are more easily broken by chemical and mechanical forces that exist in environments that are rich in bacteria and microorganisms, when mixed with carbohydrate-based polymeric materials, as contemplated in this document. Subsequently, microorganisms that naturally exist in a disposal environment (for example, in a landfill) can consume the remaining smaller molecules that are converted back to natural components (such as CO2, CH4, and H2O).

[00321] For example, really biodegradable plastics decompose into natural elements or compounds, such as carbon dioxide, methane, water, inorganic compounds or biomass through microbial ingestion (for example, the enzymatic action of microorganisms in the molecules of plastic). Plastic biodegradation can be made possible by first breaking the polymer chains through action or

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73/122 chemical or mechanical, but this can be achieved completely only by decomposing the molecules by microbial ingestion.

[00322] Plastics produced from petrochemical raw materials or derived from plant sources start life as monomers (for example, single small molecules that can react chemically with other small molecules). When the monomers are joined, they become polymers (many parts), known as plastics. Before being joined, many monomers are readily biodegradable, although after being linked together through polymerization, the molecules become so large and joined in such arrangements and bonds that microbial ingestion by microorganisms is not practical within any period of time. sensible time.

[00323] Polymers are formed with both crystalline structures (regularly packaged) and amorphous structures (randomly arranged). Many polymers contain a high degree of crystallinity with some amorphous regions randomly arranged and woven throughout the polymeric structure.

[00324] The NuPlastiQ or ESR materials available from BiologiQ are formed from starch materials that are highly crystalline, however the plastic resin material of NuPlastiQ or ESR exhibits low crystallinity (substantially amorphous). Such polymeric starch-based materials are used as a starting material in the production of articles, as described in this document. Therefore, NuPlastiQ or ESR is plastic that is produced from starch. Due to the types of natural starch-based and carefully controlled binding, the plastic molecules (size and bonds) produced with NuPlastiQ or ESR are highly susceptible to biodegradation by enzymatic reactions caused by the introduction of the unit (water) and bacteria or other microorganisms, as evidenced by the experimental test results included in this document.

[00325] Polyolefins, such as rigid forms of polyethylene and

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74/122 polypropylene has a high degree of crystallinity and is produced by converting monomer molecules (whether derived from petroleum or derived from ethanol or other small building block molecules derived from plant sources) into long chain polymers. The bonds created during the connection of the monomers to form long polymer chains are strong and difficult to break. Films and other articles formed from such polymeric materials are not biodegradable. Even if a particular article had been formed from a mixture of conventional non-biodegradable plastic material and conventional TPS, it would not normally suddenly achieve biodegradable characteristics (different from the starch portion of the blend that can sometimes biodegrade).

[00326] The applicant has developed a process for providing biodegradability to an otherwise non-biodegradable plastic material by mixing such plastic material with the carbohydrate-based polymeric materials which have low crystallinity (for example, NuPlastiQ or ESR). Typically, the non-biodegradable plastic material has greater crystallinity (for example, particularly in the case of PE or PP).

[00327] In addition to biodegradability, the resulting blend may additionally or alternatively have a modulus of elasticity (stiffness or resistivity) greater than polyethylene or other non-biodegradable plastic material and can be used to produce plastic films or other articles that are stronger than the same articles produced with pure polyethylene or other pure non-biodegradable plastic material. Such characteristics of increased resistivity are described in Patent Application No. ² US 15 / 481,806, already incorporated by reference in the present document.

[00328] Turning to Figure 1, in 106 the process 100 includes mixing the one or more polymeric materials based on petrochemical product and the one or more polymeric materials based on carbohydrate to produce a mixture of materials. In some cases, the mixing of one or more other polymeric materials and the one or more carbohydrate-based materials can be performed

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75/122 using one or more mixing devices. In a particular deployment, a mechanical mixing device can be used to mix one or more other polymeric materials and one or more carbohydrate-based polymeric materials. In an implantation, at least a portion of the components of the material mix can be combined in an apparatus, such as an extruder, an injection molding machine or the like. In other deployments, at least a portion of the components of the material mix can be combined before being fed into the apparatus.

[00329] The one or more carbohydrate-based polymeric materials can be present in the mixture of materials in a wide variety of ranges depending on the desired characteristics. In one embodiment, such inclusion may be sufficient to provide biodegradability to another, otherwise non-biodegradable, polymeric material included in the blend, to increase the resistivity to a desired degree in order to provide a certain level of “sustainable” content or with another goal. For example, the carbohydrate-based polymeric material can be included in an amount of at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5% at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at most 99%, at most 95% maximum 90%, maximum 80%, maximum 70%, maximum 60%, maximum 50%, 2% to 98%, 20% to 40%, 10% to 40%, 20% 30%, 50% to 80%, or 40% to 60% by weight of the mixture of materials. More than one carbohydrate-based polymeric material and / or more than one other plastic material can be included in the mix, if desired.

[00330] The other polymeric material may be present in the mixture of materials in an amount of at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at most 99%, at the

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76/122 maximum 95%, maximum 90%, maximum 85%, maximum 80%, maximum 75%, maximum 70%, maximum 65%, or maximum 60%, from 2% to 98%, 50% to 90%, 65% to 75%, 20% to 50%, or 40% to 60% by weight of the mixture of materials.

[00331] A compatibilizer can be present in the mix of materials. The compatibilizer can be mixed with the other polymeric material, with the carbohydrate-based polymeric material, mixed with both or supplied separately. Often, the compatibilizer can be provided with at least one of the polymeric materials, for example, included in a main batch formulation. The compatibilizer can be a modified polyolefin or other modified plastic, such as a copolymer-grafted polypropylene, a copolymer-grafted polyethylene, a copolymer-grafted polybutene or a combination thereof. The compatibilizer can also include an acrylate-based copolymer For example, the compatibilizer can include an ethylene-acrylate copolymer, an ethylene-butyl acrylate copolymer or an ethylene-ethyl-acrylate copolymer. In addition, the compatibilizer may include a poly (vinylacetate) based compatibilizer. In one embodiment, the compatibilizer may be a grafted version of the other polymeric material (for example, polyethylene grafted with copolymer in which the other polymeric material is polyethylene) or a copolymer (for example, a block copolymer) in which one of the blocks it is the same monomer as the other polymeric material (for example, a styrene copolymer in which the other polymeric material is polystyrene or ABS).

[00332] The mixture of materials may include at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at most 50%, at most 45% maximum 40%, maximum 35%, maximum 30%, maximum 25%, maximum 20%, maximum 15%, maximum 10%, maximum 9%, maximum 8%, maximum 7% at most 6%, from 0.5% by weight to 12%, from 2% to 7%, or from 4% to 6% by weight of a compatibilizer.

[00333] Although certainly not required, and in at least some

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77/122 modalities the inclusion of the same would be better avoided, it is within the scope of the present invention to include any of a variety of degradable UV and OXO, such as PDQ-M, PDQ-H, BDA and OxoTerra ™ from Willow Ridge Plastics, 0X1014 from LifeLine or organic additives such as Restore® by Enso, EcoPure® from Bio-Tec Environmental, ECM Masterbatch Pellets 1M from ECM Biofilms or Biodegradable 201 and / or Biodegradable 302 from BioSphere®. Other additives can be included, for example, for increased resistivity (for example, Dupont's Biomax® Strong) or for another purpose.

[00334] One or more additives may be included in the mixture of materials in an amount of at least 0.5%, at least 1%, at least 1.5%, at least 2%, at least 2.5%, at least minus 3%, at least 4%, at most 10%, at most 9%, at most 8%, at most 7%, at most 6%, at most 5%, from 0.2% to 12%, 1% to 10%, 0.5% to 4% or 2% by weight to 6% by weight of the mixture.

[00335] Although described mainly in the context of a mixture of thermoplastic materials that can be fused together, in order to form a desired blend, in some embodiments, it may be possible to merge the carbohydrate-based polymeric material with another polymeric material other than it is thermoplastic (for example, which is thermoset, for example, as for silicone). For example, resin components that are precursors to such other non-thermoplastic polymeric materials can be mixed with the carbohydrate-based polymeric material, and polymerization or other formation of the other non-thermoplastic polymeric material can occur in the presence of the polymeric material at carbohydrate based, which results in a finished article that is a mixture of the polymeric material based on carbohydrate and another thermoplastic or non-thermoplastic plastic material. The carbohydrate-based polymeric material can provide any one of the same benefits to such non-thermoplastic material as described in this document (for example, increased sustainability, biodegradability,

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78/122 increased resistivity, etc.) by mixing the two together.

[00336] Referring to Figures 1, at 108, particularly, where the materials are thermoplastic, process 100 may include heating the mixture of materials. In a deployment, the material mix can be heated to a temperature of at least 100 ° C, at least 110 ° C, at least 115 ° C, at least 120 ° C, at least 125 ° C, at least 130 ° C at least 135 ° C, at least 140 ° C, at most 200 ° C, at most 190 ° C, at most 180 ° C, at most 175 ° C, at most 170 ° C, at most 165 ° C, at maximum 160 ° C, maximum 155 ° C, maximum 150 ° C, 95 ° C to 205 ° C, 120 ° C to 180 ° C, or 125 ° C to 165 ° C.

[00337] The material mixture that includes the other polymeric material and the carbohydrate-based polymeric material can be heated in one or more chambers of an extruder. In some cases, one or more extruder chambers can be heated to different temperatures The speed of one or more extruder screws can be any desired rate.

[00338] In 110, an article is produced using the mixture of materials. In some cases, the article may include a film. In other cases, the article can be formed from a film. In other embodiments, the article may have a shape based on a model, such as a mold (for example, injection molded). Any conceivable article formed from plastic can be formed from the mixture, for example, including, but not limited to, films, bags, bottles, lids, covers, sheets, boxes, plates, glasses, utensils and the like. When the article is a film, the film can be formed using a matrix by injecting a gas into the heated mixture of material to form the film (that is, blowing the film). The films can be sealed and / or otherwise modified in the form of a bag or other item.

[00339] When the article is a film, the film can be comprised of a single layer or of multiple layers. The film or any individual layers may be at least 0.001 mm, at least 0.002 mm, at least 0.004 mm, at least 0.01 mm, at least 0.02 mm thick,

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79/122 at least 0.03 mm, at least 0.05 mm, at least 0.07 mm, at least 0.10 mm, at most 2 mm, at most 1 mm, at most 0.5 mm, at most 0.1 mm, from about 0.05 mm to about 0.5 mm, or from 0.02 mm to 0.05 mm. Some specific examples may include films smaller than 0.005 mm, such as 0.002 mm to 0.004 mm, or 0.0025 mm (0.003 mm (0.1 mil)) to 0.25 mm (0.254 mm (10 mil)). Although there may be some overlap in thickness values for the film and sheet articles, it will be appreciated that sheet materials of thickness greater than such film values can of course be provided, produced by any desired plastic manufacturing process.

[00340] The ability to blow very thin films of 0.0025 mm (0.1 mil) was demonstrated by the Applicant with the use of blends, as described in this document, with very thin films exhibiting significant resistivity (for example, by minus 40 g in a dart drop impact, for a 0.0025 mm (0.1 mil) film, such as 40 g to 110 g dart impact resistance, or 40 g to 100 g for such very thin films) . It is believed that the ability to blow such very thin films is possibly unique to the Applicant, with the use of blends and other parameters (for example, blowing ratios, die spans etc.) as described in this document.

