JP2020503417A - Carbohydrate polymer materials - Google Patents

Abstract

Described herein are articles that include a carbohydrate-based polymeric material and methods for forming such articles. Such articles may exhibit improved sustainability, biodegradability, increased strength, and / or various other beneficial properties. Carbohydrate-based polymeric materials can be formed from one or more starches, plasticizers (eg, glycerin), and water. Carbohydrate-based polymeric materials can exhibit very low crystallinity characteristics, such as being substantially amorphous (eg, having a crystallinity of no more than 20%, no more than 10%, such as no more than 10%). Carbohydrate-based polymer materials can be blended with non-biodegradable plastics to make these plastic materials biodegradable, which can increase the strength of films or other articles, making them sustainable It can be blended with a sustainable polymer material (such as bioPE) to improve properties (eg, 90% or more).

Description

(Cross-reference of related applications)
This application is related to U.S. Patent Application No. 15 / 481,806 filed April 7, 2017 (21132.1), and U.S. Patent Application No. 15 / 481,823 filed April 7, 2017. U.S. Patent Application No. 15 / 691,588, filed August 30, 2017, and U.S. Patent Application No. 15/836, filed December 8, 2017. No. 555 (21132.4.1), U.S. patent application Ser. No. 62 / 610,615, filed Dec. 27, 2017, and U.S. patent application Ser. 62 / 610,618 (21132.12); U.S. application Ser. No. 62 / 440,399 (21132.10) filed on Dec. 29, 2016; and filed on Jan. 4, 2017. U.S. Application No. 62 / 442,432 (21,132.11), and claims the benefit of filed April 7, 2017 U.S. Patent Application Serial No. 62 / 483,219 (21132.4). The entire contents of each of the foregoing are incorporated herein by reference. Also, U.S. Patent Application No. 14 / 853,725 (21132.6) filed on September 14, 2015, and U.S. Patent Application No. 14 / 853,780 (21132) filed on September 14, 2015. .8), and U.S. Provisional Patent Application No. 62 / 187,231, filed June 30, 2015, is also incorporated herein by reference in its entirety.

  Traditional petrochemical plastics are formulated to be strong, lightweight and durable. However, these plastics are typically not biodegradable, resulting in hundreds of millions of tons of plastic present in landfills or sea floats. In attempting to reduce the amount of plastic waste, some articles typically manufactured using petrochemical plastics are manufactured using biodegradable materials.

  Large amounts of petrochemical plastic materials such as polyethylene and polypropylene, as well as many other plastics (polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, polycarbonate, nylon, etc.) are typically readily biodegradable is not. This is usually the case even with so-called "green" plastics of such materials, which may be supplied from renewable or sustainable sources rather than petrochemical raw materials.

Most recently, UV and / or OXO additives (such as PDQ-M, PDQ-H, BDA, and OxoTerra ™ from Willow Ridge Plastics, OX1014 from LifeLine, or organic additives (Restore by Enso) There have been attempts to make such plastic materials increasingly degradable by the addition of EcoPure® by Bio-Tec Environmental, ECM Masterbatch Pellets1M by ECM Biofilms, or BioSphere® by Bio-Tec Environmental. The use of such additives is generally not favored by plastics industry associations (eg, SPC, APR, FPA, and / or BPI) and why Al, extent and rate of biodegradation biodegradability, often too slow, OXO additives usually begins fragmentation or degradation of simple structure, this is, of carbon dioxide from plastic (CO ₂₎ Instead of the desired actual conversion to natural materials such as water, (H ₂ O), and methane (CH ₄ ), it accelerates the physical degradation of such plastic materials into smaller pieces of the underlying base plastic. Because you do.

For example, such materials merely act to promote the collapse of the macrostructure of the plastic article itself due to exposure to ultraviolet light (from sunlight) and / or to oxygen. Such specialty plastics may not actually biodegrade to any significant degree within a given time frame (eg, 5, 3, or 1 year), but simply lose strength, crack, and May break up finely. As a result, the addition of UV or / and OXO additives physically degrades bottles, films, or other articles over time, while other base plastic materials remain substantially the same and actual biodegradation Since it does not actually occur, a deposit or sliver of polyethylene or other base plastic material occurs. Deterioration is merely physical as the article becomes brittle, cracked and shredded, leaving many small pieces of polyethylene or other base plastic material. Such application of the term "biodegradable" to plastic materials, there is a possibility that the complete biodegradation of the polymeric material itself does not occur in practice (e.g., significant proportion of the plastic CO _2, CH ₄ , when decomposed into H ₂ O).

  In addition, most plastics used today are not formed from renewable or sustainable resources (eg, starting materials that can be recycled within about 100 years). The terms renewable and sustainable are used interchangeably herein. Rather, polyethylene (PE), polyethylene terephthalate (PET), and other typical plastics used in large quantities in bottles, bags, and other packaging are manufactured from petroleum product starting materials that are not renewable or sustainable. You.

  In an effort to increase sustainability, some efforts have recently been made to develop processes for producing such plastic materials from renewable resources such as sugar cane, corn, or other plant products. is there. For example, such renewable materials can be used to produce ethanol, ethylene glycol, or other chemical component materials that can be further reacted to produce monomers that can be polymerized. Such efforts can help blend such "green" plastic resins with conventional petrochemical resins (e.g., bottles or other materials where a portion (e.g., 30%) of the material is sustainable). To manufacture packaging). In fact, at present some products can be made of 100% "green" plastic resin.

  While blends of such "green" materials with conventional petrochemical plastics are becoming available, all of the remaining conventional petrochemical plastics materials are subject to challenges in processing, cost, and other considerations. There are practical difficulties in replacing it with sustainable materials.

  In addition, while reducing the use of traditional non-sustainable plastic materials by replacing some of the materials with sustainable plastic materials, the resulting plastic packaging is not yet biodegradable. For example, even plastic packages made from 100% "green" plastic or containing "green" PE or parts of green "PET" are not biodegradable. Such a lack of biodegradability poses a huge and continuing problem. It would be a significant advance in the art to be able to provide an article that is biodegradable. It would also be desirable to increase the strength. It would be a further advance if such articles were formed entirely (or almost entirely) of sustainable materials.

  Further, recently, efforts have been made to reduce the use of such non-renewable petrochemical plastic materials. Some of these efforts have attempted to procure resins for producing plastic materials from renewable resources such as sugar cane or other vegetable products. Although available to some extent, plastics sourced from such renewable resources are much more expensive to manufacture than their non-renewable counterparts based on petrochemicals.

  In addition, the plastic material may have a specific strength associated with it, depending on the particular material (s) used to form the plastic film or other material, and the physical properties of the film or other article itself. Has characteristics. For example, when forming a plastic film, forming a thinner film can reduce the use of non-renewable petrochemical-based plastic resin materials, but such a reduction in material usage results in a weaker film. .

  As an example, WO2014 / 0190395 to Leufgens describes the formation of a film from a blend of polyethylene and thermoplastic starch (especially Cardia BL-F), but is comparable to that formed from polyethylene alone. The films produced therein must be very thick (eg, 3 mils) because they are weaker than conventional films and difficult to process blends containing conventional thermoplastic starch. Such very thick films are not practically capable of forming thin films, and / or the inclusion of such thermoplastic starch weakens the overall film, so that the thick film has a desired level of It does not result in a real reduction in the use of petrochemical plastic resin materials as it is needed to maintain strength.

  For example, when using plastic materials sourced from renewable resources, films and related materials that can increase strength for any given film thickness by adjusting the manufacturing parameters used during manufacturing It would be advantageous to provide a manufacturing method that: Such a method makes it possible to produce a film at a given thickness with increased strength, or to produce a film with a lower thickness but with the same strength. Such a method at the same time, the actual reduction in the amount of petrochemical plastic material used, as part of it is replaced by plastic material sourced from renewable resources and there is no need to increase the overall thickness Bring.

  In addition, replacing some of the petrochemical materials with starch or starch-based materials has shown some promise for increased sustainability, but one option for the addition of such starch or starch-based materials. The problem is that the inclusion of a significant proportion of starch or starch-based materials in the plastic composition can produce significant odors associated with the inclusion of such in articles formed from such blends. It is. For example, the material may have a slightly burnt starchy odor, a popcorn-like odor, or a caramel corn-type odor. Some people may find the smell pleasant or even more desirable, while others may find the case of plastics formed without starch or starch-based materials (e.g., formed of polyethylene or another polymer resin alone). As such, one would prefer that such a smell not be present.

  In light of the above, there remain many issues that need to be addressed in the art.

International Publication No. WO 2014/0190395

  The present disclosure is directed to various concepts that can be implemented in article manufacturing and / or manufacturing methods. In one embodiment, the present disclosure is directed to articles that exhibit increased strength and / or biodegradability. In some cases, the article comprises one or more polymeric materials (eg, synthetic, eg, petrochemical, or otherwise) and one or more, low crystallinity (ie, they are substantially amorphous). ), A glass transition temperature, a heat distortion temperature, a Vicat softening temperature, and the like. In certain examples, one or more carbohydrate-based polymeric materials may include one or more starch-based polymeric materials. By way of example, the carbohydrate-based polymeric material may be substantially amorphous, having a crystallinity of 20% or less, having a Young's modulus of at least 1.0 GPa, and / or May have a glass transition or heat distortion temperature or Vicat softening temperature of 70C to 100C. Other features of the carbohydrate-based material are described further herein.

  The process of manufacturing the article can include providing one or more polymeric materials and one or more substantially amorphous carbohydrate-based polymeric materials. One or more polymer materials and one or more carbohydrate-based polymer 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 molding machines, blow molding machines, thermoforming machines and the like. Gas can be injected into the extruded mixture to form a film. Such films can be processed into bags or other types of articles. Other articles can be extruded plastic products, injection molded plastic products, blow molded plastic products, extruded or cast sheets or films, thermoformed plastic products, and the like.

  The article may exhibit increased strength and / or biodegradability. For example, in one embodiment, mixing a substantially amorphous carbohydrate-based polymeric material with another polymeric material is useful even if the other polymeric material itself is not otherwise biodegradable by itself. Imparts biodegradability to other polymer materials. For example, polyethylene is notorious for not being biodegradable by itself. Applicants have demonstrated the ability to impart biodegradability to plastic materials such as polyethylene, but these materials are not otherwise biodegradable. Other examples of such include, but are not limited to, polypropylene, other polyolefins, polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, nylon, and polycarbonate. By way of example, under simulated disposal conditions (eg, simulated landfill conditions), the amount of an article that biodegrades within 5 years or within another given time period may be greater than the amount of carbohydrate-based polymeric material contained in the article. Good. Such simulated disposal conditions include simulated landfill conditions (eg, under any typical ASTM standard such as, but not limited to, D-5511 and / or D-5526), simulated industrial compost conditions. (Such as ASTM D-5338) or simulated marine conditions (such as ASTM D-6691). In other words, some of the otherwise non-biodegradable polymeric materials are now somehow biodegradable, as well as carbohydrate-based materials. For example, if the article is formed from a blend that includes 25% of a carbohydrate-based polymeric material, the amount of the article that biodegrades under such conditions is greater than 25% (ie, some of the other polymeric material is also degraded). And even if such other polymeric materials cannot themselves degrade under similar conditions).

  The results of third party tests obtained by the applicant show that such degradation is relatively rapid, for example, within about 180 days (within 6 months), within about 1 year, as opposed to within 5 years, This indicates that it can occur within about 2 years or about 3 years.

  In addition to or in place of biodegradability, the articles and methods provide a method for comparing an article with the strength that an article would have if the article were made solely from other polymer materials without the carbohydrate-based polymer material. It may provide increased strength (eg, at least a 5% increase in dart strength or other strength properties).

  Another aspect of the present disclosure is directed to articles formed of renewable or sustainable “green” plastic materials and carbohydrate-based (eg, starch-based) polymeric materials. For example, in one embodiment, the other polymeric material can also be a sustainable "green" polymeric material supplied from a sustainable source (e.g., a plant such as sugar cane, corn, etc.). In one embodiment, the sustainable polymer material is a polymer that exhibits similar but not otherwise identical properties to a petrochemical-based polymer (eg, “green” polyethylene, “green” polypropylene, “green” (Eg, polyethylene terephthalate (PET)). Such “green” polymers may have similar, if not identical, chemical and physical properties as compared to the same polymer formed from petrochemical feedstock (eg, polyethylene). Carbohydrate-based polymeric materials can actually impart biodegradable properties to sustainable polymer materials with which they are blended or otherwise formed, and such sustainable polymeric materials Without a layer, such biodegradable properties cannot be exhibited (or such properties can be enhanced if the sustainable polymeric material already exhibits some biodegradability).

  In addition to or instead of biodegradability, such articles may exhibit increased strength as compared to otherwise similar articles, but are formed within the incorporation of carbohydrate-based polymeric materials. For example, one embodiment relates to an article that includes one or more carbohydrate-based polymeric materials (eg, such as those described above) and one or more sustainable polymeric materials provided from a sustainable plant source. The strength is at least 5% greater than the strength that the article would have if manufactured without the carbohydrate-based polymeric material. For example, Applicants have found that by including such carbohydrate-based polymeric materials in articles (eg, as a blend of two polymeric materials), the strength is increased compared to that provided by a sustainable polymeric material alone. I found that I can do it.