[00341] Films or other articles may have resistivity characteristics that are characterized by testing, such as a dart drop impact (ASTM D-1709), tensile strength test (ASTM D-882), test tensile strength (ASTM D-882), a secant module test (ASTM D-882) and / or an Elmendorf Tear Strength Test (ASTM D-1922). Films can have a dart drop impact value of at least 150 g, at least 175 g, at least 200 g, at least 225 g, at least 250 g, at least 275 g, at least 300 g, maximum 400 g, maximum 375 g, maximum 350 g, or maximum 325 g, 140 g to 425 g, 200 g to 400 g, 250 g to 350 g, 265 g to 330 g. In an implantation, these values can be for whatever the thickness of the

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80/122 film. In another implementation, these values may be for a 0.0025 mm (1 mil) thick film formed from the mixture of materials.

[00342] The article can be have a tensile strength at a break test value in the machine direction of at least 137,895.182 kPa (3.5 kpsi), at least 151,684.7 kPa (3.7 kpsi), at least 165,474.218 kPa (3.9 kpsi), at least 179,263.736 kPa (4.1 kpsi), at least 193,053.254 kPa (4.3 kpsi) or at least 206,842.773 kPa (4.5 kpsi) ), maximum 275,790.363 kPa (5.5 kpsi) maximum 262,000.845 kPa (5.3 kpsi), maximum 248,211.327 kPa (5.1 kpsi), maximum 234,421.809 kPa (4.9 kpsi) or a maximum of 220,632.291 kPa (4.7 kpsi), from 137,895.182 kPa (3.5 kpsi) to 275,790.363 kPa (5.5 kpsi) or 172,368.977 kPa (4.1 kpsi) at 241,316.568 kPa (4.9 kpsi).

[00343] The article can be have a tensile strength at a break test value in the machine direction of at least 137,895.182 kPa (3.2 kpsi), at least 151,684.7 kPa (3.4 kpsi), at least 165,474.218 kPa (3.6 kpsi), at least 26,200,085 kPa (3.8 kpsi), at least 27,579,036 kPa (4.0 kpsi), at least 193,053.254 kPa (4.2 kpsi) ) or at least 206,842.773 kPa (5.7 kpsi), at most 275,790.363 kPa (5.5 kpsi) at most 262,000.845 kPa (5.3 kpsi), at most 248,211.327 kPa (5.1 kpsi), a maximum of 234,421,809 kPa (4.9 kpsi) or a maximum of 32,405,368 kPa (4.7 kpsi) 220,632.291 kPa (4.5 kpsi), of 137,895,182 kPa (3, 2 kpsi) at 39,300.127 kPa (5.9 kpsi) or from 24.821,133 kPa (3.6 kpsi) at 34.473.795 kPa (5.0 kpsi).

[00344] The article may have a tensile strength stress test value in the machine direction of at least 550%, at least 560%, at least 570%, at least 580%, at least 590%, at least 600 %, at least 610%, at least 620%, at most 725%, at most 710%, at most 700%, at most 680%, at most 665%, at most 650%, at most 635%, 550% 750% or 600% to 660%.

[00345] The article can have a tensile strength test value in the transverse direction of at least 575%, at least 590%, at least 600%, at least 615%, at least 630%, or at least 645 %, at the

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81/122 maximum 770%, maximum 755%, maximum 740%, maximum 725%, maximum 710%, maximum 695%, maximum 680%, 575% to 775% or 625% to 700% .

[00346] When applicable, the article may have an Elmendorf tear resistance test value in the machine direction of at least 11,023.6 g / mm (280 g / mil), at least 11811 g / mm (300 g / mil ), at least 12,598.4 g / mm (320 g / mil), at least 13,385.83 g / mm (340 g / mil), or at least 14,173.2 g / mm (360 g / mil), at most 17,716.5 g / mm (450 g / mil), maximum 16,929.13 g / mm (430 g / mil), maximum 16,141.73 g / mm (410 g / mil), maximum 15,354.33 g / mm (390 g / mil), or a maximum of 14,566.93 g / mm (370 g / mil), from 10,826.77 g / mm (275 g / mil) to 18,700.79 g / mm (475 g / mil) ) or 325 g / mil to 16,141.73 g / mm (410 g / mil).

[00347] When applicable, the article may have an Elmendorf tear resistance test value in the transverse direction of at least 18,700.79 g / mm (475 g / mil), at least 19,291.34 g / mm (490 g / mil), at least 19,685 g / mm (500 g / mil), at least 20,669.3 g / mm (525 g / mil), at least 21,259.8 g / mm (540 g / mil), or at least least 21,653.54 g / mm (550 g / mil), maximum 27,559.1 g / mm (700 g / mil), maximum 26,771.7 g / mm (680 g / mil), maximum 25,590.6 g / mm (650 g / mil), maximum 24,606.3 g / mm (625 g / mil), maximum 23,622.05 g / mm (600 g / mil), maximum 22,834.6 g / mm (580 g) / mil), or a maximum of 22,440.9 g / mm (570 g / mil), from 18,700.79 g / mm (475 g / mil) to 28,543.31 g / mm (725 g / mil) or 19,291, 34 g / mm (490 g / mil) to 25,196.85 (640 g / mil).

[00348] When applicable, the article may have a secant modulus of the tensile test value in the machine direction of at least 137,895.182 kPa (3.7 kpsi), at least 151,684.7 kPa (22 kpsi), at least 165,474.218 kPa (24 kpsi), at least 179,263.736 kPa (26 kpsi), at least 193,053.254 kPa (28 kpsi) or at least 206,842,773 kPa (30 kpsi), at most 275,790,363 kPa (40 maximum 262,000,845 kPa (38 kpsi), maximum 248,211.327 kPa (36 kpsi), maximum 234,421,809 kPa (34 kpsi) or maximum 220,632,291 kPa (32 kpsi), from 137,895,182 kPa (20 kpsi) to 275,790.363 kPa (40 kpsi) or

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172,368.977 kPa (25 kpsi) to 241,316.568 kPa (35 kpsi).

[00349] When applicable, the article may have a secant modulus of the elasticity test value in the transverse direction of at least 137,895.182 kPa (3.5 kpsi), at least 151,684.7 kPa (22 kpsi), at least 165,474 , 218 kPa (24 kpsi), at least 179,263.736 kPa (26 kpsi), at least 193,053.254 kPa (28 kpsi) or at least 206,842.773 kPa (30 kpsi), at most 275,790.363 kPa (40 kpsi) ) maximum 262,000.845 kPa (38 kpsi), maximum 248,211.327 kPa (36 kpsi), maximum 234,421.809 kPa (34 kpsi) or maximum 220,632.291 kPa (32 kpsi), 137,895,182 kPa (20 kpsi) at 275,790.363 kPa (40 kpsi) or from 172,368.977 kPa (25 kpsi) to 241,316.568 kPa (35 kpsi).

[00350] In some cases, articles that include a carbohydrate-based polymeric material formed from a mixture of two or more starches have values of resistivity properties that are higher than articles that include a carbohydrate-based polymeric material formed from a single starch. For example, an article that includes a carbohydrate-based polymeric material formed from a mixture of two or more starches may have a dart drop impact value (in grams or g / mm (g / mil) in thickness) which is at least about 5% greater than, or 10% greater than an article where the carbohydrate-based polymeric material is formed from a single starch, at least about 25% greater than, at least about 50% greater than, at least about 75% greater than, 10% greater than 150% greater than or 60% greater than 120% greater than the same article but which includes a carbohydrate-based polymeric material formed from a single starch. It has been found that the details of such increased resistivity are within the examples in the present document, and Patent Applications No. ² US 14 / 853,725 and 15 / 481,806, already incorporated by reference.

[00351] Figures 1A, 1B, and 1C further illustrate particular examples of processes according to the present disclosure. These Figures are, therefore, generally covered by the more general steps of Figure 1, and by the description provided with them, which applies

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83/122 overall. For example, Figure 1A shows similar steps 102, 104, 106, and 108, but at 110 'the article produced is, in particular, a blown film, and the film blowing apparatus is operated so that the blowing ratio either at least 2.0, and / or the matrix span is at most 500 microns. In other words, Figure 1A illustrates an exemplary process 100 'that can be used to increase the resistivity of a blown plastic film, ensuring that a renewable carbohydrate-based polymeric material is included in a blend from which the plastic film is blown, and specifically selecting a high blowing ratio and / or narrow die span. At 102, process 100 may include providing one or more "other" polymeric materials, for example, including any plastic resins that can be blown into the film, such as polyethylene, polypropylene, other polyolefins, polyethylene terephthalate, polyester, nylon, polystyrene , ABS, polyvinyl chloride or the like. The "other" polymeric material can be a polymeric material based on a petrochemical product. It can also be an ecological version ”of such polymeric materials based on a petrochemical product (for example, such as ecological polyethylene, available from Braskeem or similar). It will be apparent that a wide variety of polymers may be suitable for use as "other" polymeric material.

[00352] At 104, process 100 may include providing the one or more carbohydrate-based polymeric materials, for example, may be specifically selected for inclusion in the blend for its recognized ability to increase resistivity when blown at a high blowing rate and / or narrow array span. The renewable carbohydrate-based polymeric material can be substantially amorphous, having a maximum crystallinity of 20%. Various other characteristics related to elastic modulus (i.e. Young's modulus), glass transition temperature, heat deflection temperature, vicat softening temperature or other characteristics may be additionally or alternatively present, as described in relation to NuPlastiQ materials or ESR examples available from BiologiQ,

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84/122 as described in this document. In 106 the materials can be mixed with each other in 106, forming a mixture of the materials. In 108, they can be heated (for example, melted in the case of thermoplastic materials) in preparation to blow a film from it. At 110 ', a plastic film is blown using a film blowing device using a mixture of materials. During such a blowing film, the blowing ratio employed can be at least 2.0. As described in this document, the Applicant found that the combination of including the carbohydrate-based polymeric material in the blend, and using a blowing ratio of 2.0 or greater allows for significant increases in resistivity for the film, particularly where also accompanied by a gap narrow matrix.

[00353] Multilayer films formed from a blend of Cardia BL-F and PE are described in document n ^Q WO 2014/0190395 by Leufgens, which are significantly weaker than the films currently described, due to the different TPS material used , as well as selection of the ratio of particular blowing characteristics and / or selected matrix span. For example, the blown film in Leufgens is 80 microns thick (that is, more than 0.76 mm (3 mils)), and exhibits resistivity that is in fact less than that of 100% PE film. In contrast, the particular selections described in this document allow for resistivity in any given thickness to actually increase compared to 100% control of “other polymeric material” (for example, PE). In addition, the present methods allow the production of films that have a desired level of resistivity in much smaller thicknesses. Such an ability to achieve a desired level of resistivity in significantly less thickness also reduces the amount of material that is used in the film layer, causing additional cost savings, and greater sustainability gains.

[00354] As described in this document, the blend of particular carbohydrate-based polymeric materials as described in

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85/122 present document with another polymeric material and then blow a plastic film with a film blowing apparatus using the mixture of materials, in a blowing ratio of at least 2.0 and / or with a narrow die span (for example, no more than 500 microns) has been found by the Applicant to provide thin films (for example, less than 0.051 mm (2 mil), for example, 0.003 mm (0.1) to 0.038 mm (1.5 thousand)) that, in fact, exhibit greater resistivity than an otherwise similar film, blown with only the first polymeric material (for example, PE).

[00355] Without limiting itself to any particular theory, it is believed that particular renewable carbohydrate-based polymeric resins that are substantially amorphous, when blown in such high blowing ratios and / or narrow die spans facilitate a desirable alignment, orientation , and / or stretching of the different polymer molecules in the blend, so as to increase the resistivity of the resulting merged plastic film.

[00356] For example, polymers are formed with both crystal structures (regularly packaged) and amorphous structures (randomly arranged). Many polymers (such as polyethylene) contain a high degree of crystallinity, although they may include some amorphous regions randomly arranged and woven throughout the polymeric structure. The particular renewable carbohydrate-based polymeric materials employed are not highly crystalline, but substantially amorphous. Although not limited to any particular theory, it is believed that the combination of the first crystalline polymeric material and the amorphous renewable carbohydrate-based polymeric materials undergo orientation, alignment, and stretching of the components, so as to allow the components to blend are homogeneously mixed with each other, but aligned and stretched in an oriented manner so that it results in increased resistivity. Such increases can be observed both in the machine direction (MD) and in the transversal direction (TD), so that the observed phenomenon is not simply the change of resistivity in one direction with that in another

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86/122 direction. This is evident in dart drop impact data, which considers resistivity in both directions.

[00357] Such increased resistivity through the selection of the material based on particular amorphous carbohydrate, and selection of the high blowing ratios, for example, and / or use of a narrow die span advantageously provides increased resistivity within a film thin, often thinner than achievable with another TPS that contains blends, such as Cardia BL-F. In some cases, the films can even be blown as thin as, or even thinner than is possible when blowing the first polymeric material by itself, as described in this document. For example, the Applicant observed an ability to blow films from and a blend of polyethylene and renewable carbohydrate polymeric material that are as thin as, or even thinner than, the thinner films that can be blown with polyethylene alone ( for example, the ability to blow 0.003 mm (0.1 mil) films.

[00358] As described in this document, articles that include a carbohydrate-based polymeric material that has low crystallinity and / or other characteristics as described in this document, and another polymeric material, formed in the high blowing ratios described and / or spans Narrow matrix materials can have values of resistivity properties that are greater than articles formed from the “other” polymeric material alone. Such an increase in resistivity is advantageous and surprising, for example, compared to the state of the art. For example, although Leufgens describes films blown from a mixture of a polymeric material based on starch (Cardia BL-F) and polyethylene, the resulting films exhibit lower tensile strength (Figure 2 of Leufgens), and lower impact resistance dart drop (Figure 5 by Leufgens) compared to an otherwise similar film formed from polyethylene alone. If so, even when the blend of Cardia BL-F and polyethylene is blown in a 3: 1 blowing ratio. This is evident that the increase in resistivity may not occur

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87/122 only with any renewable carbohydrate-based polymeric material, at least in the particular conditions used in Leufgens (which also included a relatively wide matrix span of 1.6 to 1.8 mm). As the examples show, increased resistivity occurs when using the present renewable carbohydrate-based polymeric materials that have low crystallinity and / or the other specific characteristics associated with NuPlastiQ or ESR.

[00359] Increases in resistivity (for example, if it is tensile strength, resistivity to the impact of dart fall, or other resistivity measurements) can be at least about 1%, at least about 2%, at least about 3%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, from 1% to 50%, from 1% to 40%, or from 10% to 40% compared to an article that is otherwise identical, but which is formed from the “other” polymeric material by itself (that is, in the renewable polymeric material based on carbohydrate or compatibilizer).

[00360] Figures 1B and 1C illustrate particular methods for a characteristic odor provided by the inclusion of the carbohydrate-based polymeric material in the blend. As will be apparent to those skilled in the art, any of the methods described in this document can be used together (for example, blowing a film in a high blowing ratio and / or narrow matrix span while also including an odor reducing agent) . Figure 1B illustrates an exemplary process 100 according to the present invention for producing an article that includes a carbohydrate-based polymeric material, an organic odor reducing agent and the polymeric resin. In 102, process 100 may include providing one or more "other" polymeric resins. Such resins can be any of a vast number traditionally used in the manufacture of plastics, as described in this document. In 103 and 104 respectively, process 100 includes providing an organic odor reducing agent and the carbohydrate-based polymeric material.

[00361] In one embodiment, the odor reducing agent could be

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88/122 included with the carbohydrate-based polymeric material (for example, included in a main batch of the same). In other embodiments, the odor reducing agent could be added via another route, for example, with the polymeric resin, separated from both the polymeric resin and the carbohydrate-based polymer, etc. It will be evident that several ways for such an addition are contemplated and possible. The odor reducing agent is specifically selected for inclusion in the blend for its ability to cancel an odor otherwise imparted to the finished product by the carbohydrate-based polymeric material. For example, the polymeric carbohydrate-based material may otherwise give a slight odor of burnt carbohydrate (for example, slightly burnt starch odor, an odor similar to popcorn or corn with caramel) that occurs during the heating process. blends (for example, during injection molding, blow molding, film blowing, or the like), in which the mixture of components at 102, 103, and 104 are fused together, and formed while in a heated condition.

[00362] The odor reducing agent at 103 can be in any desired shape (for example, pellets, powders, pollution, paste and / or liquid). In one embodiment, the odor reducing agent may initially comprise a lyophilized powder that can be mixed into a major batch of the carbohydrate-based polymeric material during manufacture, or after the manufacture of the carbohydrate-based polymeric material. For example, where the carbohydrate-based polymeric material is formed from a mixture of powder (or powders) of starch, glycerin, and water, the odor reducing agent (for example, as a lyophilized powder) could simply be added to the mixture with the starch powder (or powders), or water, or plasticizer (eg glycerin), and mixed with them. The carbohydrate-based polymeric material could then be manufactured by the same process by which it is normally produced, allowing the odor reducing agent to be incorporated into the carbohydrate-based polymeric material as a dispersed component in it (for example, dispersed in homogeneously in it).

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89/122 [00363] In another embodiment, the powdered agent or other odor-reducing agent could simply be mixed with the carbohydrate-based polymer as it is melted and prepared for combination with other components (for example, compatibilizing) that is included in the main batch. It will be evident to those skilled in the art that numerous possibilities exist for the odor reducing agent to any of the components that come to form a plastic article from a mixture of a polymeric material based on carbohydrate and another polymeric resin. Various such alternative routes for incorporating the organic odor reducing agent may also be suitable for use.

[00364] Regardless of the route selected for introducing the odor reducing agent into the blend, the blend of components at 102, 103, and 104 can be formed through any conceivable process, such as those described above, and elsewhere at present document.

[00365] The odor reducing agent can be organic. Elements skilled in the chemical technique will verify that organic compounds are carbon-based, but exclude simple carbon compounds such as carbides, carbonates, carbon oxides (for example, CO and CO2), and cyanides. In one embodiment, the organic odor reducing agent may include a benzyl group, being an aromatic compound. Various aromatic benzene derivatives, such as benzaldehydes and / or benzyl ketones, may be suitable for use. In one embodiment, the organic odor reducing agent may be a compound that includes only carbon, oxygen, and hydrogen atoms (for example, without hetero atoms). In other embodiments, compounds that include one or more heteroatoms may prove suitable for use. In an embodiment proven to be particularly effective, the odor reducing agent comprises a benzaldehyde compound, such as 4-hydroxy-3-methoxybenzaldehyde. Such an aromatic compound is also known as vanillin, which in the chemical structure shown below.

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90/122

, .ch ₃ [00366]

OH

A very small fraction of the organic odor reducing agent was found to be sufficient to cancel the odor associated with the carbohydrate-based polymeric material. In addition to the fact that so little odor reducing agent is needed, it is also surprising that problems associated with the addition of an organic component (the carbohydrate-based polymeric material) could be solved by adding even more organic component (or components). For example, an element skilled in the art can expect such inclusion of additional organic components, particularly one that has an aromatic chemical structure, to add to the odor released by the mixture through the heating process, instead of reducing or substantially eliminating such odors.

[00367] In one embodiment, no organic agents or other odor reducing agents are included within the composition. For example, in one embodiment, no activated carbon, zeolite, or other components known to include active sites capable of binding odorous volatile molecules are included within the composition. For example, the inclusion of such odor-reducing agents that operate in a mechanism that is based on binding active sites may somehow inhibit the ability of benzaldehyde or another organic odor-reducing agent to perform its intended function (for example, such sites active substances may merely serve to bind benzaldehyde or another organic odor reducing agent).

[00368] The odor reducing agent may comprise no more than 1%, no more than 0.5%, no more than 0.25%, no more than 0.1%, no more than 0, 05%, no more than 0.01%, no more than 1,000 ppm, no more than 500 ppm, no more than 250 ppm, no more than 100 ppm, no more than 50 ppm, or no more than 20 ppm, both of the material

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91/122 mixed plastic, or a carbohydrate-based polymeric material that includes the odor reducing agent provided in it (for example, as a main batch, to be mixed with another polymeric resin). By mixing such a carbohydrate-based polymeric material with another polymeric resin, the concentration of the odor reducing agent can, of course, be further diluted. For example, the concentration of such an odor reducing agent in the blended plastic article can be no more than 15 ppm, no more than 10 ppm, no more than 5 ppm, or even 1 ppm. It has been surprisingly found by the Applicant that such tiny fractions are effective in canceling out and substantially removing the characteristic odor of a plastic that includes a carbohydrate-based polymeric material.

[00369] In addition to vanillin, other extracts from various fruits and / or vegetables may also be suitable for use as organic odor reducing agents. Possible non-limiting examples include freeze-dried extracts of vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, passion fruit or raspberry. Combinations may also be suitable for use. [00370] As noted above, in one embodiment, the odor reducing agent can be added to water and / or glycerin (for example, dissolved or dispersed in it) used to form the carbohydrate-based polymeric material, which can be particularly beneficial in ensuring homogeneous mixing of the very small fraction of the odor reducing agent throughout the finished carbohydrate-based polymeric material. For example, although a powdery odor reducing agent could be added to the other powdered materials (eg, starch (or starches)) used to produce the carbohydrate-based polymeric material, due to the fact that the amount of the addition of the odor reducing agent is so small (for example, 20 ppm in the main batch), it may be easier to ensure homogeneous distribution of the odor reducing agent by mixing it with the component (or components) instead of with the powder (or powders) solid.

[00371] Although the addition of the odor reducing agent to the material

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92/122 carbohydrate-based polymer alter the odor characteristics by substantially removing any tendency of a mixture of the carbohydrate-based polymeric material and another thermoplastic polymeric resin to exhibit the odor of caramelized corn or otherwise popcorn, such inclusion does not substantially alter any of the physical properties or other properties of NuPlastiQ or ESR material, as described in this document. As verified, the odor reducing agent can be present in the polymeric NuPlastiQ based on carbohydrate or “ESR” material in a range of, at most, 1000 ppm, 500 ppm, 250 pp, 200 ppm, 100 ppm, 50 ppm, 40 ppm, 30 ppm, 25 ppm, 20 ppm, from 5 ppm to 50 ppm, from 10 ppm to 50 ppm, or from 15 ppm to 25 ppm. The Applicant found a level of 20 ppm in the NuPlastiQ or ESR material to be particularly effective. It will be evident that, upon dilution with the polymer resin material (or materials), the concentration of odor reducing agent in the article formed from such a mixture is even lower (for example, a level of 20 ppm in the main batch of NuPlastiQ or ESR can drop to only 10 ppm, only 5 ppm, or only 1 ppm in the finished article).