  Another aspect of the present disclosure is to reduce the blow-up ratio and / or die gap used during film manufacture to increase the strength of films made from such blends of a carbohydrate-based polymeric material with another polymeric material. How to operate. In particular, Applicants have noted that the strength of most plastic films blown from various resin materials (eg, polyethylene and / or polypropylene, etc.) is not affected by changes in blow-up ratio, but is described herein. Renewable carbohydrate-based (eg, starch-based) polymer material having certain amorphous, certain glass transition temperature, Vicat softening temperature, or heat distortion temperature characteristics, and / or certain elastic modulus characteristics of However, when the film is included in the resin blend from which it is blown, its strength becomes dependent on the blow-up ratio and / or die gap, and it is possible to blow very narrow gauge films. It was discovered that. Applicants have indeed blown films of considerable strength, as thin as 0.1 mil, but such film blow molding is possible with previously known resins or manufacturing methods. I don't think it was.

  Blow-up ratio refers to the maximum diameter of the blown film divided by the diameter of the die in the film blow molding apparatus. Typically, the diameter increases as the molten resin material exits the die and begins to move upward through a "frost line" toward the bubble portion of the solidified blown film where the resin material is no longer molten. Some increase. Solidification and crystallization typically occur at the frost line, where the opacity or "frosty appearance" begins to appear in the blown bubble film. Applicants use such certain renewable carbohydrate-based polymeric materials described herein when blowing otherwise similar plastic films (but without the carbohydrate-based polymeric materials). It was observed that an increase in strength was obtained beyond that achieved with. Such an increase is achieved by choosing a high blow-up ratio and / or a narrow die gap. Such is believed to result in the alignment, orientation and / or stretching of the molecular structure of the carbohydrate-based polymeric material, which is uniformly distributed throughout the resin blend from which the film is formed. Such alignment and orientation of the amorphous renewable carbohydrate-based polymer material in the film is believed to be at least partially responsible for the observed increase in strength.

  In other words, as described herein, certain renewable carbohydrate-based polymeric materials can be used with certain described processing conditions to increase the strength of a given film, It goes without saying that the sustainability effects associated with replacing some of the other polymer content with renewable carbohydrate-based polymer materials.

  In particular, typical existing films are blow molded at an expansion ratio of about 1.5. Applicants have found that a renewable carbohydrate-based polymeric material such as NuPlastiQ or Eco Starch Resin “ESR” (available from applicant) is included in the resin blend from which the film is formed, with a blow-up ratio of at least 2 By increasing to 2.0, for example 2.2 to 2.8 (e.g., about 2.5), it was discovered that film strength increased significantly at higher blow-up ratios. For example, a blend of NuPlastiQ or ESR with a typical polymer resin (eg, polyethylene and / or polypropylene) is a film that is otherwise identical, but does not include NuPlastiQ or ESR, with a blow-up ratio of 1.5. Can exhibit strength characteristics that are substantially the same as the strength of

  Since such films (without NuPlastiQ or ESR) do not show any significant increase in strength when the blow-up ratio is increased, there is no reason to manipulate this value when blowing such films. . Applicants have discovered that when NuPlastiQ or ESR is included in the resin blend, using a high blow-up ratio (eg, at least 2.0) significantly increases the strength, as described above.

  In addition, NuPlastiQ or ESR inhibits their ability to be used to form relatively thin films (eg, 2 mils or less, typically 1.5 mils or less, eg, 0.1 mil to 1.5 mil). Does not suffer from many of the problems of alternative thermoplastic starch materials. Such a combination of discoveries is compared to a film formed of the same material but without NuPlastiQ or ESR (or without compatibilizer-ie formed only from other polymeric materials, for example polyethylene). Applicants have thus made it possible to form films of a given thickness exhibiting increased strength. Such findings also allow for the production of films having the same strength but reduced thickness when using NuPlastiQ or ESR in the blend. Such a result is surprising and advantageous, allowing the production of films containing a significant proportion of renewable resins, while at the same time increasing the strength. This is achieved by manipulating the blow-up ratio and / or die gap. Applicants have also discovered that it is possible to increase strength by ensuring that the die gap used in the film blow molding apparatus is relatively narrow. Again, as evidenced by Leufgens (the die gap used was 1.6-1.8 mm), narrow die gaps are not practically possible with many conventional thermoplastic starch blends. The present invention can use die gaps of 1000 micrometers or less, more typically 500 micrometers or less. Thus, blow-up ratio and / or die gap can be used in accordance with the present method to increase film strength.

  As an example, one embodiment relates to a method for providing increased strength to a blown plastic film, the method comprising blowing a plastic film using a film blow molding apparatus, wherein the film comprises: , A first polymeric material (eg, polyethylene, another polyolefin, or other conventional polymeric material) and a blend comprising a renewable carbohydrate-based polymeric material. The renewable carbohydrate-based polymeric material may be substantially amorphous, having a crystallinity of 20% or less, having a Young's modulus of at least 1.0 GPa, and / or May have a glass transition temperature, Vicat softening temperature, or heat distortion temperature of 70C to 100C. The film blow molding apparatus can operate with a high blow-up ratio and / or a narrow die gap, such as a blow-up ratio of at least 2.0 when blowing plastic films, or a die gap of 500 micrometers. It can be: A high blow-up ratio and / or a narrow die gap may have an increased strength (e.g., as compared to all others but with a lower blow-up ratio and / or a larger die gap). A plastic film may be provided.

  Another embodiment relates to a method of increasing the strength of a blown plastic film by manipulating a blow-up date, the method comprising blowing the plastic film using a film blow molding apparatus. The film is blown from a blend comprising a first polymeric material and a second polymeric material comprising a renewable carbohydrate-based polymeric material. The renewable carbohydrate-based polymer material can be substantially amorphous, have a degree of crystallinity of 20% or less, have a Young's modulus of at least 1 GPa, and / or It may have a glass transition temperature, Vicat softening temperature, or heat distortion temperature of 100 ° C. The method is to select a high blow-up ratio of at least 2.0 to increase the strength of the film (e.g., all the same but with a lower blow-up ratio). It may further include manipulating the blow-up ratio of the film blowing device. In addition to or instead of manipulating the blow-up ratio, the method operates the die gap of the film blower (ie, specifically selecting) to select a narrow die gap of 500 micrometers or less. That the narrow die gap and / or high blow-up ratio increase the strength of the film (eg, all else being the same, but having a higher die gap and / or lower blow-up ratio). Up ratio).

  Another aspect of the present disclosure is directed to a method of reducing the characteristic odor due to including a starch-based polymeric material, or other carbohydrate-based polymeric material, as well as articles with reduced such odor. The carbohydrate-based polymer materials described herein, as well as other similar carbohydrate-based polymer materials, exhibit a characteristic slightly burnt starch, popcorn, or caramel corn type odor. Some articles, which are not usually overwhelming, but are formed from blends of materials including carbohydrate-based polymeric materials, especially where the geometry of the finished product can be relatively "closed" (e.g., cups) Or other enclosed structures where the volume is surrounded by plastic material on two, three or more sides. Such unique odors accumulate in such enclosed volumes so as to be noticed by consumers or other uses (eg, when the user snouts and sniffs such cups). There can be a tendency.

  Applicants desire to eliminate or minimize such characteristic odors, so that the articles are instead similar in odor to those present when formed from standard (eg, petrochemical-based) polymeric materials. Or make it the same. For example, an article according to the present invention can be formed from a blend of such a standard "other polymeric material" with a carbohydrate-based polymeric material, as described above and elsewhere herein. it can. Applicants have discovered that by adding very small amounts of odor reducing agents, especially organic odor reducing agents, the characteristic odor can be substantially eliminated or minimized.

  Some attempts have previously been made by others to reduce the odor arising from distilled grain dry grain (DDG) material, as described, for example, in WO 2009/058426. The treatment required the addition of a relatively high percentage of activated carbon or steam activated anthracite material. Probably somewhat effective, but the concentration of such materials required is high, and the cost of such materials is prohibitive, so commercial applications of such embodiments are not particularly feasible. Absent. In addition, it may not be desirable to add a high percentage of dark activated carbon or activated anthracite material because it tends to act as a pigment under certain conditions to color the plastic material. This can be particularly problematic if a highly transparent film, light colored article, or other similar article is desired.

  Accordingly, one embodiment of the present invention is directed to a sustainable plastics material that includes carbohydrate-based polymeric materials, other polymeric materials as described above, but also includes odor reducers. In the absence of an odor-reducing agent, the carbohydrate-based polymeric material will give the charred carbohydrate odor characteristic of a sustainable plastic material. In one embodiment, the odor reducing agent can be organic and includes an aromatic compound (eg, containing a benzene ring) such as a benzaldehyde compound, a benzyl ketone compound, or other benzene derivatives. In one embodiment, the organic odor-reducing agent can include lyophilizates or other extracts from fruits or vegetables, such as vanillin. Organic odor reducing agents can in fact be extracted from such fruits, vegetables, or other plants, or are aromatic compounds typically found in such extracts but made synthetically (Eg, synthetic vanillin or another synthetic aromatic compound may be suitable). Vanillin is an aromatic benzaldehyde compound also known as 4-hydroxy-3-methoxybenzaldehyde.

  Applicants have surprisingly found that only a small percentage of such odor reducing agents are characteristic of carbohydrate-based polymeric materials contained in blends that would otherwise constitute a sustainable plastics material. Odor was found to be sufficient to substantially remove. For example, the weight ratio of odor reducing agent to carbohydrate-based polymer material to substantially remove odor is on the order of 1: 1000 or less. Even small amounts, such as 100 ppm, 50 ppm, or even 20 ppm or less, are sufficient to remove all practical signs of the characteristic odor.

  This is particularly surprising, given that only a small amount of odor reducer is required to remove the odor. The mechanism of action is the characteristic carbohydrate odor as little is needed and the odor does not seem to be replaced or masked by any odor provided, typically by odor reducers. Is simply not possible. Although such mechanisms are probably not fully understood, such aromatic or other organic odor-reducing agents, and their melting and heating of carbohydrate-based polymeric materials during molding of the thermoplastic blend into the desired article. There may then be a chemical interaction with the particular odorous compounds that arise.

  An odor reducing agent can be included with the carbohydrate-based polymeric material, for example, in its masterbatch. Thus, one embodiment may be directed to such a low-odor, sustainable thermoplastic carbohydrate-based polymer material that includes an organic odor-reducing agent pre-blended with the carbohydrate-based polymer material. The weight ratio of organic odor-reducing agent to carbohydrate-based polymeric material can be up to 1: 1000 (ie, at least 1000 times more carbohydrate-based polymeric material compared to the amount of odor-reducing agent). In one embodiment, the ratio of the odor-reducing agent to the carbohydrate-based polymeric material can be much more dilute, such as 1: 50,000.

  It will be apparent that the present disclosure also includes related methods, for example, methods of reducing the characteristic odor of a material blend comprising a carbohydrate-based polymeric material, for example, by including a small amount of an organic odor reducing agent in the blend. . If the carbohydrate-based polymer material is provided as a masterbatch, the odor reducing agent may be provided in a masterbatch already blended with the carbohydrate-based polymer material. Thus, the masterbatch is then blended with a polymeric resin material (eg, any of a number of different plastic resins, such as PE, PP, other polyolefins, polyesters, polystyrene, PBAT, polycarbonate, or others). Sometimes, the blended material also now contains an odor reducing agent blended therein.

(Summary of exemplary concepts that may be claimed)
1. An article having a crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a heat distortion temperature, a Vicat softening temperature, a specific Young's modulus and / or other physical properties of NuPlastiQ or ESR1 An article comprising one or more substantially amorphous carbohydrate-based polymer materials (eg, a starch-based polymer material) and one or more polyolefin-based polymer materials, wherein the article has a dart drop impact test of at least about 140 g / mil thickness. An article having a value.

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

4. The article of claim 1, wherein the one or more polyolefin-based polymeric materials comprises polyethylene.
5. The article of claim 1, wherein the article is a bag having a thickness of about 0.01 mm to about 0.1 mm, wherein the bag includes a cavity having a volume of about 1 L to about 100 L.

  6. The one or more starch-based polymeric materials comprise about 20% to about 40% by weight of the article, and the one or more polyolefin-based polymeric materials comprise about 60% to 80% by weight of the article. The article of claim 1, wherein the article has a thickness of about 0.02 mm to about 0.05 mm and the article has a dart drop impact test value of about 265 g to about 330 g per mil thickness.

7. The article of claim 1, further comprising a compatibilizer present in an amount of up to 8% by weight of the article.
8. An article, formed from a mixture of a first amount of a first starch and a second amount of a second starch, having a crystallinity of less than 20% and less than 10%, a specific glass transition temperature, One or more substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) having a heat distortion temperature, Vicat softening temperature, specific Young's modulus and / or other physical properties of NuPlastiQ or ESR; A polyolefin-based polymer material, wherein the article comprises: (i) a polyolefin-based polymer material; and a first starch-based polymer material formed from a single starch comprising the first starch. Dart drop impact test value of 1; (ii) a second starch-based polymer formed from a single starch consisting of a polyolefin-based polymer material and a second starch. Have greater dart drop impact test values than the second dart drop impact test value of the second article comprising a material, the article.