[00372] In some embodiments, NuPlastiQ or ESR could be supplied in a main batch formulation that may include the carbohydrate-based polymeric material as described above, the odor reducing agent, and an amount of one or more compatibilizers. The main batch may also include one or more "other" polymeric resins already included in the same (for example, the same polymeric resin with which the carbohydrate-based polymeric resin must be mixed to form a target article). Such main batch formulation pellets could be mixed with pellets of the "other" polymeric resin material at the processing time. Any conceivable reasons can be used in mixing such different pellets, depending on the desired percentage of NuPlastiQ or ESR and / or compatibilizer and / or conventional polymeric resin in the finished article.

[00373] As noted above, the odor reducing agent can be

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93/122 typically present in the carbohydrate-based polymeric material at a very low level, such as no more than 1%, no more than 0.1%, no more than 0.01%, no more than 1000 ppm, no more than 100 ppm, no more than 50 ppm, or no more than 20 ppm. By mixing the carbohydrate-based polymeric material that includes an odor-reducing agent with the polymeric resin, the level of odor-reducing agent in the resulting blended plastic article is reduced, depending on the mixing ratio between the carbohydrate-based polymeric material for the polymeric resin material. As noted in this document, a wide variety of mixing ratios are suitable. As an example, at a 1: 1 mixing ratio, if the initial level of odor reducing agent in the main batch of polymer-based carbohydrate material is 20 ppm, it has now dropped to only 10 ppm in the finished article plastic formed from the mixture. As the mixing ratio between 25% of the carbohydrate-based polymeric material and 75% of the polymeric resin material, an initial level of 20 ppm for the odor reducing agent has now dropped to 5 ppm.

[00374] It will be evident that, although the concentration of the odor reducing agent has decreased, the ratio of the odor reducing agent to the carbohydrate-based polymeric material remains unchanged due to such a mixture. For example, the weight ratio of the odor reducing agent to the carbohydrate-based polymer can be 1: 1000, or even more diluted. For example, the ratio can be 1: 1000, 1: 2000, 1: 5000, 1: 10,000, 1: 15,000, 1: 20,000, 1: 25,000, 1: 30,000, 1: 35,000, 1: 40,000, 1: 45,000 , 1: 50,000, 1: 60,000, 1: 70,000, 1: 80,000, 1: 90,000 or 1: 100,000. The ratio can be within the range between any two such values (for example, 1: 1,000 to 1: 100,000, or 1: 10,000 to 1: 80,000, or about 1: 50,000). A level of 20 ppm for the odor reducing agent in the carbohydrate-based polymeric material can be equivalent to a ratio of about 1: 50,000. Even when mixed with the polymeric resin material, this ratio can remain substantially constant since the addition of the polymeric resin material does not change the amount of the odor reducing agent

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94/122 or the carbohydrate-based polymeric material in the blend.

[00375] It will be evident that, although the odor reducing agent may be organic, it may be important that this component is not volatile, so that it is not simply separated during the hot pressing of the article (according to the residual water content in the carbohydrate-based polymeric material can be). For example, the odor reducing agent can be a solid, rather than a liquid at room temperature (eg 25 ° C) and pressure (eg 0.10 Mpa (1 atm)). If a liquid, the odor-reducing agent may exhibit a volatility that is less than that of water (for example, as measured against vapor pressures at a given temperature and pressure (for example, STP as noted above)). In one embodiment, the odor reducing agent may have a boiling point greater than any temperatures associated with processing at 108 and 110. The odor reducing agent may have a melting point that is less than a temperature associated with processing at 108 and / or 110. For example, the odor reducing agent can be a solid at room temperature (for example, 25 ° C), but it can be a liquid at an elevated temperature (for example, 125 ° C to 165 ° C ) in which processing occurs. 4-hydroxy-3-methoxybenzaldehyde is an example of such an odor reducing agent.

[00376] For example, the odor reducing agent may have a melting point that is at least 30 ° C, at least 50 ° C, less than 200 ° C, less than 190 ° C, less than 180 ° C, less than 175 ° C, less than 170 ° C, less than 165 ° C, less than 160 ° C, less than 150 ° C, less than 145 ° C, less than 140 ° C , less than 135 ° C, than 130 ° C, less than 125 ° C, less than 120 ° C, less than 115 ° C, less than 120 ° C, less than 115 ° C, less than 110 ° C, less than 100 ° C, 50 ° C to 180 ° C, 50 ° C to 150 ° C, or 60 ° C to 100 ° C. The odor-reducing agent may have a boiling point greater than 150 ° C, greater than 160 ° C, greater than 170 ° C, greater than 180 ° C, greater than 200 ° C, greater than 225 ° C, greater than 250 ° C, from 150 ° C to 500 ° C, from 200 ° C to 400 ° C,

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95/122 or 250 ° C to 300 ° C. For example, vanillin melts at 81 ° C to 83 ° C, and boils at 285 ° C.

[00377] Although Figure 1B illustrates how an article can be produced from a polymeric resin (in 102), an odor reducing agent (in 103), and a carbohydrate-based polymeric material (in 104), Figure 1C illustrates a 100 'process by which the odor reducing agent can be incorporated into the carbohydrate-based polymeric material. For example, the odor reducing agent can be supplied in 103, the carbohydrate-based polymeric material is supplied in 104, and they are mixed together in 106. As an example, this can occur where the odor reducing agent organic is mixed with the carbohydrate-based polymeric material when formulating a main batch (for example, in which the odor reducing agent is added to the carbohydrate-based polymeric material while also adding a compatibilizer or other components to be included in the main batch) . In another embodiment, the odor reducing agent can be mixed with the starting material (or materials) from which the carbohydrate-based polymeric material is formed (for example, by mixing the odor reducing agent in one or more among water, glycerin, or starch components, of which the polymeric material based on carbohydrate is formed). In any case, the selected method results in a carbohydrate-based polymeric material that includes the odor reducing agent dispersed in it. Its concentration can be very low (for example, 20 ppm), as described in this document. In 110 ', such a carbohydrate-based polymeric material (which includes the odor reducing agent) can be used to produce an article by mixing with a polymeric resin (for example, which typically involves the application of heat, to melt and mix the thermoplastic materials with each other).

[00378] Returning to the standard characteristics that can apply to any of the modalities described in this document, subject to biodegradation test (for example, if potential biomethane test, or any applicable ASTM standard, such as ASTM D-5511, ASTM D-5526,

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ASTM D-5338, or ASTM D-6691) can be characterized. Upon such a test, and within a given period of time (for example, 30 days, 60 days, 90 days, 180 days, 365 days (1 year), 2 years, 3 years, 4 years, or 5 years, the article may show substantial biodegradation of the total polymer content, and / or any “other” non-biodegradable polymer content (separate from the carbohydrate-based polymer content). The potential biomethane test is typically conducted for 30 or 60 days, although sometimes for 90-day period. The largest time period tests are most typically performed under any of the ADTM standards mentioned above. For example, an article that can be free or substantially free of a biodegradation enhancing additive may show biodegradation that is greater than the content of the carbohydrate-based polymeric material therein, indicating that the other plastic material (or materials) is also biodegradable (or exhibits the potential to biodegrade under a potential biomethane test).

[00379] Particularly, when submitting articles to a test that simulates biodegradation under landfill or other conditions of disposal and / or degradation (for example, composting conditions, or marine conditions) for 180 days, 200 days, 365 days (1 year) ), 2 years, 3 years, or 5 years, biodegradation may be greater than the weight percentage of carbohydrate-based polymeric materials within the article. In other words, the inclusion of the described carbohydrate-based polymeric materials can result in at least one biodegradation of an "other" otherwise non-biodegradable polymeric material.

[00380] For example, an article that is formed from a mixture of polymeric materials based on carbohydrate and PE can exhibit biodegradation after such periods of time which is greater than the weight fraction of the polymeric materials based on carbohydrate in film, indicating that PE (until now considered non-biodegradable) is in fact biodegraded, with the polymeric material based on carbohydrates. Such results are surprising and particularly advantageous.

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97/122 [00381] The potential biomethane test determines the potential for anaerobic biodegradation based on methanogenesis as a percentage of total methanogenesis potential. The potential biomethane test can be used to predict biodegradability of the samples tested according to the ASTM D-5511 standard and the potential biomethane test can be conducted using one or more conditions of the ASTM D-5511 standard. For example, the potential biomethane test can take place at a temperature of about 52 ° C. In addition, the potential biomethane test may have some conditions that are different from those of ASTM D-5511, for example, to speed up the test to be completed within the typical 30, 60, or sometimes, the duration of 90 days. The potential biomethane test can employ an inoculum that has 50% to 60% by weight of water and 40% to 50% by weight of organic solids. For example, an inoculum used in the potential biomethane test can have 55% by weight of water and 45% by weight of organic solids. The potential biomethane test can also occur at other temperatures, such as from 35 ° C to 55 ° C or from 40 ° C to 50 ° C.

[00382] When submitted to the biodegradation test, an article that has no more than about 2% by weight of a biodegradation intensification additive (or preferably, being free of it) and that has a quantity of polymeric material to carbohydrate-based and “other” polymeric material as described in this document may exhibit marked degradation as a result of the introduction of the carbohydrate-based polymeric material in the article. For example, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% of the polymeric non-carbohydrate material (for example, the “other” polymeric material) can biodegrade for a period of at least about 1 year, at least about 2 years, at least about 3 years, or at least about

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98/122 of 5 years when submitted to landfill, composting, and / or marine conditions (or conditions that simulate such). Such biodegradation is particularly notable and advantageous. In this way, not only the polymeric material based on biodegraded carbohydrates, but the “other” polymeric material as well, even where the material is otherwise non-biodegradable on its own.

[00383] The examples show that, with increased time, the amount of biodegradation can be very high, so that, in at least some deployments, substantially the entire biodegraded article (for example, biodegradation of at least about 85%, at least least about 90%, or at least about 95% within 180 days, or 200 days, or 365 days (1 year), within 2 years, within 3 years, within 5 years, or another period). [00384] Figure 2A illustrates components of an exemplary manufacturing system 200 for producing articles in accordance with the present disclosure. In some cases, manufacturing system 200 can be used in process 100 of Figure 1, or any of those in Figure 1A to 1C. In an illustrative example, manufacturing system 200 is an extruder, such as a single screw extruder or twin screw extruder.

[00385] In an implantation, one or more non-biodegradable plastic materials and one or more polymer-based carbohydrate materials are supplied by means of a first hopper 202 and a second hopper 204. A compatibilizer can be included with either one or both. materials (for example, in a main batch of the same).

[00386] The one or more carbohydrate-based polymeric materials and the one or more non-biodegradable plastic materials can be mixed in a first chamber 206 to produce a mixture of materials. In some cases, the mix of materials may include from 5% by weight to 40% by weight of the one or more carbohydrate-based polymeric materials, from 60% by weight to 94% by weight of one or more non-biodegradable plastic materials , and from 1% by weight to 9% by weight of the one or more compatibilizers. As described in this document, a small amount of odor reducing agent

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99/122 may also be present. Of course, the ranges can be varied outside of the above ranges, depending on the desired characteristics.

[00387] In the exemplary implantation shown in Figure 2A, the mixture of materials can pass through several chambers, such as the first chamber 206, a second chamber 208, a third chamber 210, a fourth chamber 212, a fifth chamber 214, and a sixth optional 216 camera. The material mix can be heated in chambers 206, 208, 210, 212, 214, 216. In some cases, a temperature in one chamber may be different from the temperature in the other chamber. In an illustrative example, the first chamber 206 is heated to a temperature of 120 ° C to 140 ° C; the second chamber 208 is heated to a temperature of 130 ° C to 160 ° C; the third chamber 210 is heated to a temperature of 135 ° C to 165 ° C; the fourth chamber 212 is heated to a temperature of 140 ° C to 170 ° C; the fifth chamber 214 is heated to a temperature of 145 ° C to 180 ° C; and the optional sixth chamber 216 is heated to a temperature of 145 ° C to 180 ° C.

[00388] The heated mixture can then be extruded using a matrix 218 to form an extruded object, such as a film, sheet or the like. Injection molding, thermoforming, or other plastic production processes can be used to manufacture various items such as utensils, plates, cups, bottles, covers or lids of the same or similar. In the blowing film, a gas can be injected into the extruded object to expand it with a pressure of 10.5 Mpa (105 bar) to 14 Mpa (140 bar). The resulting tube 220 can be drawn through rollers 222 to create a film 224 with a thickness typically from 0.02 mm (about 0.8 mil) to 0.051 mm (about 2 mil). Even thinner films can be made using blends as described in this document, for example, having a thickness as small as (0.1 mil) (0.0025 mm). Of course, thicknesses greater than 2 thousand can also be achieved. In some cases, film 224 can be comprised of a single layer. In other cases, the film 224 can be comprised of multiple layers. Where

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100/122 multiple layers are present, at least one of the layers can include the carbohydrate-based polymeric material. In some embodiments, the carbohydrate-based polymeric material may be present in one or more outer layers. In another embodiment, the carbohydrate-based polymeric material may be present in an inner layer. Where no carbohydrate-based polymeric material is included in the outer layer (or layers), biodegradation of the outer layer (or layers) may not occur. [00389] Figures 2B and 2C schematically illustrate the matrix 218, and the bubble formation 220, which shows additional details in relation to the blown film apparatus of Figure 2, and which shows particularly how the blowing ratio characteristics vary from matrix can be particularly selected for increased resistivity. As shown in Figures 2B and 2C, matrix 218 can include an outer member 218a and an inner member 218b, with a matrix gap 226 defined between them. As described in this document, matrix 218 can be particularly configured to provide a narrow matrix span, for example, less than 1000 microns, less than 900 microns, less than 800 microns, less than 700 microns, less than than 600 microns, or less than 500 microns (for example, 200 to 500 microns). This narrow die span is in sharp contrast to the wide die spans used (and perhaps necessary) in the prior art when blowing films that include other thermoplastic starch components. For example, Leufgens describes matrix spans from 1.6 to 1.8 mm (i.e., 1600 to 1800 microns). Even at a high blowing rate, the use of such a large matrix span may make it possible to obtain the increases in resistivity described in this document.

[00390] Figure 2B further illustrates the relatively high blowing ratio, which is defined as the ratio between the maximum bubble diameter (Db) divided by the diameter in the matrix gap (Dd). Stated differently, in relation to the flat width of the film, the blowing ratio is equal to 0.637 * (Flat Width) / Do. The freezing line 228 is also shown in

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Figure 2B, the point at which the previously melted material of the bubble begins to crystallize, in order to have a more translucent appearance above such a region of crystallization in the freezing line 228. As described in this document, the blowing ratio is at least 2.0, for example, 2,1,2,2, 2,3, 2,4, 2,5, 2,6, 2,7, 2,8, 2,9, 3,0, 2,2 at 2.8, or about 2.5. The Applicant observed increased resistivity for the film simply by increasing the blowing ratio, from a typical blowing ratio of blowing, for example, 1.5 to a value of at least 2, such as 2.5 . It was observed that the resistivity was observed to increase to values of up to about 3, after which no significant increase in resistivity was observed, so that values of 2 to 3, 2.2 to 2.8, or about 2, 5 are particularly appropriate. As described in this document, the matrix span can be maintained at a restricted value, to also contribute to increases in resistivity, by blowing blends that include the particularly described polymer materials based on renewable carbohydrates.

[00391] As an example, matrix spans of less than 500 microns and blowing ratios of at least 2 (for example, 2.2 to 2.8, or about 2.5) are particularly suitable for blowing films of such blends that are up to 0.038 mm (1.5 mil) thick (for example, 0.003 mm (0.1 mil) to 0.038 mm (1.5 mil)). In order to blow thicker films (where a thicker film was needed), the matrix gap may need to be increased to accommodate the flow of the molten material through it. For example, in order to blow a very thick film of 0.254 mm (10 mil), or even 5 mils, the matrix gap may need to be increased in some way (although the value may be even less than 1000 microns, or even less than 500 microns).

[00392] The concepts described in this document will be further described in the following examples.

EXAMPLES

EXAMPLE 1 [00393] Eleven starch-based polymers were formed from 27%

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102/122 tallow glycerin (99% pure glycerin) and 73% starch, exclusive of water. Each finished starch-based polymer exhibited <about 1% water, and was mixed with LLDPE and anhydride-modified LLDPE in proportions of 25%, 70%, and 5%, respectively, by weight. The resulting mixtures were then extruded and blown onto films. 70% of each film was LLDPE, 25% was the starch-based polymer, and 5% of each film was LLDPE modified with anhydride. The films were then tested using a drop dart impact test in accordance with ASTM D-1709. The combinations of starches tested and resistivity test results (in grams) are shown in Table 3. The results in Table 3 show that samples formed from the starch mixture have dart drop impact values that are greater than the values of dart drop impact of samples formed from a single starch.

TABLE 3

Sample N ^and Starch content (%) Thickness (mm (mil)) Dart test (g) Dart impact resistance (g / mil) Percentage of increased dart impact resistivity (%) Potato Corn Tapioca 1 0 100 0 0.039 (1,535) 347 8,901.57 (226.1) AT 2 100 0 0 0.039 (1,535) 362 9,283.46 (235.8) AT 3 0 0 100 0.0394 (1,550) 367 9,322.83 (236.8) AT 4 80 20 0 0.0394 (1,550) 387 9,830.70 (249.7) 6.8% 5 0 20 80 0.0394 (1,550) 387 9,830.70 (249.7) 6.4% 6 0 80 20 0.0394 (1,550) 387 9,830.70 (249.7) 9.4% 7 0 10 90 0.0394 (1,550) 387 9,830.70 (249.7) 5.9% 8 33.33 33.33 33.33 0.0381 (1,500) 387 258 10.9% 9 80 0 20 0.0381 (1,500) 387 10,157.5 (258) 9.3%

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Sample N ^and Starch content (%) Thickness (mm (mil)) Dart test (g) Dart impact resistance (g / mil) Percentage of increased dart impact resistivity (%) Potato Corn Tapioca 10 10 0 90 0.0381 (1,500) 387 10,157.5 (258) 9.0% 11 0 90 10 0.0381 (1,500) 387 10,157.5 (258) 13.6%

[00394] Figure 5 graphically shows impact test resistivity for different thickness films (0.013 mm (0.5 mil)), 0.025 mm (1 mil), 0.038 (1.5 mil), 0.051 mm (2.0 thousand)) based on the percentage of NuPlastiQ based on starch or “ESR” in the film. The NuPlastiQ or ESR used in the formed films shown in Figure 5 was formed from a mixture of starches that includes 90% corn starch and 10% potato starch. Figure 5 shows how the resistivity of the film increases with a percentage of NuPlastiQ or increasing ESR, up to a maximum resistivity of about 20% to about 25% of NuPlastiQ or ESR. The balance of the blend included polyethylene and an appropriate compatibilizer, as described in this document.

[00395] Figure 6A graphically shows impact test resistivity for different thickness films (from about 0.003 mm (0.1 mil) to 0.051 mm (2 mil)) for films that include 25% polymeric material based on carbohydrate, with the balance being a small fraction of compatibilizer (for example, about 5%) as described in this document, and PE (about 70%). Figure 6 also shows comparative resistivity for 100% PE films, which are at all lower points than for the blend according to the present disclosure. Figure 6 additionally shows several other benchmarks tested for production bags (for example, bags provided to consumers in a supermarket production section to maintain production), for various “walk” bags (for example, grocery and other plastic bags provided for making), and for potato bags (plastic bags typically used to hold (2,268

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104/122 kilograms, 4,536 kilograms or 9,072 kilograms 5, 10 or 20 pounds) of potatoes in the production section of a supermarket). Example 8 is similar, but it shows results for a blend in which the “other” polymeric material is biopolyethylene, instead of synthetic LLDPE derived from oil sources. [00396] Figure 7 graphically shows impact test resistivity for different thickness films (from less than 0.013 mm (0.5 mil) to about 0.051 mm (2 mil)) for several films merged in accordance with this development, as well as comparative films (eg 100% LLDPE, 100% recycled LLDPE (rLLDPE). In addition to showing resistivity characteristics for a film formed from virgin materials (25% NuPlastiQ or ESR, 70% LLDPE, 5% compatibilizer (labeled 25% NuPlastiQ or ESR / 75% LLDPE), Figure 7 also shows resulting resistivity when such recycled material (rLDESR) is then mixed with virgin materials (labeled 25% NuPlastiQ or ESR / 25% rLDESR / 50% LLDPE), or where recycled LLDPE (rLLDPE) is used in the blend (labeled 25% NuPlastiQ or ESR / 25% rLLDPE / 50% LLDPE) .Resistability results are improved compared to use of polymeric PE materials as shown, additional the previously described characteristics of increased renewability and biodegradability. EXAMPLE 2 [00397] Three samples were tested for 349 days to determine biodegradable characteristics according to ASTM D-5511. The test was designed to replicate the conditions of a full-scale anaerobic digester (landfill). The results of the three samples (referred to as 1342, 1343, and 1344) are shown in Figures 8A to 8B and Table 4. Figure 8A shows results for all samples 1343, 1343, and 1344, compared to controls. Figure 8B shows the results for sample 1344 alone, compared to samples. Sample 1342 was formed from 30% NuPlastiQ or ESR (the substantially amorphous carbohydrate-based polymeric material with less than 10% crystallinity), 67% PBAT, and 3%

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105/122 compatibilizer, and had a thickness of 1.1 mil. Sample 1343 was formed from 27.5% NuPlastiQ or ESR, 70% PBAT and 2.5% compatibilizer, and had a thickness of 0.025 mm (1.0 mil) Sample 1344 was formed of 40% NuPlastiQ or ESR, 56% LLDPE and 4% compatibilizer, and had a thickness of 0.025 mm (1.0 mil)

TABLE 4

Inoculum Negative Positive 1342 1343 1344 Cumulative Gas Volume (ml) 4,064.3 4898.8 12330.2 18429.0 20233.7 31171.1 Percentage of CH ₄ (%) 43.2 43.6 41.4 48.8 53.7 51.7 Volume CH ₄ (ml) 1757.0 2135.1 5101.0 8992.6 10865.0 16106.6 Mass CH ₄ (g) 1.26 1.53 3.64 6.42 7.76 11.5 Percentage of CO ₂ (%) 40.4 37.8 41.9 35.5 35.7 38.0 Volume of CO ₂ (ml) 1643.0 1852.9 5160.5 6547.5 7230.7 11838.7 Mass CO ₂ (g) 3.23 3.64 10.14 12.86 14.20 23.25 Sample Mass (g) 10 10 10 20.0 20.0 20 Theoretical Sample Mass (g) 0.0 8.6 4.2 9.8 9.8 13.7 Biodegraded Mass (g) 1.82 2.14 5.50 8.33 9.69 14.97 Percentage of Biodegraded (%) 3.7 87.1 66.4 80.2 95.8

[00398] Figures 8A to 8B show that after 204 days, the negative control showed 2.5% degradation, the positive control showed 86.5% degradation, sample 1342 showed 43.3% degradation, sample 1343 showed 53.9% degradation, and sample 1344 showed 77.2% degradation. At 349 days, the degradation values are as shown in Table 4.