9. The article of claim 8, wherein the starch-based polymeric material is formed from one or more plasticizers.
10. The first starch comprises or is derived from one of a potato starch, a corn starch, or a tapioca starch, and the second starch is a different one of a potato starch, a corn starch, or a tapioca starch. 9. The article of claim 8, comprising or derived from one.

  11. 9. The starch-based polymeric material is present in an amount from about 20% to about 30% by weight of the article, and the polyolefin-based polymeric material is present in an amount from about 65% to about 75% by weight of the article. Goods.

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

  13. The mixture of starches from which the starch-based polymeric material is formed comprises a third starch, wherein the third starch comprises from about 10% to about 35% by weight of the mixture of starches from which the starch-based polymeric material is formed. Wherein the dart drop impact test value of the article comprises a third starch-based polymer material formed from a single starch consisting of a polyolefin-based polymer material and a third starch. 13. The article of claim 12, which is greater than a dart drop impact test value.

  14． 9. The article of claim 8, wherein the article has a longitudinal elongation at break greater than the elongation at break of an additional article formed from a polyolefin-based polymer material that does not include a starch-based polymer material. Goods.

15. 10. The article of claim 9, further comprising a compatibilizer present in an amount up to 8% by weight of the article.
16. A process for providing one or more petrochemical-based polymeric materials, a crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a Vicat softening or heat distortion temperature, a specific Young's modulus And / or providing one or more substantially amorphous carbohydrate-based polymer materials having NuPlastiQ or other physical properties of ESR, and one or more petrochemical-based polymer materials and one or more carbohydrates Mixing with the base polymer material to produce a mixture of materials, heating the mixture of materials to a temperature in the range of about 120 ° C. to about 180 ° C., and producing a film using the mixture of materials. Producing a film, wherein the film has a dart drop impact test value of about 250 g to about 350 g per mil thickness.

  17． 17. The process of claim 16, wherein producing a film using the mixture of materials comprises extruding the mixture of materials to produce an extruded body, and injecting gas into the extruded body.

  18. One or more carbohydrate-based polymer materials are formed from the first starch and the second starch, and the film comprises: (i) one or more petrochemical-based polymer materials and a single starch comprising the first starch. A first dart drop impact test value of a first article comprising a first carbohydrate-based polymer material formed from a starch of the present invention, and (ii) one or more petrochemical-based polymer materials and a second starch. 17. A dart drop impact test value that is greater than a second dart drop impact test value of a second article comprising a second carbohydrate-based polymer material formed from a single starch. process.

  19. The mixture of materials further comprises one or more compatibilizers, wherein the mixture of materials comprises about 10% to about 40% by weight of one or more carbohydrate-based polymeric materials, about 60% to about 89% by weight of 1%. 17. The process of claim 16, comprising one or more petrochemical-based polymer materials and about 1% to 8% by weight or less of one or more compatibilizers.

20. 17. The process of claim 16, wherein the article comprises a film having a thickness from about 0.02 mm to about 0.05 mm.
1. An article,
A polymer-containing, less than 20% or less than 10% crystallinity formed from at least the first starch, a particular glass transition temperature, a Vicat softening or heat distortion temperature, a particular Young's modulus and / or Polymer inclusions comprising a substantially amorphous carbohydrate-based polymer material (eg, a starch-based polymer material) having NuPlastiQ or other physical properties of the ESR;
And another polymer material;
A biomethane potential test conducted at a temperature of about 52 ° C. using an inoculum having about 55% by weight of water and about 45% by weight of organic solids, where the amount of polymer content that biodegrades after 91 days. An article, based on the results of, which is greater than the amount of starch-based polymeric material.

  2. Using an inoculum having about 55% by weight of water and about 45% by weight of organic solids, the starch-based polymeric material is substantially as determined when measured according to the biomethane potential test performed at a temperature of about 52 ° C. 2. The article of claim 1, wherein all biodegrade after 91 days.

3. The article of claim 1, wherein the article further comprises a biodegradation enhancing additive present in an amount from about 0.5% to about 2.5% by weight.
4. The article of claim 1, wherein the article is substantially free of a biodegradation enhancing additive.

  5. The article is based on the results of a biomethane potential test conducted at a temperature of about 52 ° C. using an inoculum having about 55% by weight of water and about 45% by weight of organic solids. 5. The article of claim 4, wherein the article has an amount of biodegradation of the article after 91 days that is about 5% to about 60% greater than the amount of material.

6. The article of claim 1, wherein the starch-based polymeric material is formed from a material that includes one or more plasticizers.
7. A starch-based polymeric material is formed from a first starch and a second starch, wherein the first starch comprises or is derived from one of a potato starch, a corn starch, or a tapioca starch. 2. The article of claim 1, wherein the second starch comprises or is derived from a different one of potato starch, corn starch, or tapioca starch.

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

9. The article of claim 1, further comprising a compatibilizer present in an amount of up to 8% by weight of the article.
10. An article,
Less than 20%, less than 10% crystallinity, a particular glass transition temperature, a Vicat softening or heat distortion temperature, a particular Young's modulus and / or a polymer content formed from one or more carbohydrates. A polymer content comprising one or more substantially amorphous carbohydrate-based polymer materials (eg, starch-based polymer materials) having NuPlastiQ or other physical properties of the ESR;
One or more petrochemical-based polymeric materials;
Using an inoculum having an amount of polymer content that biodegrades after 91 days having from about 50% water to about 60% water and from about 40% organic solids to about 50% organic solids by weight. And wherein the article is greater than the amount of one or more carbohydrate-based polymeric materials based on the results of a biomethane potential test conducted at a temperature of about 40C to about 50C.

  11. 11. The article of claim 10, wherein the article comprises from about 20% to about 40% by weight of one or more carbohydrate-based polymeric materials and from about 65% to about 85% by weight of one or more petrochemical-based polymeric materials. Articles as described.

  12. The amount of polymer content that biodegrades after 91 days is reduced to a temperature of about 52 ° C. using an inoculant having about 55% by weight of water and about 45% by weight of organic solids. 12. The article of claim 11, wherein the article is between about 30% and about 50% based on the results of the potential test.

  13. The amount of polymer content that biodegrades after 62 days is reduced to about 52% by weight of biomethane performed using an inoculum having about 55% water and about 45% organic solids by weight. The article of claim 10, wherein the article is between about 25% and about 35% based on the results of the potential test.

  14. The one or more petrochemical polymer materials include a first petrochemical polymer material and a second petrochemical polymer material, wherein the second petrochemical polymer material complies with the ASTM D-6400 standard The article of claim 10, wherein the article is compostable according to:

15. Process
Providing one or more petrochemical polymer materials;
Less than 20%, less than 10% crystallinity, specific glass transition temperature, Vicat softening temperature or heat deformation temperature, specific Young's modulus and / or other physics of NuPlastiQ or ESR formed from one or more carbohydrates Providing one or more substantially amorphous carbohydrate-based polymeric materials (e.g., starch-based polymeric materials) having mechanical properties;
Mixing one or more petrochemical-based polymer materials with one or more carbohydrate-based polymer materials to produce a mixture of materials;
Heating the mixture of materials at a temperature comprised within the range of about 120C to about 180C;
Producing a film using the mixture of materials, wherein the film comprises a polymer inclusion composed of one or more petrochemical-based polymer materials and one or more carbohydrate-based polymer materials;
A biomethane potential test conducted at a temperature of about 52 ° C. using an inoculum having about 55% by weight of water and about 45% by weight of organic solids, where the amount of polymer content that biodegrades after 91 days. Wherein the amount of the one or more carbohydrate-based polymeric materials is greater than the amount of the one or more carbohydrate-based polymeric materials based on the results of the above.

16. One or more carbohydrate-based polymer materials
Formed from a first starch and a second starch;
Based on the results of a biomethane potential test conducted at a temperature of about 52 ° C. using an inoculum having about 55% by weight of water and about 45% by weight of organic solids, substantially no carbohydrate-based polymer material 16. The process of claim 15, wherein all biodegrade after 91 days.

17． The mixture of ingredients
Up to 8% by weight of one or more compatibilizers;
About 10% to about 40% by weight of one or more carbohydrate-based polymeric materials;
About 60% to about 90% by weight of one or more petrochemical-based polymeric materials.

18. 16. The process of claim 15, further comprising manufacturing a bag from the film.
19. 16. The process of claim 15, wherein the bag has a thickness between about 0.02 mm and about 0.05 mm, and wherein the bag includes a cavity having a volume between about 5 L and about 20 L.

20. The mixture of ingredients
Heated in multiple chambers of the extruder,
A first chamber of the extruder is set at a first temperature;
The process according to claim 15, wherein the second chamber of the extruder is set at a second temperature different from the first temperature.

21. An article,
A polymer-containing, less than 20% or less than 10% crystallinity formed from at least the first starch, a particular glass transition temperature, a Vicat softening or heat distortion temperature, a particular Young's modulus and / or Polymer inclusions comprising a substantially amorphous carbohydrate-based polymer material (eg, a starch-based polymer material) having NuPlastiQ or other physical properties of the ESR;
A synthetic polymer material;
An article wherein the amount of polymer content that biodegrades after about one year under simulated landfill, simulated compost, or simulated marine conditions is greater than the amount of starch-based polymeric material.

22. 22. The article of claim 21, wherein at least 25% of the synthetic polymeric material biodegrades within about three years.
23. A starch-based polymeric material is formed from a first starch and a second starch, wherein the first starch comprises or is derived from one of a potato starch, a corn starch, or a tapioca starch. 22. The article of claim 21, wherein the second starch comprises or is derived from a different one of potato starch, corn starch, or tapioca starch.

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

25. 22. The article of claim 21, further comprising a compatibilizer.
1. An article,
A degree of crystallinity of less than 20%, less than 10%, a specific glass transition temperature, a Vicat softening temperature or a heat distortion temperature, a specific Young's modulus and / or a composition configured to provide biodegradability to other materials of the article. A substantially amorphous carbohydrate-based polymer material having NuPlastiQ or other physical properties of the ESR (eg, a starch-based polymer material);
And sustainable polymeric materials sourced from sustainable plant sources.
An article wherein the amount of the article that biodegrades within five years under simulated landfill conditions is greater than the amount of the carbohydrate-based polymer material.

2. The article of claim 1, wherein the carbohydrate-based polymer material comprises a starch-based polymer material.
3. The article of claim 1, wherein the sustainable polymeric material comprises one or more of polyethylene, polypropylene, or polyethylene terephthalate formed from a sustainable plant source.

4. 4. The article of claim 3, wherein the sustainable polymeric material is formed from one or more of sugarcane or corn.
5. The article of claim 2, wherein the starch-based polymeric material is formed from one or more starches including one or more of potato starch, corn starch, or tapioca starch.

  6. A starch-based polymeric material is formed from two or more starches, wherein a first starch comprises one of a potato starch, a corn starch, or a tapioca starch, and a second starch is a potato starch, a corn starch, Or the article of 5, comprising one or more of the other tapioca starches.

7. The amount of the first starch is
Comprising from about 50% to about 90% by weight relative to the total weight of the first starch and the second starch, wherein the amount of the second starch is based on the total weight of the first starch and the second starch. From about 10% to about 50% by weight,
The amount of carbohydrate-based polymer material comprises from about 10% to about 40% by weight of the total weight of the carbohydrate-based polymer material and the sustainable polymer material, and the amount of carbohydrate-based polymer material is The article of claim 6, wherein the amount comprises about 60% to about 90% by weight of the combined weight of the carbohydrate-based polymeric material and the sustainable polymeric material.

  8. 8. The article of claim 7, wherein the strength of the article is at least about 5% greater than the strength that the article would have if made from only a sustainable polymer material without the carbohydrate-based polymer material.

9. The article of claim 1, wherein at least 90% of the polymer content of the article is sourced from a sustainable source.
10. The article of claim 1, wherein the article comprises a film.

11. The article of claim 1, wherein the article comprises at least one of a bottle or a sheet.
12. An article,
A degree of crystallinity of less than 20%, less than 10%, a particular glass transition temperature, a Vicat softening or heat distortion temperature, a particular Young's modulus and / or One or more substantially amorphous carbohydrate-based polymeric materials (eg, starch-based polymeric materials) having NuPlastiQ or other physical properties of the ESR;
One or more sustainable polymeric materials sourced from sustainable plant sources;
An article wherein the strength of the article is at least about 5% greater than the strength that the article would have if made from only a sustainable polymer material without the carbohydrate-based polymer material.

13. 13. The article of claim 12, wherein the article comprises a film and has a dart drop impact strength of at least about 100 g / mil thickness.
14． 13. The article of claim 12, wherein the sustainable polymeric material comprises one or more of polyethylene, polypropylene, or polyethylene terephthalate formed from a sustainable plant source.

15. 15. The article of claim 14, wherein the sustainable polymeric material is formed from one or more of sugarcane or corn.
16. 13. The article of claim 12, wherein the carbohydrate-based polymer material comprises a starch-based polymer material.

  17． 17. The article of claim 16, wherein the starch-based polymeric material is formed from one or more starches, including one or more of potato starch, corn starch, or tapioca starch.

  18. A starch-based polymeric material is formed from two or more starches, wherein a first starch comprises one of a potato starch, a corn starch, or a tapioca starch, and a second starch is a potato starch, a corn starch, 18. The article of claim 17, comprising one or more of the other tapioca starches.