[00399] Biodegradation after 349 days is particularly excellent. Per

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106/122 example, although samples including PBAT (1342 and 1343) show very satisfactory biodegradation, with the percentage of biodegradable being much higher than the fraction of the carbohydrate-based polymeric material included in the film, sample 1344 (see Figure 8B) is even more surprising, showing almost 96% biodegradation (even greater than the positive control), where the plastic non-biodegradable material is polyethylene, which, under normal circumstances, is evidently not biodegradable (for example, consult the negative control, in Table 4 which was 100% polyethylene). Such results of biodegradation are remarkable, and particularly advantageous.

EXAMPLE 3 [00400] Potato packaging bags made with a mixture of 25% NuPlastiQ or ESR, 70% LLDPE and 5% compatibilizer were tested for anaerobic biodegradation after 60 days, 107 days, 202 days, 317 days, 439 days, 573 days, and 834 days according to ASTM D-5526. The test was designed to replicate the conditions of a full-scale anaerobic digester (landfill). The test was conducted under various conditions, with an inoculum that has about 35%, 45%, and 60% organic solids with the balance being water. The results for the inoculum that includes 35% organic solids (and 65% water) are shown in Figure 9 and Table 5A. Table 5B shows results for several other inocula, and for other samples. The potato bags had a thickness of 0.343 mm (1.35 mil). These bags are referred to as sample 1072.

TABLE 5A

35% Solids in 60 days 35% Solids in 107 days 35% Solids in 202 days 35% Solids in 317 days 35% Solids in 439 days 35% Solids in 573 days 35% Solids in 834 days 7.60% 11.80% 24.10% 39.40% 60.50% 71.70% 80.70%

[00401] Potato bags produced with 25% NuPlastiQ or ESR, and

70% LLDPE showed remarkable 81% biodegradation for 834 days under

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107/122 simulated landfill conditions. NuPlastiQ or ESR is homogeneously mixed with polyethylene, and results advantageously in the long carbon chains of polyethylene being broken down, and digested by the same microorganisms that consume the NuPlastiQ material or carbohydrate polymeric ESR. Such results show that the entire bag, which includes polyethylene, is biodegraded into carbon dioxide, methane and water. Such results are surprising and particularly advantageous.

[00402] The test conducted with 45% organic solids and 60% organic solids also showed results in which the percentage of biodegradation exceeded the percentage of NuPlastiQ or ESR included in the potato bag. Tests were also carried out with similar potato bags that include 1% of a biodegradation enhancing additive (sample 1073), and other similar potato bags that include compostable resin EcoFLEX ™, and metallocene LLDPE (sample 1075).

TABLE 5B

Negative Control Positive Control Percentage of solids 60% 45% 35% 60% 45% 35% Percentage of biodegraded in 834 days 1.20% 0.5% 1.5% 91.2% 91.2% 91.4%

Sample 1072 Sample 1073 Percentage of solids 60% 45% 35% 60% 45% 35% Percentage of biodegraded in 834 days 58.3% 67.7% 80.7% 54.5% 67.9% 80.3% Sample 1075 Percentage of solids 60% 45% 35%

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Percentage of biodegraded in 834 days

72.7%

83.3% 86.1%

EXAMPLE 4 [00403] Films made with a mixture of NuPlastiQ or ESR and LLDPE were tested for anaerobic biodegradation after 201 days and 370 days according to ASTM D-5338. The conditions were intended to be conditions of simulated aerobic digestion and / or industrial compound. The tested films are labeled 1345 and 1346 in Table 6 and Figures 10A to 10B, which show the results after 370 days. In 201 days, samples 1345 and 1346 respectively showed adjusted percentage values of 74.2% and 72.4%, while the negative control showed -3.3% and the positive control showed 100%. Figures 10A to 10B plot actual% biodegradation. Sample 1345 included 25% NuPlastiQ or ESR, 72.5% LLDPE, and 2.5% compatibilizer. Sample 1346 included 40% NuPlastiQ or ESR, 56% LLDPE, and 4% compatibilizer. Both films had a thickness of 0.025 mm (1.0 mil)

TABLE 6

Inoculum Negative Positive 1345 1346 Cumulative Gas Volume (ml) 3168.2 2864.3 10740.0 27603.3 24364.9 Percentage of CO ₂ (%) 81.4 82.6 83.5 89.3 87.8 Volume of CO ₂ (ml) 2577.8 2366.4 8965.3 24638.1 21400.0 Mass CO ₂ (g) 5.06 4.65 17.61 48.40 42.04 Sample Mass (g) 1000 10 10 20.0 20.0 Theoretical Sample Mass (g) 0.0 8.6 4.2 15.0 13.7 Biodegraded Mass (g) 1.38 1.27 4.80 13.20 11.46

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Inoculum Negative Positive 1345 1346 Percentage of Biodegraded (%) -1.3 81.1 78.8 73.5 Adjusted percentage of biodegraded (%) -1.6 100.0 97.2 90.7

[00404] Biodegradation after 370 days, especially in sample 1345, is particularly excellent. This sample (see Figure 10B) shows more than 97% biodegradation in which the plastic non-biodegradable material is polyethylene, which under normal circumstances is, of course, non-biodegradable (for example, see the negative control in Table 6 which had 100% polyethylene). Such results of biodegradation are remarkable, and particularly advantageous.

EXAMPLE 5 [00405] Films made with a mixture of NuPlastiQ or ESR and PBAT were tested for anaerobic biodegradation after 205 days in accordance with ASTM D-6691, which is intended to simulate marine conditions. The tested films are labeled 1439 and 1440 in Table 7 and Figure 11. In 205 days, samples 1439 and 1440 respectively showed adjusted biodegraded percentage values of 49.6% and 53.6%. Sample 1439 included 30% NuPlastiQ or ESR, 67% PBAT, and 3% compatibilizer. Sample 1440 included 27% NuPlastiQ or ESR, 70% PBAT, and 2.5% compatibilizer. Sample film 1439 had a thickness of 0.0279 mm (1.1 mil), and sample film 1440 had a thickness of 0.025 mm (1.0 mil)

TABLE 7

Inoculum Negative Positive 1439 1440 Cumulative Gas Volume (ml) 22.0 25.4 86.7 61.6 65.2 Percentage of CO ₂ (%) 91.8 85.4 88.7 91.7 91.3 Volume of CO ₂ (ml) 20.2 21.7 76.9 56.4 59.5

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Inoculum Negative Positive 1439 1440 Mass CO ₂ (g) 0.040 0.043 0.151 0.111 0.117 Sample Mass (g) 0.080 0.080 0.080 0.080 Theoretical Sample Mass (g) 0.069 0.034 0.039 0.039 Biodegraded Mass (g) 0.011 0.012 0.041 0.030 0.032 Percentage of Biodegraded (%) 1.2 90.0 49.6 53.6

EXAMPLE 6 [00406] Additional fabricated films were tested for biodegradability. Table 8 below summarizes the results of such a test, some of which are described in detail above. Such a test shows excellent biodegradability results across a wide range of fractions of carbohydrate-based polymeric materials, and different polymeric materials, under various simulated conditions (for example, landfills, composting, marine environments).

TABLE 8

Sample 1072 Sample MBR 16011801 Sample MBR 15121706 Sample MBR 16011801 Sample MBR 16070601 Sample MBR 15120101 Sample MBR 15121703 Test Condition ASTM D5526 landfill Landfill ASTM D-5511 ASTM of Compound D-5338 ASTM of Compound D-5338 ASTM of Compound D-5338 ASTM D-6691 in Marine Environment ASTM D6691 in Environment Marine % in NuPlastiQ or ESR 25% 40% 25% 40% 40% 30% 27% Compatibilizer + PE 75% 60% 75% 60% 11% 3% 3%

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Sample 1072 Sample MBR 16011801 Sample MBR 15121706 Sample MBR 16011801 Sample MBR 16070601 Sample MBR 15120101 Sample MBR 15121703 % PBAT% 0% 0% 0% 0% 49% 67% 70% Thickness 0.343 mm (1.35 mil) 0.0254 mm (1 mil) 0.0254 mm (1 mil) 0.0254 mm (1 mil) 0.0381 mm (1.5 thousand) 0.0254 mm (1 mil) 0.0254 mm (1 mil) Days 573 204 201 201 59 205 205 % Degraded 71.1% 77.2% 74.2% 72.4% 96.9% 49.6% 53.6%

EXAMPLE 7 [00407] Additional test was carried out to evaluate the biodegradability to evaluate the loading levels of the carbohydrate-based polymeric material, according to the present invention. The test was in accordance with ASTM D5511. The level of carbohydrate-based polymeric material in the tested samples was 0% (a control), 1%, 5%, 10%, and 20% by weight of the blend. Table 9 below summarizes the results of such a test. Even with 1% loading, the percentage of biodegradation after 65 days (2.7%) is higher than the loading quantity (only 1%), indicating that the polyethylene included in the mixture is degraded as well. This trend continues in the data observed in 95 days, in which the percentage of biodegradation continues to increase (for example, 5% in 95 days). More accelerated results are observed in greater loads of 5%, 10%, and 20% of the polymeric material based on carbohydrate. It is expected that in all samples loaded with the biodegradable carbohydrate-based polymeric material, the entire non-biodegradable plastic content will be degraded, for example, within a reasonable period of time (for example, within 1 year, 2 years, 3 years, 4 years, or 5 years) under such disposal conditions.

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TABLE 9

Sample N ^Q % of NuPlastiQ or ESR Biodegradation after 65 days Biodegradation after 95 days 1515 0% -0.1% 1.3% 1516 1.0% 2.7% 5.0% 1518 5.0% 7.8% 9.4% 1519 10% 22.2% 27.2% 1520 20% 42.5% 50.5%

EXAMPLE 8 [00408] Films were manufactured from a mixture of biopolyethylene (from Braskem), NuPlastiQ or ESR, and a Bynel® compatibilizer. Once formed, the resulting films were tested for resistance to the impact of the dart (for example, according to ASTM D-1709). Films were blown in various thicknesses, from 0.013 mm (0.5 mil) to 0.051 mm (2 mil), and in various percentages of a polymeric starch-based material (NuPlastiQ or ESR) ranging from 0% to 35% NuPlastiQ or ESR by weight. The results are shown in Figures 12A and 12B.

[00409] As is evident from Figure 12A, biopolyethylene alone (in NuPlastiQ or ESR) provides a dart impact resistance of about 120 g for a thickness of 0.013 mm (0.5 mil), a resistivity the impact of the dart of about 155 g for a thickness of 0.025 (1 mil), a resistance to the impact of the dart of about 200 g for a thickness of 0.038 mm (1.5 mil), and a resistance to the impact of the dart 270 g for a thickness of 0.051 mm (2 mil). The approximate dart impact resistivities are shown in Table 10A. Table 10B shows percentage increases in resistivity compared to pure biopolyethylene film. It is readily apparent that there are increases for all thicknesses, and all percentages of NuPlastiQ or ESR tested on the film. The increases in resistivity are particularly high as the films become thicker (that is, the percentage increase is even more drastic

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113/122 for thicker films compared to thinner films).