19. The amount of the first starch is
Comprising from about 50% to about 90% by weight relative to the total weight of the first starch and the second starch, wherein the amount of the second starch is based on the total weight of the first starch and the second starch. From about 10% to about 50% by weight,
The amount of carbohydrate-based polymer material comprises from about 10% to about 40% by weight of the total weight of the carbohydrate-based polymer material and the sustainable polymer material, and the amount of carbohydrate-based polymer material is 19. The article of claim 18, wherein the amount comprises about 60% to about 90% by weight of the combined weight of the carbohydrate-based polymeric material and the sustainable polymeric material.

  20. 13. The article of 12, wherein the strength of the article is at least 10% greater than the strength that the article would have if made from only a sustainable polymer material without the carbohydrate-based polymer material.

21. 13. The article according to 12, wherein at least 90% of the polymer content of the article is sourced from a sustainable source.
22. The article of claim 12, wherein the article comprises a film.

23. The article of claim 12, wherein the article comprises at least one of a bottle or a sheet.
1. A method of imparting biodegradability to a plastic material that is not otherwise biodegradable by itself,
Providing plastic materials that are not biodegradable by themselves;
One or more substantially having a degree of crystallinity of less than 20%, less than 10%, a particular glass transition temperature, Vicat softening or heat distortion temperature, a particular Young's modulus and / or other physical properties of NuPlastiQ or ESR. Resisting an amorphous carbohydrate-based polymer material, wherein one or more carbohydrate-based polymer materials are selected for their ability to impart biodegradability to a plastic material that is not itself biodegradable; Providing one or more carbohydrate-based polymeric materials;
Blending a carbohydrate-based polymer material with a plastic material.

2. The method of claim 1, wherein the one or more carbohydrate-based polymer materials comprises one or more starch-based polymer materials.
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.

  4. The method of claim 3, wherein the one or more starches comprises one or more of potato starch, corn starch, or tapioca starch, and the plasticizer comprises glycerin.

5. 4. The method of claim 3, wherein the starch-based polymeric material is formed from a blend of at least two different starches.
6. The two different starches from which the starch-based polymeric material is formed are (i) one of a potato starch, a corn starch, or a tapioca starch, and (ii) another of a potato starch, a corn starch, or a tapioca starch. 6. The method of claim 5, wherein (ii) is selected to be different from (i).

  7. The two different starches from which the starch-based polymer material is formed are selected from one of the columns of the following table:

The method of claim 6.

8. The method of claim 1, wherein the plastic material comprises a polyolefin.
9. The method according to claim 1, wherein the plastic material comprises polyethylene.
10. 10. The method of claim 9, wherein the plastic material comprises a polyethylene film, wherein the film is formed from a blend of a carbohydrate-based polymer material and polyethylene.

  11. 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.

The method of claim 1, wherein blending 12.5% by weight or more of the carbohydrate-based polymer material with the plastic material is sufficient to render the plastic material biodegradable.
13. The method of claim 1, wherein the blend of the carbohydrate-based polymer material and the plastic material comprises at least 5% by weight of the carbohydrate-based polymer material.

14． The method of claim 1, wherein the blend of the carbohydrate-based polymer material and the plastic material comprises 5% to 50% by weight of the carbohydrate-based polymer material.
15. The method of claim 1, wherein the blend of the carbohydrate-based polymer material and the plastic material comprises 10% to 50% by weight of the carbohydrate-based polymer material.

16. The method of claim 1, wherein the blend of the carbohydrate-based polymer material and the plastic material comprises 20% to 40% by weight of the carbohydrate-based polymer material.
17． The method of claim 1, wherein the blend of the carbohydrate-based polymer material and the plastic material further comprises a compatibilizer.

18. 18. The method of claim 17, wherein the compatibilizer comprises no more than 10% by weight of the blend.
19. A method of imparting biodegradability to a plastic material that is not otherwise biodegradable by itself,
Providing plastic materials that are not biodegradable by themselves;
One or more substantially having a degree of crystallinity of less than 20%, less than 10%, a particular glass transition temperature, Vicat softening or heat distortion temperature, a particular Young's modulus and / or other physical properties of NuPlastiQ or ESR. Resisting an amorphous carbohydrate-based polymer material, wherein one or more carbohydrate-based polymer materials are selected for their ability to impart biodegradability to a plastic material that is not itself biodegradable; Providing one or more carbohydrate-based polymeric materials;
A method of blending a carbohydrate-based polymer material with a plastic material, wherein the carbohydrate-based polymer material comprises rendering the plastic material biodegradable and blending.

1. A method of increasing the strength of a blow molded film,
Blow molding a plastic film in a film blow molding apparatus, wherein the film is blow molded from a blend comprising a first polymer material and a renewable starch-based polymer material, wherein the renewable starch-based polymer is blown. The material is (i) substantially amorphous, having a degree of crystallinity of 20% or less, (ii) having a Young's modulus of at least 1.0 GPa, and / or (iii) 70 ° C to 100 ° C. C., including blow molding a plastic film having a glass transition temperature, Vicat softening temperature, or heat distortion temperature of
here:
(A) When the film blow molding apparatus blows a plastic film, it operates at a high blow-up ratio of at least 2.0, and the high blow-up ratio increases the strength of the blown plastic film. And / or (B) the die gap of the film blow molding apparatus is selected to be a narrow die gap of 500 micrometers or less, wherein the narrow die gap increases the strength of the blown plastic film. Give, the way.

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

4. The method of claim 1, wherein the first polymeric material comprises at least one of polyethylene or polypropylene.
5. The method of claim 1 wherein the blown plastic film has a thickness of 0.1 mil to 10 mil.

6. The method according to claim 1, wherein the blow-up ratio is between 2.2 and 2.8.
7. The method of claim 1 wherein the blow-up ratio is about 2.5.
8. The method of claim 1, wherein the renewable starch-based polymeric material is formed from a blend of at least two different starches.

9. A method for increasing the strength of a blown plastic film by manipulating a blow-up ratio,
Blow molding a plastic film with a film blow molding apparatus, wherein the film is blow molded from a blend comprising a first polymer material comprising a renewable starch-based polymer material and a second polymer material. The renewable starch-based polymer material is (i) substantially amorphous with a crystallinity of 20% or less, (ii) having a Young's modulus of at least 1.0 GPa, and (iii) B) blow molding a plastic film having a glass transition temperature, Vicat softening temperature, or heat distortion temperature of 70 ° C to 100 ° C;
Manipulating the blow-up ratio of the film blow-molding device to select a high blow-up ratio of at least 2.0 to increase the strength of the blown film.

10. 10. The method of claim 9, wherein the strength is increased by at least 1% by choosing a high blow-up ratio.
11. 10. The method of claim 9, wherein the strength is increased by at least 10% by selecting a high blow-up ratio.

12. The method according to claim 9, wherein the blow-up ratio is between 2.2 and 2.8.
13. 10. The method of claim 9, wherein the blow-up ratio is about 2.5.
14． The method of claim 9 wherein the blown plastic film has a thickness of 0.1 mil to 10 mil.

15. A method for increasing the strength of a blown plastic film by manipulating a blow-up ratio and a die gap,
Blow molding a plastic film with a film blow molding apparatus, wherein the film is blow molded from a blend comprising a first polymer material comprising a renewable starch-based polymer material and a second polymer material. The renewable starch-based polymer material is (i) substantially amorphous with a crystallinity of 20% or less, (ii) having a Young's modulus of at least 1.0 GPa, and / or (Iii) blow molding a plastic film having a glass transition temperature, Vicat softening temperature, or heat distortion temperature of 70C to 100C;
Operating the die gap of the film blow molding apparatus to select a narrow die gap of 500 micrometers or less;
When blow molding plastic films, operating the blow-up ratio at a value of at least 2.0, wherein high blow-up ratios and / or narrow die gaps increase the strength of the blown plastic film. Manipulating the blow-up ratio.

16. The method according to claim 15, wherein the blow-up ratio is at least 2.0.
17． The method according to claim 15, wherein the blow-up ratio is between 2.2 and 2.8.
18. The method according to claim 15, wherein the blow-up ratio is about 2.5.

19. The method of claim 15, wherein the die gap is between 250 micrometers and 500 micrometers.
20. 16. The method of claim 15, wherein the blown plastic film has a thickness of 0.1 mil to 10 mil.

1. A sustainable plastic material exhibiting reduced odor,
A polymer resin,
An organic odor reducing agent,
A hydrocarbon-based polymer material, wherein the carbohydrate-based polymer material imparts a charred carbohydrate odor characteristic of a sustainable plastic material in the absence of an odor reducing agent.

2. The material of claim 1, wherein the organic odor reducing agent comprises a lyophilized powder.
3. The material of claim 1, wherein the organic odor reducing agent comprises a vanilla extract.
4. The material of claim 1, wherein the organic odor reducing agent comprises vanillin.

  5. The organic odor reducing agent has the following chemical structure:

The material according to claim 1, comprising:

6. The material of claim 1, wherein the organic odor reducing agent consists essentially of 4-hydroxy-3-methoxybenzaldehyde.
7. The material of claim 1, wherein the organic odor reducing agent comprises no more than 1% of the plastic material.

8. The material of claim 1, wherein the organic odor reducing agent comprises no more than 0.1% of the plastic material.
9. The material of claim 1, wherein the organic odor reducing agent comprises no more than 0.01% of the plastic material.

10. The material of claim 1, wherein the organic odor reducer comprises less than 1000 ppm of the plastic material.
11. The material of claim 1, wherein the organic odor reducing agent comprises no more than 100 ppm of the plastic material.

12. The material of claim 1, wherein the organic odor reducing agent comprises no more than 50 ppm of the plastic material.
13. The material of claim 1, wherein the organic odor reducing agent comprises no more than 20 ppm of the plastic material.

14． The material of claim 1, wherein the organic odor reducing agent is present in a ratio of 1: 1000 to 1: 100,000 relative to the carbohydrate-based polymeric material.
15. The material of claim 1, wherein the organic odor reducing agent is present in a ratio of 1: 25,000 to 1: 75,000 relative to the carbohydrate-based polymeric material.

16. The material of claim 1, wherein the organic odor reducing agent comprises a fruit extract.
17． 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 combinations thereof. Item 17. The material according to Item 16.

18. 17. The material of claim 16, wherein the lyophilized organic fruit extract is present in the plastic material in a ratio of 1: 1000 or less to the carbohydrate-based polymer material.
19. The material of claim 1, wherein the carbohydrate-based polymer material is a starch-based polymer material.

20. Sustainable thermoplastic carbohydrate-based polymer material exhibiting reduced odor,
An organic odor reducing agent,
A carbohydrate-based polymer material;
A material wherein the weight ratio of organic odor-reducing agent to carbohydrate-based polymeric material is 1: 1000 or less such that there are at least 1000 times more carbohydrate-based polymeric materials than odor-reducing agents.

  21. Further comprising a thermoplastic polymer polymer resin blended with a sustainable thermoplastic carbohydrate-based polymer material, wherein a burnt carbohydrate odor is present when hot blending the sustainable thermoplastic carbohydrate-based polymer material with the thermoplastic polymer resin 21. The material of claim 20, wherein the material is due to the presence of an organic odor reducing agent.

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

23. 23. The material of claim 22, wherein the blend of the carbohydrate-based polymer material and the thermoplastic polymer resin comprises from 5% to 50% by weight of the carbohydrate-based polymer material.
1. Process
Providing one or more other polymers (eg, petrochemical-based polymer materials);
Providing one or more carbohydrate-based polymeric materials;
Mixing one or more other polymeric materials with one or more carbohydrate-based polymeric materials to form a mixture;
Heating the mixture at a temperature ranging from about 120 ° C to about 180 ° C;
Making a film using the mixture, wherein the film has a thickness of about 1 to about 6 micrometers and a dart drop impact test value of about 40 g to about 100 g.

1. Process
Providing one or more carbohydrate-based polymeric materials;
Providing one or more other polymers (eg, PBAT, or bio-PE);
Mixing one or more other polymeric materials with one or more carbohydrate-based polymeric materials to form a mixture;
Heating the mixture at a temperature ranging from about 120 ° C to about 180 ° C;
Making a film using the mixture, wherein the film has a thickness of about 10 to about 100 micrometers and a dart drop impact test value of about 200 g to about 600 g.

  These and other advantages and features of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.

  To illustrate the manner in which the above disclosure is enumerated and other advantages and features may be obtained, a more particular description of the embodiments briefly described above is set forth in the accompanying drawings. It will be provided by reference to specific embodiments. It is understood that these drawings depict only typical embodiments of the invention, and thus should not be considered as limiting the scope thereof, which is not to be construed as limiting the present invention. Will be described and explained with additional specificity and details.

5 is a flowchart of an exemplary process for forming an article according to the present disclosure. 1 is a flowchart of an exemplary process for increasing the strength of a blown plastic film by manipulating the blow-up ratio. 1 is a flow diagram of an exemplary process for including an odor reducing agent in a blend of a material comprising a carbohydrate-based polymeric material and another polymeric material. 1 is a flow diagram of an exemplary process for forming a carbohydrate-based polymeric material that includes an odor reducing agent that counteracts the characteristic odor of a carbohydrate-based polymeric material, and then using the carbohydrate-based polymeric material with an odor reducing agent to produce an article. FIG. 2 illustrates components of an exemplary manufacturing system for manufacturing an article according to the present disclosure. FIG. 2B is an enlarged schematic view of the film blow molding apparatus of FIG. 2A, showing a die, a die gap, a blown film bubble having a high blow-up ratio, and a frost line of the bubble. FIG. 2B is an enlarged schematic cross-sectional view through a portion of the die of FIG. 2B showing a narrow die gap. Figures showing the elastic modulus and elongation at break data for various petrochemical plastics that are not normally biodegradable or compostable (designated as standard plastics), as well as various plastics that are "greener" in one or more embodiments. . X of an exemplary NuPlastiQ or "ESR" carbohydrate-based polymeric material commercially available from BiologiQ, compared to a blend of native corn starch and native potato starch used to form NuPlastiQ or ESR. The figure which shows a line diffraction pattern. FIG. 3 shows the dart strength of films of different thickness based on the proportion of carbohydrate-based polymer material in the film. Different thickness films formed from a blend of 25% carbohydrate-based polymeric material, about 5% compatibilizer, and about 70% PE compared to 100% PE film (from about 0.1 mil to Figure 2 shows a dart strength of 2 mils, and also shows a comparison of existing agricultural, carrying and potato bags. FIG. 4 is a diagram showing dart strength for various blend films including NuPlastiQ and ESR, as well as comparative films formed from unused or recycled materials with different thicknesses. FIG. 7 shows the biodegradation measured over 349 days according to tests performed under ASTM D-5511 for three samples formed according to the present disclosure. FIG. 7 shows the biodegradation measured over 349 days according to tests performed under ASTM D-5511 for three samples formed according to the present disclosure. Measured over 843 days on potato bags manufactured under simulated landfill conditions with 25% NuPlastiQ or ESR, 70% PE, and 5% compatibilizer according to tests performed according to ASTM D-5526. The figure which showed the biodegradation rate. FIG. 4 shows the percent biodegradation measured over 370 days according to tests performed under ASTM D-5338 for various samples made in accordance with the present disclosure. FIG. 4 shows the percent biodegradation measured over 370 days according to tests performed under ASTM D-5338 for various samples made in accordance with the present disclosure. FIG. 7 shows the biodegradation rates measured over 205 days according to ASTM D-6691 for marine conditions for various samples made according to the present disclosure, as well as for controls. FIG. 9 shows dart strength for films made with a blend of NuPlastiQ or ESR carbohydrate-based polymer material and biopolyethylene or “green” PE. Darts strength is shown as a function of NuPlastiQ or ESR percentage for films of various thicknesses. FIG. 12B presents data similar to FIG. 12A, but shows dart strength as a function of film thickness for blends containing various proportions of NuPlastiQ or ESR. At a blow-up ratio of 2.5, 25% NuPlastiQ or ESR material compared to the dart strength for a film formed entirely of polyethylene (this polyethylene film does not show a blow-up ratio dependent strength). The figure which shows the dart strength of the film formed from the blend containing the compatibilizer and the balance which is polyethylene.

I. DefinitionsAll publications, patents and patent applications cited herein, whether above or below, are shown as if each individual publication, patent or patent application was specifically and individually incorporated by reference. To the same extent as is incorporated herein by reference.

  The term "comprising", which is synonymous with "including", "containing", or "characterized by", is inclusive or non-limiting, and is a enumeration. It does not exclude additional elements or method steps not described.

  The term "consisting essentially of" refers to claims that depart from a particular material or step "and do not substantially affect the basic and novel features of the claimed invention." Limited to.

The term "consisting of" as used herein excludes any element, step, or ingredient not specified in the claims.
The terms "a", "an", "the" and similar referents used in the context of describing features of the invention, particularly in the context of the following claims, unless otherwise indicated, or Unless expressly denied by, shall be taken to include both the singular and the plural. Thus, for example, reference to "starch" may include one, two or more starches.

  As used herein, “film” refers to one or more polymers that can be used to separate areas or volumes, hold items, act as barriers, and / or act as printable surfaces Refers to a thin continuous article containing material.

As used herein, "bag" refers to a container made from a relatively thin, flexible film that can be used to contain and / or transport goods.
As used herein, a "bottle" can be made of the presently disclosed plastics, is typically of a greater thickness than a film, and is typically of a relatively large size adjacent to an opening. Refers to a container containing a narrow neck. Such bottles can be used to hold a wide variety of products, such as beverages, shampoos, conditioners, lotions, personal care products such as soaps, detergents, and the like.

Unless otherwise specified, all percentages, ratios, parts, and amounts used and described herein are by weight.
Any number, percentage, ratio, or other value described herein may include that value, as well as other values that are near or at the stated values, as will be appreciated by those skilled in the art. Accordingly, the stated values may include values that are at least sufficiently close to the stated values to perform the desired function or achieve the desired result, and / or may be rounded to the stated values. Should be interpreted broadly enough. The stated values include at least the expected variation in typical manufacturing processes, including values that are within 25%, 15%, 10%, 5%, 1%, etc. of the stated values. May be. Furthermore, as used herein, the terms “substantially”, “similarly”, “about” or “approximately” will still serve the desired function. Or an amount or state close to the stated amount or state that achieves the desired result. For example, the term "substantially""about" or "approximately" can refer to an amount that is within 25%, 15%, 10%, 5%, or 1% of the stated amount or value. it can.

  Several ranges are disclosed herein. Additional ranges may be defined between any of the values disclosed herein as exemplary of particular parameters. All such ranges are contemplated and are within the scope of the present disclosure. Further, the recitation of ranges of values herein is intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise stated herein, each individual value is incorporated herein as if it were individually described herein.

  It is to be understood that all numbers expressing quantities of ingredients, components, conditions, etc. used herein and in the claims are modified in all cases by the term "about". Although numerical ranges and parameters that describe the broad scope of the invention are approximations, the numerical values set forth in specific examples have been reported as accurately as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective test measurements.

  As used herein, "free of" or similar phrases means that the composition contains 0% of the recited component, ie, that component has not been intentionally added to the composition. . However, it is understood that such components may be accidentally formed under appropriate circumstances and may be accidentally present in another included component, for example, as an accidental contaminant. Let's do it.

  As used herein, the phrase "substantially free of" or a similar phrase means that the composition preferably contains 0% of the described ingredients, for example, accidental formation. It should be understood that very low concentrations may be present, even by accidental contamination, or even intentional addition. Such components, if any, are less than 1%, less than 0.5%, less than 0.25%, less than 0.1%, less than 0.05%, less than 0.01%, 0.005% Less than 0.001%, or less than 0.0001%.

II. Introduction The present disclosure is directed, inter alia, to articles formed from blends that include a renewable or sustainable carbohydrate-based polymeric material in combination with another polymeric material. In addition to increased sustainability, such articles may exhibit increased biodegradability and / or strength. Mixing one or more carbohydrate-based polymeric materials with one or more other polymeric materials (eg, a petrochemical or "green" sustainable polymer version of such a plastic resin), heating the mixture, and then heating the article By forming, for example, an article can be formed by extrusion, injection molding, blow molding, blow forming, or the like. In various embodiments, the carbohydrate-based polymeric material is substantially amorphous and / or has a glass transition temperature, heat distortion temperature, Vicat softening temperature, Young's modulus, low modulus as described herein. Starch-based polymeric materials that exhibit other specific properties related to crystallinity and the like can be included.

  The articles described herein can be manufactured in the form of any possible structure, including but not limited to bottles, boxes, other containers, cups, plates, cooking utensils, sheets, films, bags, and the like. . Thin films for bags and film wraps (eg, for wrapping around or on the product) can be easily manufactured using blown film forming equipment. Other processes that can be used for forming articles can include, but are not limited to, injection molding, blow molding, thermoforming, and other plastic manufacturing processes.

  Examples of suitable carbohydrate-based or starch-based polymeric materials for use in forming such articles are available from BiologiQ under the trade name NuPlastiQ or ESR ("Eco Starch Resin"). Specific examples include, but are not limited to, GS-270, GS-300, and GS-330. Certain features of such NuPlastiQ or ESR materials will be described in further detail herein. NuPlastiQ or ESR available from BiologiQ is merely a non-limiting example of a suitable carbohydrate- or starch-based polymer material because other carbohydrate- or starch-based polymer materials with similar properties may be suitable for use. It is.

  In one embodiment, the "other" polymeric material included in the blend (other than the carbohydrate-based polymeric material) can be a sustainable polymeric material formed, for example, from plants or other renewable resources (bacterial products). Thus, all or substantially all (eg, 90% or more, 95% or more, 97% or more, 98% or more, 99% or more) of the polymer content of the article is plant derived polymer or other regenerated Can be formed from available resources. Such a feature is particularly advantageous from a sustainability point of view. As described herein, a small amount of a compatibilizer may be present in addition to the polymer inclusion to enhance compatibility between the "other" polymer resin material and the carbohydrate-based polymer material. . In some embodiments, such a compatibilizer may be the only component not sourced or derived from a sustainable source. In other embodiments, such compatibilizers may be sustainable so that 100% of the article may be potentially sourced in a sustainable manner.

  In addition to the desirable sustainability properties, the carbohydrate-based polymeric material is biodegradable, the material with which it is blended (such as "green" PE (or biopolyethylene), "green" PP, or bioPET). ("Green" sustainable polymer material). In other words, the "green" sustainable polymer material, if not itself biodegradable, can actually become biodegradable when included in an article that also includes a carbohydrate-based polymer material. Such a result is also very advantageous.

  In addition, many articles (e.g., particularly thin films) do not have particularly good strength when formed from conventional plastic materials (e.g., petrochemical-based polymeric materials), and therefore, at a given thickness. It would be desirable to increase the strength of the steel. Such "green" plastic materials also do not have particularly good strength, since "green" plastic materials exhibit similar physical properties to their corresponding conventional petrochemical analogues. A means for increasing strength without increasing the thickness of the article would be desirable. When blended with a carbohydrate-based polymeric material, as described herein, such increased strength results are achievable. For example, a polyethylene film (eg, either biopolyethylene ("green" PE) or metallocene petrochemical PE) can have a dart impact strength of about 150 g for a 1 mil thick film, It would be advantageous if it was possible to increase the intensity without increasing the heat. The present embodiment can provide such an increase in strength. For example, when blended with a carbohydrate-based polymeric material as described herein, strength can be increased by at least 5%. Typical results of some embodiments may result in an increase in strength of 20% or even more.

  The article mixes the carbohydrate-based polymer material with a sustainable polymer material, heats the mixture, molds the mixture (eg, injection molded), extrudes the mixture, blows the mixture, and blows the mixture. It can be manufactured by, for example, forming the mixture and thermoforming the mixture. Various other plastic manufacturing processes will be apparent to those skilled in the art in light of the present disclosure.

  With respect to biodegradability, the present methods and articles may comprise blending such a plastic material with a carbohydrate-based (eg, starch-based) polymer material having certain characteristics, including low crystallinity, as described herein. This can provide useful biodegradability to plastic materials that are not themselves biodegradable. Such embodiments, in that they do not remain in a stable state of the polymer indefinitely, but can easily biodegrade a large number of discarded plastic items in landfills or similar environments. Is especially useful in

  In addition, Applicants have noted that when articles are stored in typical storage and use environments (eg, stored in homes, offices, warehouses, etc.), biodegradation of such articles does not readily occur, It was observed that biodegradation generally only started when the article simulated or was in a landfill, compost or other typical disposal conditions. For example, such conditions often include (i) temperatures somewhat above normal ambient "use" or "storage" temperatures, (ii) exposure to high moisture levels, and (iii) landfill or Includes exposure to certain types of microorganisms unrelated to compost and similar disposal environments. High temperatures and humidity will not cause such articles to degrade unless the required microorganisms are also present. Such a combination of conditions begins to biodegrade articles formed from such blends of materials. Third party tests described herein have shown that not only are carbohydrate-based polymeric materials biodegradable, but plastic materials that are not otherwise biodegradable are in fact biodegradable as well. I have confirmed.

  Although the mechanism by which such biodegradation is possible when blended with a carbohydrate-based polymeric material cannot be fully understood, blending the two plastic materials together is likely to be a particular feature of the carbohydrate-based polymeric material. Microorganisms that, in combination with some, will break down the hygroscopic barriers associated with non-biodegradable plastic materials and biodegrade carbohydrate-based polymer materials will not only biodegrade carbohydrate-based polymer materials, but also neighboring plastic molecules. It is thought to be possible to biodegrade. Carbon bonds have been broken, and biodegradation has been confirmed based on third-party tests that capture and measure the emissions of carbon dioxide and methane. Such a result is surprising, unexpected and particularly advantageous.

  Another aspect of the present disclosure is directed, in at least some embodiments, to a method for providing increased strength to blow molded plastic films by manipulating blow-up ratios and / or die gaps. Such methods can include blow molding a plastic film using a film blow molding apparatus, wherein the film is made of a polymer material (eg, polyethylene, etc.) and a renewable as described herein. The renewable carbohydrate-based polymer material is blown from a blend comprising a suitable carbohydrate-based (eg, starch-based) polymer material, and is substantially amorphous, eg, having a crystallinity of 20% or less. And / or other specific features. For example, the renewable carbohydrate-based polymer material may have a Young's modulus of at least 1.0 GPa and / or have a glass transition temperature, Vicat softening temperature, or heat distortion temperature of 70C to 100C. May be. The film blow molding apparatus is specifically operated with a high blow-up ratio of at least 2.0 and / or with a narrow die gap (eg, 500 micrometers or less) when blowing plastic films. . When using a carbohydrate-based polymeric material, such a feature can be attributed to a strength that would be provided at a lower, more typical blow-up ratio (eg, 1.5), or a wider die gap. Surprisingly provides increased strength to plastic films. Such a comparison indicating an increase in strength may use the same material, simply changing either the blow-up ratio or the die gap. Such an increase in strength is due to only "other" polymer materials (eg, polyethylene) without NuPlastiQ or ESR or other renewable carbohydrate-based polymer materials having certain characteristics as identified herein. Can be shown in comparison with the strength provided when blown the film. When PE is blow-molded alone, the blow-up ratio and die gap do not significantly affect the strength.