TABLE 10A

Dart impact resistance (g) % of NuPlastiQ or ESR 0.013 mm (0.5 mil) 0.0254 mm (1 mil) 0.0381 mm (1.5 mil) 0.051 mm (2 mil) 0% 120 g 160 g 200 g 270 g 15% 165 g 225 g 290 g 385 g 25% 135 g 195 g 275 g 395 g 35% 125 g 190 g 275 g 410 g TABLE 10B Percentage of increased dart impact resistivity (%) % of NuPlastiQ or ESR 0.013 mm (0.5 mil) 0.013 mm (1 thousand) 0.0381 mm (1.5 mil) 0.0381 mm (2 mil) 0% - - - - 15% 38% 41% 45% 43% 25% 13% 22% 38% 46% 35% 4% 19% 38% 70%

[00410] When forming and testing such films, the Applicant noted that the results of increased resistivity generally corresponded with the results seen with the use of synthetic petrochemical polyethylenes. As noted above, it was observed that when using the biopolyethylene material in the blend, the improvement in resistivity increased more quickly, as the thickness increased (that is, the percentage of increase is the most drastic for thicker films compared to thinner films).

[00411] It was also observed that a key point for NuPlastiQ based on starch or ESR with biopolyethylene can be about 15%, instead of about 25% observed with polyethylene of petrochemical origin. However, increases in resistivity were similarly observed when mixing NuPlastiQ or ESR with any resin base.

[00412] Finally, films formed according to Example 8 include

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114/122 much more than 40% biological content, which is a particular advantage, since both resin-based (for example, any non-sustainable ecological polymeric material such as those described in this document) and NuPlastiQ based on carbohydrate or starch-based or ESR material are derived from sustainable materials. The only component in the films that did not count for the biological content is the compatibilizer (and where available, a sustainable compatibilizer could be used). The biological content can therefore be at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least at least 80%, at least 85%, at least 90%, or at least 95% by weight of the film or other product. The films of Example 8 consisted of biological content, different from the compatibilizer Bynel®, so that they included more than 90% biological content by weight.

[00413] Finally, the films of Example 8 are substantially fully biodegradable, in a similar manner as described for the various other polyethylenes tested in the examples described above. The present invention thus provides polymer films of very high biological content and other products, which are not only sustainable, but also biodegradable.

EXAMPLE 9 [00414] This example is illustrative of the blowing ratio and / or matrix span effect. The dart impact test resistivity is measured for several films, including films formed from polyethylene alone, and films formed from a mixture of NuPlastiQ or ESR, polyethylene and a compatibilizer. The films formed from the blend include 25% renewable polymeric material based on carbohydrate, 5% compatibilizer, and 70% polyethylene. All films are blown at a blow rate of about 2.5. The Applicants noted that, although an increase in resistivity is observed when blowing films at increased blowing ratios with blends, the blowing ratio has no significant effect of resistivity when blowing a polyethylene film alone.

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In other words, with polyethylene alone, the resistivity is substantially the same if the blowing ratio is 1.5, 3, or any point in between. Table 11 below shows approximate darts impact resistance values (in g) for various thickness films of the present invention compared to a control, as well as the percentage of increased resistivity for the various blends compared to the control.

TABLE 11

Thickness (mm (mil)) 100% PE (BUR from 1.5 to 2.5) Control 10% NuPlastiQ or ESR (BUR = 2.5) 20% NuPlastiQ or ESR (BUR = 2.5) 25% NuPlastiQ or ESR (BUR = 2.5) 30% NuPlastiQ or ESR (BUR = 2.5) 0.013 (0.5) 150 152 1% 160 7% 170 13% 195 30% 0.025 (1.0) 210 240 14% 260 24% 265 26% 275 31% 0.038 (1.5) 250 320 28% 340 36% 350 40% 335 34% 0.51 (2.0) 290 380 31% 420 45% 430 48% 380 31%

[00415] Figure 13 shows additional comparative dart impact resistivity data for 100% polyethylene films in various film thicknesses, compared to films formed from the mixture of polyethylene and 25% polymer material based on renewable carbohydrate of NuPlastiQ or carbohydrate-based ESR, for example, in a blowing ratio of about 2.5. Figure 13 shows the ability to produce a film that has a thickness of as little as 0.003 mm (0.1 mil). As described in this document, there can be considerable difficulty in forming such a thin film from the polyethylene material itself. As shown in Figure 13, the resistivity of 100% polyethylene film is substantially independent of the blowing ratio (that is, the resistivity is substantially the same at a blowing ratio of 1.5, or a blowing ratio of 2, 0, or 2.5, or 3.0). In all points, the resistivity of films formed from the 25% polymeric material based on renewable carbohydrate from NuPlastiQ or mixed carbohydrate-based ESR are higher than those from the film formed from polyethylene

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116/122 alone.

EXAMPLE 10 [00416] Examples 10-14 are illustrative of the addition of an odor reducing agent. Example 10 is a comparative example. Samples are prepared from a mixture of a polymeric material based on carbohydrate and another polymeric resin (selected as polyethylene), as well as a PE compatibilizer modified by maleic anhydride. The compatibilizer is included in an amount of 5% by weight. The amount of the carbohydrate-based polymeric material ranges from 5% to 50% by weight, with the balance being polyethylene polymeric resin. These samples do not include any odor reducing agent, and exhibit a slight odor characteristic of the polymeric carbohydrate-based material, which can be described as an odor similar to popcorn, an odor similar to caramelized corn, or a slightly burnt starch odor. Although the odor is almost unobservable when the geometry of the article is relatively open (for example, a flat sheet or film of the material), the odor becomes more pronounced in that the geometry is relatively closed (for example, in the form of a glass, or where the film is rolled up on a roll).

EXAMPLE 11 [00417] Samples are prepared which are identical to those of Example 10, but which include a small fraction of 4-hydroxy-3-methoxybenzaldehyde (vanillin) in them as an odor reducing agent. The odor reducing agent is supplied as a powder, for example, as a lyophilized powder. The powder is mixed with the liquid components used to produce the polymeric material based on carbohydrate (for example, water and / or glycerin) to obtain homogeneous dispersion of the odor reducing agent in it. The carbohydrate-based polymeric material is then formed from water, glycerin, and starches in the same manner as in Example 10 (and Example 1), so that the finished carbohydrate-based polymeric material includes the odor reducing agent dispersed in it at a level of 20 ppm (0.002%) by weight. In each sample, the ratio of the carbohydrate-based polymeric material to the

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117/122 odor reducing agent (ratio of NuPlastiQ or ESR to ORA) is 50,000: 1. [00418] Characteristics for the samples are as shown in Table 12.

TABLE 12

Sample A Sample B Sample C Sample D Sample E Sample F Sample G Polymeric material based on carbohydrates 5% 10% 20% 25% 30% 40% 50% Polyethylene 90% 85% 75% 70% 65% 55% 45% Compatibilizer 5% 5% 5% 5% 5% 5% 5% Odor reducing agent in the blend 1 ppm 2 ppm 4 ppm 5 ppm 6 ppm 8 ppm 10 ppm The ratio of NuPlastiQ / ESR to ORA 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1

[00419] In contrast to the otherwise identical samples of Example 10, these samples no longer exhibit the slight characteristic odor described in Example 10. The odor difference is particularly evident with relatively closed geometries, such as where the blend is modeled in the shape of a glass. For comparison, cups formed from such blends as shown in Table 12 do not exhibit a discernible odor, similar to cups formed from 100% polyethylene. It is surprising that so little of the odor-reducing agent is sufficient to cancel the otherwise characteristic odor typically associated with a carbohydrate-based polymer content.

EXAMPLE 12 [00420] Samples are prepared which are identical to those of Example 10, but which include a small fraction of freeze-dried strawberry powder in them as an odor reducing agent. The powdery odor reducing agent is dispersed in the carbohydrate-based polymeric material at a level of 20 ppm

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118/122 (0.002%) by weight.

[00421] Articles are formed in the same manner as in Example 10, but include a small fraction of the odor reducing agent dispersed therein.

TABLE 13

Sample A Sample B Sample C Sample D Sample E Sample F Sample G Polymeric material based on carbohydrates 5% 10% 20% 25% 30% 40% 50% Polyethylene 90% 85% 75% 70% 65% 55% 45% Compatibilizer 5% 5% 5% 5% 5% 5% 5% Odor reducing agent in the blend 1 ppm 2 ppm 4 ppm 5 ppm 6 ppm 8 ppm 10 ppm The ratio of NuPlastiQ / ESR to ORA 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1

[00422] In contrast to the otherwise identical samples from Example 10, these samples no longer exhibit the slight characteristic odor described in Example 10. The odor difference is particularly evident with relatively closed geometries, such as where the blend is modeled in the shape of a glass. For comparison, cups formed from such blends as shown in Table 13 do not exhibit a discernible odor, similar to cups formed from 100% polyethylene. It is surprising that so little of the odor-reducing agent is sufficient to cancel the otherwise characteristic odor typically associated with a carbohydrate-based polymer content.

EXAMPLE 13 [00423] Samples are prepared that are identical to those in Example 10, but that include a small fraction of freeze-dried blueberry powder

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119/122 as an odor reducing agent. The powdery odor reducing agent is dispersed in the carbohydrate-based polymeric material at a level of 20 ppm (0.002%) by weight.

[00424] Articles are formed in the same manner as in Example 10, but include a small fraction of the odor reducing agent dispersed therein.

TABLE 14

Sample THE Sample B Sample Ç Sample D Sample AND Sample F Sample G Polymeric material based on carbohydrates 5% 10% 20% 25% 30% 40% 50% Polyethylene 90% 85% 75% 70% 65% 55% 45% Compatibilizer 5% 5% 5% 5% 5% 5% 5% Odor reducing agent in the blend 1 ppm 2 ppm 4 ppm 5 ppm 6 ppm 8 ppm 10 ppm The ratio of NuPlastiQ / ESR to ORA 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1 50,000: 1

[00425] In contrast to the otherwise identical samples of Example 10, these samples no longer exhibit the slight characteristic odor described in Example 10. The odor difference is particularly evident with relatively closed geometries, such as where the blend is modeled in the shape of a glass. For comparison, cups formed from such blends as shown in Table 14 do not exhibit a discernible odor, similar to cups formed from 100% polyethylene. It is surprising that so little of the odor-reducing agent is sufficient to cancel the otherwise characteristic odor typically associated with a carbohydrate-based polymer content.

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EXAMPLE 14 [00426] Samples are prepared similarly to Example 10, but which includes several small fractions of lyophilized vanillin powder therein as an odor reducing agent. The powdery odor reducing agent is dispersed in the carbohydrate-based polymeric material at levels from 5 ppm (0.0005%) to 100 ppm (0.01%) by weight.

[00427] Articles are formed in the same manner as in Example 10, but include a small fraction of the odor reducing agent dispersed therein.

TABLE 15

Sample THE Sample B Sample Ç Sample D Sample AND Sample F Polymeric material based on carbohydrates 25% 25% 25% 25% 25% 25% Polyethylene 70% 70% 70% 70% 70% 70% Compatibilizer 5% 5% 5% 5% 5% 5% Odor reducing agent in NuPlastiQ / ESR 5 ppm 10 ppm 30 ppm 50 ppm 75 ppm 100 ppm Odor reducing agent in the blend 1 ppm 2 ppm 4 ppm 6 ppm 8 ppm 10 ppm The ratio between NuPlastiQ / ESR for NOW 50,000: 1 25,000: 1 8,333: 1 5,000: 1 3,333: 1 2,500: 1

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121/122 [00428] In contrast to the otherwise identical samples from Example 10, these samples no longer exhibit the slight characteristic odor described in Example 10. The odor difference is particularly evident with relatively closed geometries, such as where the blend is modeled in the shape of a cup. For comparison, cups formed from such blends as shown in Table 15 do not exhibit a discernible odor, similar to cups formed from 100% polyethylene. It is surprising that so little of the odor-reducing agent is sufficient to cancel the otherwise characteristic odor typically associated with a carbohydrate-based polymer content. Relatively high levels of vanillin (for example, 100 ppm and higher) may start to include a characteristic pleasant vanilla odor.