  Such a method is intended to control the strength of the resulting blown film, as opposed to other purposes where it is conceivable to manipulate the blow-up ratio (eg, perhaps to manipulate the lay flat width of the resulting film). May include specifically selecting a high blow-up ratio and / or a narrow die gap.

  For example, Applicants have found that when blowing films from only "other" polymer materials such as polyethylene, the blow-up ratio is manipulated with no significant effect on strength. In addition, Applicants have found that when a renewable carbohydrate-based polymeric material such as NuPlastiQ or ESR is added to the blend from which the film is blown, the same typical, commonly used blown film is used. It has been found that there is no significant decrease in the strength of such a blend film when blown at a 1.5 blow-up ratio, as compared to a 100% polyethylene or other polymeric material film. However, the Applicant further suggests that when blowing a blended film comprising a renewable carbohydrate-based polymer material such as NuPlastiQ or ESR, the blow-up ratio may be, for example, at least 2.0, preferably 2.2-2. It has been found that by increasing to .8 (eg, 2.5), an increase in strength can indeed be achieved.

  It is not fully understood why the strength increases at higher expansion ratios, as films formed from only "other" polymer materials do not have such an effect on strength, but the blow-up ratio is increased. As such, there may be some sort of aligned orientation, stretching, or regular arrangement of the amorphous or other structure of the molecules of the blend, which would result in increased strength. In any case, although perhaps not completely understood, Applicants have observed and measured the increase in strength under the conditions and methods described herein.

  Manufacture an article by mixing a renewable carbohydrate-based polymer material with another polymer material (eg, a polyolefin such as polyethylene, or other plastic), heating the mixture, and feeding the molten mixture to a film blow molding apparatus. The film blow molding apparatus can be specifically operated with a high blow-up ratio and / or a narrow die gap, and the selection (s) can be made to provide increased strength of the resulting film. It is specifically performed. Blown films can be further processed into a wide variety of possible structures, including but not limited to plastic bags, film wraps, and the like.

  Another aspect of the present disclosure is that the typical carbohydrate-specific odors that occur during typical heating and molding or other molding of plastic materials include only a small percentage of odor reducers, preferably organic odor reducers It is intended for embodiments to be counteracted by such. In one embodiment, the odor-reducing agent may be included with the carbohydrate-based polymer material (eg, as part of a masterbatch of carbohydrate-based polymer material).

  In one embodiment, the carbohydrate-based polymeric material may be present in a much higher proportion than the odor reducing agent. For example, the carbohydrate-based polymeric material may be at least 1000 times, 10,000 times, or 50,000 times more odor reducing agent. Even at very low concentrations (eg, 1 part odor reducing agent for 50,000 parts carbohydrate-based polymer material), effective control of popcorn, caramel corn, or slightly burnt starch odor (ie, Substantially complete removal) can be achieved. It is surprising that such a small amount of odor reducing agent is sufficient to achieve such a result.

  The masterbatch comprising the odor control agent and the carbohydrate-based polymer material can be blended with any practically conceivable polymer resin material and used to produce the desired plastic article. For example, an article may be obtained by mixing a carbohydrate-based polymer material (including an odor reducing agent) with a polymer resin, heating the mixture, molding the mixture (eg, injection molding), extruding the mixture, and blowing the mixture. It can be made by blow molding, blow-forming the mixture (eg, forming a blown film), and thermoforming the mixture. The foregoing list of plastic manufacturing processes is, of course, not exhaustive, and various other plastic manufacturing processes will be apparent to those skilled in the art.

  A small amount of odor reducing agent may be included in the carbohydrate-based polymer material and introduced with the polymer resin with which the carbohydrate-based polymer material is blended, or otherwise introduced into the blend. In one embodiment, a masterbatch of a carbohydrate-based polymeric material may be provided with an odor reducing agent already contained therein. In another embodiment, the odor reducing agent can be added separately from the carbohydrate-based polymer material and / or separately from the polymer resin included in the blend forming the article. It is clear that in addition to NuPlastiQ or ESR available from BiologiQ, other carbohydrate-based or starch-based polymeric materials can also benefit from the addition of small amounts of odor reducers as described herein. There will be.

III. Exemplary Articles and Methods FIG. 1 illustrates an exemplary “basic” process 100 according to the present invention. Including an odor reducing agent, or with respect to blow-up ratio and / or die gap, provided that the "other" polymeric material includes the sustainable resin itself (eg, "green" PE, bio-PET, etc.) It will be apparent from the present disclosure that various details may be added, such as the particular choice when blowing the film. At 102, the process 100 includes one or more “other” polymeric materials, such as, but not typically, non-biodegradable materials (eg, polyethylene, polypropylene, other polyolefins, polyethylene terephthalate, polyester) , Polystyrene, ABS, polyvinyl chloride, nylon, or polycarbonate). At 104, the process 100 provides one or more carbohydrate-based polymeric materials that are substantially amorphous and exhibit a crystallinity of 20% or less (eg, more typically less than 10%). May be included. Other features may alternatively or additionally be present (e.g., a Young's modulus of 1.0 GPa or more, a glass transition temperature of at least 70C, at least 80C, or 80C to 100C, a Vicat softening temperature or Heat distortion temperature). The one or more carbohydrate-based polymeric materials can include a starch-based polymeric material. The carbohydrate-based polymer material and other polymer materials can be provided in any desired form, such as pellets, powders, noodles, slurries, and / or liquids. In certain embodiments, the material may be in the form of a pellet. The method further includes blending another polymeric material with the carbohydrate-based polymeric material.

  Such a blend may be formed into the desired article during manufacturing by any conceivable process. An example of such would be an extrusion process. For example, other polymeric materials and carbohydrate-based polymeric materials can be fed to an extruder (eg, to one or more hoppers thereof). Different materials can be introduced into the extruder along the screw in the same chamber, in different chambers at about the same time (eg, via the same hopper), or at different times (eg, via different hoppers, one earlier than the other). Provided). It will be clear that many possibilities are possible.

  In some cases, other polymeric materials can include polyolefins. For example, such plastic or polymer materials can include, but are not limited to, polyethylene, polypropylene, polyethylene terephthalate, other polyolefins, polyesters, polystyrene, ABS, polyvinyl chloride, nylon, polycarbonate, and the like. Such plastic materials may be sourced from petrochemical sources, or so-called “green” or sustainable sources (eg, “green” PE, bio-PET, etc.).

  In some cases, the “other” polymer material itself may be sustainable (eg, a sustainable polyolefin). For example, such sustainable polymer materials include "green" polyethylene (Bio-PE), "green" polypropylene (Bio-PP), bio-PET, or other materials that can be formed from sustainable plant sources. Examples include, but are not limited to, plastic materials. As a non-limiting example, a "green" PE can be derived from ethanol that can be formed from sugar cane, other sugar crops (eg, sugar beet) or grains (eg, corn, wheat, etc.). “Green” PE (sometimes referred to as “bioPE”) has a chemical structure similar to PE formed from petrochemical feedstocks, except that the ethanol or ethylene monomer used for polymerization is petroleum Derived from sustainable raw materials, not chemical raw materials. "Green" PP can also be formed from propylene, which can be derived from propanol (or possibly isopropanol) from sugar cane, other sugar crops, or cereals such as corn. Another example of a "green" sustainable polymeric material is that the monomers used to form, for example, poly (ethylene terephthalate) (e.g., typically ethylene glycol and terephthalic acid) include sugarcane, other Bio-PET that can be derived from sugar sources or plant sources such as cereals. PET is the most common thermoplastic resin based on polyester. Another polyester that can also be formed from sustainable plant sources is polybutyrate adipate terephthalate (Bio-PBAT). PBAT can be formed as a copolyester of adipic acid, 1,4 butanediol and dimethyl terephthalate. One or more of such starting materials can be from a sustainable plant source. Another possible "green" polymeric resin material that can be used is poly (lactic acid). As will be appreciated by those skilled in the art, PLA is typically made from monomers of lactic and / or lactide esters. One or more starting materials for PLA production can be from a sustainable plant source. Other possible "green polymers" that may be used and will be familiar to those skilled in the art include PBS (polybutylene succinate) or PCL (polycaprolactone).

  Those skilled in the art will be familiar with the methods for synthesizing such polymers. One or more of the components used to make such a polymer can be derived from a suitable renewable plant or other renewable biological source (eg, bacterial origin). "Green" PE is available from Braskem, and bioPET is available from Plant Bottle (TM) of Coca Cola (TM), as well as from other plastic manufacturers. PE, PP, PET and PBAT are examples of “green” bioplastics that can be formed from materials derived from sustainable plant sources, but they are at least partially formed from sustainable materials (eg, plant sources) It will be appreciated that a number of other "green" plastics may also be suitable for use, as long as they can be done. In addition, sugar cane, other sugar crops, corn, wheat and other cereals may be illustrative and non-limiting examples of plant material from which such `` green '' polymeric materials may be derived. It will be appreciated that a large number of plants and materials may also be suitably used.

  Carbohydrate-based polymeric materials can be formed from multiple materials (eg, mixtures) that include one or more starches. For example, one or more starches can be produced from one or more plants such as 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 starch, which the applicant has found to provide a synergistic increase in strength, may be used. Plasticizers are also present in the mixture of components from which the carbohydrate-based polymeric material is formed. Water may also be used in forming the carbohydrate-based polymer material, but there is only a small to negligible amount of water in the finished carbohydrate-based polymer material.

  Thus, it will be appreciated that in some embodiments, the entire polymer content (or substantially the entire polymer content) of the article may be derived from plant material. "Green" polymeric materials typically use polymerizable monomers or other small molecule polymerizable components that can be derived from ethanol (or the like) formed from the desired plant material, but with carbohydrate-based ( Or starch-based) polymeric materials may be formed from starch (and glycerin or other plasticizers) rather than processing such starch or other plant material to form smaller polymerizable monomers. Thus, the molecular weight of the starch used to make the starch-based polymer material is lower than the molecular weight of the relatively small molecule monomer that is made to use to make the "green" sustainable polymer material. Usually can be orders of magnitude larger. For example, plant-derived monomers or other polymerizable components used to make "green" sustainable polymeric materials typically have less than about 500 daltons, less than 400 daltons, less than 300 daltons, The molecular weight of the starch (s) used to make the starch-based polymeric material may be less than 100 daltons, or less than 100 daltons, typically much higher, often above 500 daltons and often It is measured in thousands, tens of thousands, or even more (eg, greater than 500 daltons, at least 1000 daltons, at least 10,000 daltons, at least 25,000 daltons, at least 40,000 daltons, etc.). In other words, the starch material used to form the starch-based material (eg, native starch) is typically the monomer or other polymer used to make the "green" sustainable polymer material. It is a more complex molecule than the sex component. 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, in the range of about 20,000 daltons to about 4,000,000 daltons (eg, amylose ranges from about 20,000 daltons to about 2,000,000 daltons). , While amylopectin can range from about 65,000 daltons to about 400,000,000 daltons). Tapioca starch can have a molecular weight ranging from about 40,000 daltons to about 340,000 daltons. The glycerin used to form the starch-based polymeric material can also be from a sustainable source. Glycerin also has a molecular weight of 92 Dalton, of course.

  Returning to the characteristics of the carbohydrate-based polymer material, the one or more carbohydrate-based polymer materials can be formed mostly from 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 attributed to one or more starches. In one embodiment, 65% to 90% by weight of the finished carbohydrate-based polymeric material may be attributable to one or more starches. Other than negligible moisture content, the balance of the finished carbohydrate-based polymer material can be attributed to plasticizers (eg, glycerin). The above percentages can represent the percentage of starch relative to the starting material from which the carbohydrate-based polymer material is formed, or the ratio of the finished carbohydrate-based polymer material from or resulting from the plasticizer (eg, at least 65% of the carbohydrate-based polymer material % May be attributable to (formed from) the starch (s) as the starting material). Although some water may be used to form the carbohydrate-based polymer material, substantially the remainder of the carbohydrate-based polymer material may be due to glycerin or other plasticizers. Very little residual water (eg, less than 2%, typically less than about 1%) may be present in the finished carbohydrate-based polymeric material.

  For example, the material from which the one or more carbohydrate-based polymeric materials are formed is at least 12%, at least 15%, at least 18%, at least 20%, at least 22%, 35% or less, 32% or less, 30% or less, 28% or less. % Or less than 25% plasticizer. Such percentages can represent the percentage of the finished carbohydrate-based polymer material that is derived from or attributable to the plasticizer (eg, at least 12% of the carbohydrate-based polymer material is attributable to the plasticizer as a starting material). (May be formed from).

  Exemplary plasticizers include glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, hydrogen-bond-forming organic compounds without hydroxyl groups, anhydrides of sugar alcohols, animal proteins, vegetable proteins, fatty acids, phthalates Acid esters, dimethyl and diethyl succinates and related esters, glycerol triacetate, glycerol monoacetate and diacetate, mono, di, and tripropionate, glycerol butanoate, tearate, lactate, citrate, adipate, stearin Examples include, but are not limited to, acid esters, oleic esters, other acid esters, or combinations thereof. Glycerin may be preferred.

  The finished carbohydrate-based polymer material is 5% or less, 4% or less, 3% or less, 2% or less, 1.5% or less, 1.4% or less, 1.3% or less, 1.2% by weight or less. It may contain up to 1% by weight, or up to 1% by weight of water. NuPlastiQ or ESR materials available from BiologiQ are examples of such finished carbohydrate-based polymer materials, but other materials available elsewhere (eg, in the future) may also be suitable for use. Will also be understood.

  In some embodiments, a mixture of different starches may be used in forming the carbohydrate-based polymeric material. The use of such a mixture of different starches (eg, from different plants) has surprisingly been found to be associated with a synergistic increase in strength in articles comprising such carbohydrate-based polymeric materials. In such a starch mixture, the starch is present in the mixture in at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 5%, based on the total weight of the plurality of starches. 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, 95% or less, 90% or less, 85% or less, 80% It can be present in an amount of up to 75% by weight, up to 70% by weight, up to 65% by weight, up to 60% by weight, up to 55% by weight, up to 50% by weight, or from 10% to 50% by weight. Some non-limiting exemplary mixtures 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 second starch. It may contain one starch and 50% of a second starch. Mixtures of more than two starches (eg, using three or four different starches) can also be used.

  Examples of suitable carbohydrate-based (eg, starch-based) polymeric materials for use in forming films and other articles are under the trade name NuPlastiQ or ESR ("Eco Starch Resin") from BiologiQ, Idaho Falls, Idaho. Available. Specific examples include, but are not limited to, GS-270, GS-300, and GS-330. NuPlastiQ or ESR may be provided in pellet form. The physical properties of GS-270 and GS-300 are shown in Table 1 below.

The above features shown for GS-270 and GS-300 are examples of other NuPlastiQ or ESR products available from BiologiQ, although the values may vary somewhat. For example, NuPlastiQ or ESR products from BiologiQ generally have 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 from about 70 ° C to about 100 ° C, Alternatively, it may have a glass transition temperature, Vicat softening temperature or heat distortion temperature in the range of 80C to 100C. One skilled in the art will appreciate that the glass transition temperature, Vicat softening temperature, and heat distortion temperature can be indicative of crystallinity. The values for melting temperature range, density, Young's modulus, and water content can be the same or similar to those shown in Table 1 above. Some features may also vary somewhat (eg, ± 25%, or ± 10%) from the values shown for GS-270 and GS-300. NuPlastiQ or ESR has an amorphous structure (eg, more amorphous than typical raw starch). For example, typical raw starch powder has a nearly crystalline structure (eg, greater than 50%), while NuPlastiQ or ESR has a nearly amorphous structure (eg, less than 10% crystals). Any suitable standard can be used to measure the glass transition temperature, heat distortion temperature, Vicat softening temperature or any other physical property. By way of example, the glass transition temperature can be determined according to the heat distortion temperature according to ASTM D-3418, ASTM D-648, and the Vicat softening temperature according to ASTM D-1525.

  NuPlastiQ or ESR has a very low water content, as described. Since NuPlastiQ or ESR absorbs moisture, it exhibits plastic behavior and becomes flexible. Upon removal from the moist environment, the material dries and becomes hard again (eg, again showing less than about 1% moisture content). Moisture present in NuPlastiQ or ESR (eg, in the form of pellets) can be released in the form of steam during processing as shown in FIG. As a result, non-biodegradable plastic materials typically contain no or negligible water, and the water in NuPlastiQ or ESR can usually be released during the manufacture of the desired article, Films or other articles made from a starch-based polymer material such as NuPlastiQ or ESR blended with a non-biodegradable plastic material may exhibit lower moisture content.

  Low water content in carbohydrate-based polymer materials can be important, especially if the article requires the formation of thin films, as high water content can cause incompatibility with non-biodegradable plastic materials . For example, as water evaporates, this can create voids in films or other articles, as well as create other problems. When blown thin films, the carbohydrate-based polymeric material used may preferably contain up to about 1% water.

  Low water content is not achieved in NuPlastiQ or ESR materials by esterification, as is common in some conventional TPS materials, which may include relatively low water content. Such esterification is expensive and can be complicated to perform. The same applies to etherification. In addition, NuPlastiQ or ESR materials, which are examples of carbohydrate-based polymeric materials that can be used herein, may also be used because NuPlastiQ or ESR or other carbohydrate starting materials have been chemically reacted and / or changed. Typically, they do not themselves contain any identifiable starch or identifiable glycerin. An X-ray diffraction pattern of an exemplary carbohydrate-based polymeric material, such as that shown below (eg, shown in FIG. 4), demonstrates such chemical changes, and the finished polymeric material exhibits such distinct natural forms Indicates that it may be substantially free of starch. In other words, the carbohydrate-based polymeric material is not simply recognized as a mixture comprising starch and glycerin. The low water content achievable in carbohydrate-based polymeric materials is due, at least in part, to thermoplastic polymers that do not retain water, such as native starch, or the chemical transformation of starch and plasticizer materials into conventional thermoplastic starch. it is conceivable that.

  Returning to FIG. 1, processing at relatively high temperatures may release some of the volatile glycerin (eg, appearing as smoke). If necessary (e.g., if the stored pellets may have absorbed additional water), drying of the pellets may be accomplished by introducing warm dry air, e.g. Absorbed water is also sufficient to drive off). Especially when forming a film, the pellets should be dried before processing to a moisture content of less than about 1%. NuPlastiQ or ESR pellets can be easily stored in a closed container with desiccant in a dry place to minimize hygroscopicity and prevent unwanted degradation.

  In addition to NuPlastiQ or ESR being thermoplastic, NuPlastiQ or ESR is also thixotropic, where the material is solid at ambient temperature but flows as a liquid when heat, pressure and / or frictional motion is applied Means that. Advantageously, NuPlastiQ or ESR pellets can be used in standard plastic manufacturing processes in the same way as petrochemical pellets (any typical non-biodegradable plastic resin pellets). NuPlastiQ or ESR materials and products made therefrom may exhibit gas barrier properties. Products made using such NuPlastiQ or ESR pellets (eg, films) exhibit oxygen gas barrier properties (see, eg, examples of Applicants' earlier application, which are already incorporated by reference). . NuPlastiQ or ESR materials can be non-toxic and edible, all manufactured using edible raw materials. NuPlastiQ or ESR and products made therefrom can be water-resistant but water-soluble. For example, NuPlastiQ or ESR may resist swelling under humid heating conditions to such an extent that the pellets (eg, 3-4 mm size) do not completely dissolve in boiling water within 5 minutes, while the pellets may have Dissolves in mouth within. NuPlastiQ or ESR may be stable in that it may not show any significant aging, even when left under relatively high humidity conditions, which have different properties than many other thermoplastic starch materials. Of course, products manufactured with NuPlastiQ or ESR may also exhibit such properties. If NuPlastiQ or ESR is stored in a humid condition, the excess moisture absorbed can be easily evaporated and if the moisture content is less than about 1%, the formation of films or other articles Can be used for

  NuPlastiQ or ESR materials are also typically found in relatively humid conditions when there are no other conditions typical of landfills, composts or similar disposal environments containing certain required microorganisms. Does not undergo biodegradation under storage conditions. It will be appreciated that when such conditions are present, NuPlastiQ or ESR not only biodegrades, but also surprisingly biodegradable non-biodegradable plastic materials blended with it. Evidence for such surprising results is included in the Examples section included herein.

  NuPlastiQ or ESR can be cost competitive and is 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 the like. The non-biodegradable polymers described above can be made biodegradable by blending with NuPlastiQ or ESR, but NuPlastiQ or ESR can be polylactic acid (PLA), poly (butylene adipate-co-terephthalate) (PBAT) Already biodegradable and / or compostable polymers such as, polybutylene succinate (PBS), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), other so-called thermoplastic starches and various others It will be understood that they can also be blended with. PBS, PCL, and PHA are polyesters. EcoFLEX ™ is another example of a plastic material that can be blended with NuPlastiQ or ESR carbohydrate-based polymer materials. For example, the method is not limited to blending a carbohydrate-based polymeric material (eg, NuPlastiQ or ESR) with only a non-biodegradable plastic material, but also a biodegradable plastic (other than NuPlastiQ or ESR), if necessary. It will also be appreciated that the

  As a further explanation, PLA is compostable, meaning that it can degrade under high temperature conditions (ie, composting conditions), but is not technically "biodegradable." Some of the above materials, such as PBS, PCL, and PHA, can be both biodegradable and compostable. EcoFLEX ™ has been certified as compostable. The FTC Green Guidelines unconditionally state that a plastic is "degradable" unless it degrades within "reasonably short time" after "conventional disposal" (most recently defined as within 5 years). States that it cannot be asserted.

  In some embodiments, NuPlastiQ or ESR may be provided in a masterbatch formulation that may include a carbohydrate-based polymeric material as described above, and an amount of one or more compatibilizers. The masterbatch may also include one or more non-biodegradable plastic materials. Such masterbatch formulation pellets can be mixed with non-biodegradable plastic material pellets during processing. Depending on the desired ratio of NuPlastiQ or ESR and / or compatibilizer and / or conventional non-biodegradable plastic material in the finished product, use any conceivable proportion when mixing such different pellets. be able to.

  NuPlastiQ or ESR contains a very low water content. For example, raw starch (eg, used to form ESR) can typically contain about 13% by weight of water, while the finished NuPlastiQ or ESR pellets available from BiologiQ contain less than about 1% water. including. NuPlastiQ or ESR materials are biodegradable, and as described herein, starch-based NuPlastiQ or ESR materials are not only biodegradable, but also non-biodegradable PE, PP, PET, polyester, When blended with other polymers, such as polystyrene, ABS, polyvinyl chloride, nylon, and other non-biodegradable plastic materials, the blended material becomes substantially completely biodegradable. Such a result is indeed surprising and particularly advantageous. The examples herein provide evidence of such surprising results. Typical thermoplastic starch materials do not claim or exhibit such properties when blended with other plastic materials.

  NuPlastiQ or ESR materials may exhibit some elasticity, but that elasticity may be less than many other polymers (e.g., "green" sustainable polymers, especially those that mimic petrochemical polymers and the like) . Films and other articles may be formed from a blend of NuPlastiQ or ESR with any desired other polymer (s), increasing the strength at a given article thickness compared to the other polymer alone Provides elastic results. Films are described and often used in embodiments of the specification where strength is often of greater importance, but articles other than films (eg, bottles, sheets, boxes, cups, plates, utensils, or other It will also be apparent that the configuration of Example 1) can provide increased strength. Table 2 below shows, for comparison, elongation at break and modulus values for various standard plastic ("SP") materials, various "green" plastic materials, and NuPlastiQ or ESR. "Environmentally friendly" refers to one or more environmentally desirable properties, such as that the material is derived from at least partially sustainable materials, is compostable, and / or is biodegradable. It is possible to have. NuPlastiQ or ESR in Table 2 had a tensile strength of 40 MPa.

FIG. 3 shows the same data as in Table 2 in a chart format. It will be appreciated that some of the products listed in the table and listed as standard plastics shown in FIG. 3 include, but are not limited to, BioPET, "green" PP, "green" PE, And "green" congeners that can be derived from sustainable sources such as bioPBAT. PLA is compostable, meaning that it can degrade under high temperature conditions (ie, composting conditions), but is not technically "biodegradable." These other exemplary materials, such as EcoFlex, PBS, PCL, PHA, etc., can be both biodegradable and compostable. The FTC Green Guidelines unconditionally state that a plastic is "degradable" unless it degrades within "reasonably short time" after "conventional disposal" (most recently defined as within 5 years). States that it cannot be asserted.

  NuPlastiQ or ESR materials described as suitable for use herein as carbohydrate-based (eg, starch-based) polymeric materials are substantially amorphous. For example, raw starch powders (eg, those used in the production of NuPlastiQ or ESR and various other thermoplastic starch materials) have about 50% crystalline structure. NuPlastiQ or ESR materials available from BiologiQ differ from many other commercially available thermoplastic starch (TPS) materials in their crystalline versus amorphous properties. See, for example, Kris Frost (September 2010), "Thermoplastic Starch Composites and Blends," Ph.D. 62-63 state that "of particular interest in TPS is the formation of V-type amylose crystals, with any integrity toward gelatinization during processing and subsequent degradation." Frost further continues, "Gelatinization involves loss of granular and crystalline structure, often by heating with water, often by including other plasticizers or modified polymers." The deterioration is due to the rewinding of the amylose spiral coil. Starch molecules broken during gelatinization slowly rewind into their native helical configuration or a new single helical conformation known as V-type, rapidly weakening the TPS film and increasing optical clarity. You will lose. Thus, conventional TPS tends to reform the crystal structure after the gelatinization process used to make TPS from raw starch. In contrast, NuPlastiQ or ESR materials available from BiologiQ hardly revert to a crystalline structure. In addition, it is stable and useful to form relatively optically clear films (eg, by sandwiching a NuPlastiQ or ESR containing layer between polyethylene or other polyolefin layers) Relatively high optical clarity can be maintained.