IV. CONCLUSION [00429] In short, although the various implementations were described in language specific to structural resources and / or methodological actions, it should be understood that the matter defined in the attached representations is not necessarily limited to the specific resources or actions described. Instead, specific resources and actions are revealed as exemplary ways of implementing the revealed matter.

[00430] In short, it should be understood that the modalities of the resources of the invention revealed in this document are illustrative of the principles of inventive resources. Other modifications that can be employed are within the scope of inventive resources. Thus, by way of example, but not limitation, alternative configurations of the inventive resources can be used in accordance with the teachings in this document. Consequently, inventive resources are not limited to this precisely as shown and described.

[00431] It will be found that the scope of the present disclosure extends to rewriting any of the claims to depend on any other claim, to include multiple dependencies on any combination of other claims, and / or to combine multiple claims with each other. Such

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122/122 also extends to “summary of concepts to be claimed” as described in the Summary section. The scope of the present disclosure also extends to inserting and / or removing any combination of features from any claim, for insertion into another claim, or drafting a new claim including any combination of such features from any other claim (or claims).

Claims (51)

1. Article characterized by the fact that it comprises: a substantially amorphous carbohydrate-based polymeric material that has a maximum crystallinity of 20%; and other polymeric material mixed with the substantially amorphous carbohydrate-based polymeric material; where at least one of: a resistivity of the article is at least 5% greater than the resistivity that the article would have had it been produced only from the other polymeric material, without the carbohydrate-based polymeric material; or an amount of the article that biodegrades in 5 years under simulated landfill conditions is greater than an amount of the carbohydrate-based polymeric material. 2. Article according to claim 1, characterized by the fact that the other polymeric material comprises a polyolefin. 3. Article according to claim 1, characterized by the fact that the substantially amorphous carbohydrate-based polymeric material has a crystallinity of less than 20%, preferably less than 15%, more preferably less than 10%. 4. Article according to claim 1, characterized by the fact that the substantially amorphous carbohydrate-based polymeric material has a glass transition temperature, heat deflection temperature or vicat softening temperature greater than 70 ° C, greater than 75 ° C, greater than 80 ° C, 70 ° C to 100 ° C or 80 ° C to 100 ° C. 5. Article according to claim 1, characterized by the fact that the substantially amorphous carbohydrate-based polymeric material has a Young's modulus of at least 1.0 GPa. 6. Article according to claim 1, characterized by the fact that the other polymeric material comprises a polyethylene. Petition 870190059088, of 6/26/2019, p. 132/277 2/8 7. Article, according to claim 6, characterized by the fact that the article comprises a film, the film being formed from a mixture of polymeric material based on carbohydrate and polyethylene. 8. Article according to claim 1, characterized by the fact that the other polymeric material comprises a polymeric material based on a petrochemical product that is not biodegradable in itself. 9. Article according to claim 1, characterized by the fact that the other polymeric material comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride, PBAT or polycarbonate. 10. Article according to claim 1, characterized by the fact that 5% by weight of the carbohydrate-based polymeric material is sufficient to make the other polymeric material biodegradable, so that a quantity of the article that biodegrades in 5 years under simulated landfill conditions is greater than an amount of the carbohydrate-based polymeric material. 11. Article according to claim 1, characterized by the fact that the mixture of the carbohydrate-based polymeric material with the other polymeric material includes at least 5% by weight of the carbohydrate-based polymeric material. 12. Article according to claim 1, characterized by the fact that the mixture of the carbohydrate-based polymeric material with another polymeric material includes from 5% to 50% by weight of the carbohydrate-based polymeric material. 13. Article according to claim 1, characterized by the fact that the mixture of the carbohydrate-based polymeric material with another polymeric material includes from 10% to 50% by weight of the carbohydrate-based polymeric material. Petition 870190059088, of 6/26/2019, p. 133/277 3/8 14. Article according to claim 1, characterized by the fact that the article comprises a film, the film having a thickness that is less than 0.005 mm, preferably from 0.002 mm to 0.004 mm. 15. Article, according to claim 1, characterized by the fact that the article comprises a film, the thickness of which is 0.0025 mm (0.1 mil) to 0.25 mm (10 mil) ). 16. Article according to claim 1, characterized in that the carbohydrate-based polymeric material comprises a starch-based polymeric material. 17. Article according to claim 16, characterized by the fact that the polymeric material based on starch is formed from a starch and a plasticizer. 18. Article according to claim 17, characterized by the fact that the starch comprises one or more of potato starch, corn starch or tapioca starch and the plasticizer comprises glycerin. 19. Article according to claim 16, characterized by the fact that the polymeric starch-based material is formed from a mixture of at least two different starches. 20. Article according to claim 1, characterized by the fact that the article comprises a film, the film having a dart impact resistance of at least 100 g per thousand (0.0254mm) thickness, preferably , at least 140 g per thousand (0.0254mm) thickness. 21. Article, according to claim 1, characterized by the fact that the resistivity of the article is at least 10% greater than the resistivity that the article would have had it been produced only from the other polymeric material, without the polymeric material at carbohydrate base. 22. Article according to claim 1, characterized by the fact that the other polymeric material comprises an unsustainable polymeric material. Petition 870190059088, of 6/26/2019, p. 134/277 4/8 23. Article according to claim 22, characterized by the fact that the other polymeric material comprises an unsustainable polymeric material formed from one or more of sugarcane or corn. 24. Article, according to claim 22, characterized by the fact that at least 90% of the polymeric content of the article comes from sustainable sources. 25. Article according to claim 22, characterized by the fact that the article comprises at least one of a film, a sheet, a bottle or another container. 26. Article, according to claim 22, characterized by the fact that the non-sustainable polymeric material comprises one or more among polyethylene, polypropylene or polyethylene terephthalate formed from sustainable sources. 27. Article, according to claim 1, characterized by the fact that the mixture of substantially amorphous carbohydrate-based polymeric material and the other polymeric material additionally comprises an odor reducing agent, the odor reducing agent being preferably, an organic odor reducing agent, in which in the absence of the odor reducing agent, the carbohydrate-based polymeric material gives the article a characteristic odor of burnt carbohydrate. 28. Article according to claim 27, characterized by the fact that the organic odor reducing agent comprises a lyophilized powder. 29. Article according to claim 27, characterized by the fact that the organic odor reducing agent comprises a vanilla extract. 30. Article according to claim 27, characterized by the fact that the organic odor reducing agent comprises vanillin. 31. Article according to claim 27, characterized by the fact that the organic odor reducing agent has the following chemical structure: Petition 870190059088, of 6/26/2019, p. 135/277 5/8 Ο ·.,, · Η Ύ

32. Article according to claim 27, characterized by the fact that the organic odor reducing agent essentially consists of 4-hydroxy-3-methoxybenzaldehyde. 33. Article according to claim 27, characterized by the fact that the organic odor reducing agent comprises at most 1%, preferably at most 0.1%, more preferably, at most 0.01%, with more preferably, at most 1,000 ppm, more preferably, at most 100 ppm, more preferably, at most 50 ppm and, most preferably, at most 20 ppm of the blend. 34. Article according to claim 27, characterized by the fact that the organic odor reducing agent is present in a ratio of 1: 1,000 to 1: 100,000, based on carbohydrate polymer material, preferably 1: 25,000 to 1: 75,000. 35. Article according to claim 27, characterized by the fact that the organic odor reducing agent comprises a fruit extract. 36. Article according to claim 35, characterized by the fact that the organic odor reducing agent comprises a lyophilized organic fruit extract selected from extracts of vanilla, strawberry, blueberry, banana, apple, peach, pear, chili , mango, passion fruit, raspberry or a combination of them. 37. Article according to claim 36, characterized by the fact that the lyophilized organic fruit extract is present in the plastic material in a ratio of, at most, 1: 1000 in relation to the carbohydrate-based polymeric material. Petition 870190059088, of 6/26/2019, p. 136/277 6/8 38. Article according to claim 27, characterized by the fact that the organic odor reducing agent is included within the carbohydrate-based polymeric material. 39. Method for providing increased sustainability to a plastic article while also providing at least one among increased resistance or biodegradability to the plastic article, the method being characterized by the fact that it comprises: provide a polymeric material; mixing a substantially amorphous carbohydrate-based polymeric material that has a maximum crystallinity of 20% with the polymeric material; heating the mixture to a temperature in the range of 120 ° C to 180 ° C to melt the polymeric material with the substantially amorphous carbohydrate-based polymeric material; and forming a plastic article from the mixture of the polymeric material with the substantially amorphous carbohydrate-based polymeric material in which at least one of: a resistivity of the article is at least 5% greater than the resistivity that the article would have had it been produced only from the other polymeric material, without the carbohydrate-based polymeric material; or an amount of the article that biodegrades in 5 years under simulated landfill conditions is greater than an amount of the carbohydrate-based polymeric material. 40. Method, according to claim 39, characterized by the fact that the polymeric material, by itself, is not biodegradable on its own, since the mixture of the carbohydrate-based polymeric material with it provides biodegradability to the polymeric material, so that a difference in the quantity of the article that biodegrades in 5 years under simulated landfill conditions compared to the quantity attributable to the Petition 870190059088, of 6/26/2019, p. 137/277 7/8 carbohydrate-based polymeric material is attributable to the biodegradation of the polymeric material which, by itself, is not biodegradable on its own. 41. Method according to claim 40, characterized by the fact that at least 25% of the polymeric material which, by itself, is not biodegradable on its own biodegrades in 3 years. 42. Method according to claim 39, characterized in that the article comprises a film, the film having a dart impact resistance of at least 100 g per thousand (0.0254mm) thickness, preferably , at least 140 g per thousand (0.0254mm) thickness. 43. Method according to claim 39, characterized by the fact that the resistivity of the article is at least 10% greater than the resistivity that the article would have had it been produced only from the other polymeric material, without the polymeric material at carbohydrate base. 44. Method according to claim 39, characterized by the fact that the formation of the plastic article comprises blowing a plastic film with a film blowing apparatus, the film being blown from the mixture of the polymeric material with the material substantially amorphous polymer based carbohydrate, in which: (A) the film blowing apparatus operates at a high blowing ratio of at least 2.0 during the blowing of the plastic film, the high blowing ratio providing the blown plastic film with increased resistivity; and / or (B) a matrix span of the film blowing apparatus is selected to be a matrix span of a maximum of 500 microns, the narrow matrix span providing the blown plastic film with increased resistivity. 45. Method according to claim 44, characterized by the fact that the film has a thickness that is about 0.0025 mm (0.1 mil) to 0.25 mm (10 mil). Petition 870190059088, of 6/26/2019, p. 138/277 8/8 46. Method according to claim 45, characterized in that the film has a thickness that is less than 0.005 mm, preferably from 0.002 mm to 0.004 mm. 47. Method, according to claim 44, characterized by the fact that the blowing ratio is 2.2 to 2.8. 48. Method according to claim 44, characterized by the fact that the blowing ratio is 2.5. 49. Method, according to claim 44, characterized by the fact that the resistivity of the plastic film is increased by selecting the high blowing ratio. 50. Method, according to claim 44, characterized by the fact that the blowing ratio is selected at a value of at least 2.0 and the matrix span is selected at a maximum of 500 microns. 51. Method according to claim 44, characterized by the fact that the matrix span is selected from 250 microns to 500 microns.