  In contrast to typical TPS materials, NuPlastiQ or ESR materials, which are suitable examples of starch-based polymeric materials for use in forming the articles described in this application, have an amorphous microstructure and surface properties. It has physical properties as shown in FIG. The difference in molecular structure between the conventional TPS and the NuPlastiQ or ESR material is that the NuPlastiQ or ESR material described herein is less than the conventional thermoplastic starch-based material as shown by the X-ray diffraction shown in FIG. The diffraction pattern results for the NuPlastiQ or ESR material (Sample 1), which is evidenced by much lower crystallinity and is available from BiologiQ, is shown in FIG. Compare with a raw potato starch blend. The NuPlastiQ or ESR diffraction pattern as seen in FIG. 4 is much less crystalline (eg, less than about 10% crystallinity) than that of the native starch blend (about 50% crystallinity). Differences in the diffraction patterns demonstrate that processing native starch into NuPlastiQ or ESR resulted in a substantial chemical change in the material. For example, native starch has significant diffraction peaks between 20-25 °, but such peaks are not found in NuPlastiQ or ESR. Native starch further shows a strong peak at about 45 ° (intensity of 0.5-0.6), which is significantly reduced in NuPlastiQ or ESR (only about 0.25-0.3). As shown, the diffraction intensity is higher for native starch than for NuPlastiQ or ESR over almost the entire spectrum except for about 18 ° to about 22 °. The high diffraction intensity seen over a wide spectrum indicates a greater degree of crystallinity of native starch compared to NuPlastiQ or ESR. As shown, there are many other differences as well.

  By way of example, carbohydrate-based (eg, starch-based) polymeric materials used in making films according to the present disclosure can have a crystallinity of less than about 40%, less than about 35%, less than about 30%. It may have a crystallinity of 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%. Any suitable test mechanism for determining crystallinity can be used, including, but not limited to, FTIR analysis, X-ray diffraction, and symmetric reflection and transmission techniques. Various suitable test methods will be apparent to those skilled in the art.

  In addition to differences in the microstructure of the finished NuPlastiQ or ESR compared to starting materials, films, bottles, sheets, disposable cooking utensils, plates, cups, or other articles made from blends containing carbohydrate-based polymeric materials, other Although similar in point, they differ from articles formed using only conventional TPS and starch powder, or non-biodegradable plastic materials. For example, an article formed by blending a carbohydrate-based polymeric material, such as NuPlastiQ or ESR, described herein with a non-biodegradable plastic material can be used when blending a conventional TPS material with a polymeric material, such as polyethylene. Does not have the general "sea island" feature. The properties of the different films can be determined by comparing the physical properties of the films, as shown in Table 11 of Example 5 of Applicant's US Patent Application No. 15 / 481,806, which is already incorporated by reference. You can see. In particular, this table shows that films made by blending the carbohydrate-based polymeric materials contemplated herein with non-biodegradable polyethylene versus conventional TPS blended with PE (Cardia BL-F). Compare the physical properties of In addition to the property differences seen in Table 11 of Example 5 of Applicant's U.S. Patent Application No. 15 / 481,806, films based on conventional TPS materials, such as Cardia BL-F blended with PE, Not biodegradable and cannot be composted.

  As described herein, blends of the carbohydrate-based polymeric materials and non-biodegradable plastic materials described herein not only allow the carbohydrate-based material to be biodegradable, but also The plastic material actually becomes a biodegradable plastic material (even though non-biodegradable plastic materials alone are not biodegradable). Such results do not occur when blended with typical TPS materials. This difference in biodegradability is due to the fact that the entire composite structure (ie, the film or other structure) can now be biodegraded as shown in the various examples below, so that the resulting film and It clearly illustrates that there are significant structural and / or chemical differences in other articles.

Without being bound by any particular theory, carbohydrate-based polymer resins can cause water and bacteria to degrade the placement and bonding of otherwise non-biodegradable plastics blended with carbohydrate-based polymer resin materials. In a manner that allows the blended product to have reduced crystallinity and interfere with the crystallinity and / or hygroscopic barrier properties of polyethylene or other non-biodegradable plastic materials. I have. In other words, long polymer chains of polyethylene or other non-biodegradable plastic materials, when blended with carbohydrate-based polymer materials as contemplated herein, are chemically and chemically rich in bacterial and microbial rich environments. And are more easily destroyed by mechanical forces. Subsequently, microorganisms naturally present in the disposal environment (eg, landfills) can consume the remaining smaller molecules so that they are free of natural components (eg, CO ₂ , CH ₄ , and H _2). O).

  For example, truly biodegradable plastics can be converted to natural constituents or compounds, such as carbon dioxide, methane, water, inorganic compounds, or biomass, through microbial assimilation (eg, microbial enzymatic action on plastic molecules). Decompose. Biodegradation of plastics is made possible by first breaking down the polymer chains, either by chemical or mechanical action, but can only be fully achieved by the breakdown of the molecule by assimilation of microorganisms.

  Plastics made from petrochemical raw materials or obtained from vegetable sources are reborn as monomers (eg, a single small molecule that can chemically react with other small molecules). When the monomers are linked together, they become a polymer ("a lot") known as a plastic. Many monomers are readily biodegradable before being linked together, but after being linked together by polymerization, the molecules can become very large and linked in such an arrangement and linkage. However, assimilation of microorganisms by microorganisms is not practical within a reasonable time frame.

  Polymers are formed using both crystalline (regularly packed) and amorphous (randomly arranged) structures. Many polymers contain a high degree of crystallinity with some amorphous regions randomly arranged and entangled throughout the polymer structure.

  The NuPlastiQ or ESR material available from BiologiQ is formed from a starting starch material that is highly crystalline but the finished NuPlastiQ or ESR plastic resin material exhibits low crystallinity (substantially amorphous). Such a starch-based polymeric material is used as a starting material in the manufacture of an article as described herein. Thus, NuPlastiQ or ESR is a plastic made from starch. The molecules (size and link) of plastics made with NuPlastiQ or ESR, as evidenced by the experimental test results included herein, due to their natural starch-based origin and carefully controlled linkage types In addition, it is very sensitive to biodegradation by humidity (water) and enzymatic reactions caused by the introduction of bacteria or other microorganisms.

  Rigid forms of polyolefins, such as polyethylene and polypropylene, have a high degree of crystallinity and form monomer molecules (whether derived from petroleum or from ethanol or other small building block molecules derived from vegetable sources). Manufactured by converting to long chain polymers. The linkages that occur when linking 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 given article is formed from a blend of a conventional non-biodegradable plastic material and a conventional TPS, it will not usually suddenly acquire biodegradable properties (sometimes biodegradable) Excluding the starch portion of the blend).

  Applicants have proposed a method for providing biodegradability to other non-biodegradable plastic materials by blending such a plastic material with a carbohydrate-based polymer material having low crystallinity (eg, NuPlastiQ or ESR). Was developed. Typically, non-biodegradable plastic materials have a higher degree of crystallinity (eg, especially for PE or PP).

  In addition to being biodegradable, the resulting blend may additionally or alternatively have a higher modulus (stiffness, or strength) than polyethylene or other non-biodegradable plastic materials, such as pure polyethylene or It can be used to make stronger plastic films or other articles than the same articles made of other pure non-biodegradable plastic materials. Such strength-enhancing properties are described in U.S. Patent Application No. 15 / 481,806, which is already incorporated herein by reference.

  Returning to FIG. 1, at 106, the process 100 includes mixing one or more other polymeric materials with one or more carbohydrate-based polymeric materials to produce a mixture of materials. In some cases, mixing one or more other polymeric materials with one or more carbohydrate-based materials can be performed using one or more mixing devices. In certain implementations, a mechanical mixing device can be used to mix one or more other polymer materials with one or more carbohydrate-based polymer materials. In one implementation, at least some of the components of the mixture of materials can be combined in an apparatus such as an extruder, injection molding machine, or the like. In other implementations, at least some of the components of the mixture of materials can be mixed before being provided to the device.

  The one or more carbohydrate-based polymeric materials can be present in the mixture of materials over a wide variety of ranges depending on the properties desired. In one embodiment, such inclusions provide biodegradability to other non-biodegradable "other" polymeric materials included in the blend and provide a given level of strength to increase strength to a desired degree. It may be sufficient to provide a “sustainable” content or for another purpose. By way of example, the carbohydrate-based polymeric material comprises 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% of the mixture of materials. , At least 25%, at least 30%, at least 35%, at least 40%, at least 45%, 99% or less, 95% or less, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, % To 98%, 20% to 40%, 10% to 40%, 20% to 30%, 50% to 80%, or 40% to 60% by weight. If desired, two or more carbohydrate-based polymeric materials, and / or two or more other plastic materials can be included in the blend.

  Other polymeric materials comprise 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% of the mixture of materials. %, At least 30%, at least 35%, at least 40%, at least 45%, at least 50%, 99% or less, 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, Be present in the mixture of materials in an amount of 65% or less, 60% or less, 2% to 98%, 50% to 90%, 65% to 75%, 20% to 50%, or 40% to 60% by weight. Can be.

  The compatibilizer may be present in the mixture of materials. The compatibilizer can be mixed with other polymeric materials, carbohydrate-based polymeric materials, mixed with both, or provided separately. In many cases, a compatibilizer may be provided, for example, with at least one polymeric material included in a masterbatch formulation. The compatibilizer can be a modified polyolefin or other modified plastic such as maleic anhydride-grafted polypropylene, maleic anhydride-grafted polyethylene, maleic anhydride-grafted polybutene, or a combination thereof. The compatibilizer can also include an acrylate-based copolymer. For example, the compatibilizer can include an ethylene methyl acrylate copolymer, an ethylene butyl-acrylate copolymer, or an ethylene ethyl acrylate copolymer. Further, the compatibilizer may include a poly (vinyl acetate) -based compatibilizer. In one embodiment, the compatibilizer is a grafted version of another polymer material (eg, maleic anhydride-grafted polyethylene if the other polymer material is polyethylene) or one of the blocks is another polymer material. May be a copolymer (eg, a block copolymer) that is the same monomer as that of (eg, a styrene copolymer where the other polymer material is polystyrene or ABS).

  The mixture of materials is at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less , 25% or less, 20% or less, 15% or less, 10% or less, 9% or less, 8 or less%, 7% or less, 6% or less, 0.5% to 12%, 2 to 7% by weight, or 4% % To 6% by weight of a compatibilizer.

  Certainly, but not necessarily, in at least some embodiments it would be best to avoid such inclusion, but any of a variety of UV and OXO degradable additives, such as PDQ from Willow Ridge Plastics -M, PDQ-H, BDA, and OxoTerra (TM), OX1014 from LifeLine, Restore by Enso (R), or EcoPure (registered trademark) by Bio-Tec Environmental, ECM Masterbatch Pellets1M by ECM Biofilms or Biodegradable201 and, It is within the scope of the present invention to include an organic additive such as Biodegradable 302 BioSphere®. That. For example, other additives to increase strength (eg, Biomax® Strong from Dupont) or other additives may be included.

  The one or more additives may comprise at least 0.5%, at least 1%, at least 1.5%, at least 2%, at least 2.5%, at least 3%, at least 4%, at most 4%, at most 9% of the mixture. Up to 8%, up to 7%, up to 6%, up to 5%, 0.2% to 12%, 1% to 10%, 0.5% to 4%, or 2% to 6% by weight And may be included in a mixture of materials.

  Although primarily described with respect to a mixture of thermoplastic materials that can be melted together to form a desired blend, in some embodiments, the carbohydrate-based polymer material is replaced with another non-thermoplastic polymer material (e.g., Is thermosetting and may be able to be blended with, for example, in the case of silicones). For example, a resin component that is a precursor of such a non-thermoplastic "other" polymer material can be blended with a carbohydrate-based polymer material to polymerize the non-thermoplastic "other" polymer material or other Formation can occur in the presence of the carbohydrate-based polymer material, resulting in a finished product that is a blend of the carbohydrate-based polymer material and a thermoset or other non-thermoplastic material. Carbohydrate-based polymeric materials have the same advantages (eg, increased sustainability, increased biodegradability, increased strength) when blending the two together into a non-thermoplastic material as described herein. Etc.).

  Referring to FIG. 1, at 108, the process 100 may include heating a mixture of materials, particularly if the materials are thermoplastic. In one implementation, the mixture of materials is 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, 200 ° C or less, 190 ° C or less, 180 ° C or less. Heat to a temperature below 175 ° C, below 170 ° C, below 165 ° C, below 160 ° C, below 155 ° C, below 150 ° C, 95 ° C to 205 ° C, 120 ° C to 180 ° C, or 125 ° C to 165 ° C. be able to.

  The mixture of materials, including other polymeric materials and carbohydrate-based polymeric materials, can be heated in one or more chambers of the extruder. In some cases, one or more chambers of the extruder can be heated at different temperatures. The speed of the one or more screws of the extruder can be any desired speed.

  At 110, an article is manufactured using the mixture of materials. In some cases, the article can include a film. In other cases, the article can be formed from a film. In other embodiments, the article can have a shape (injection molded) based on a design such as a mold. Any possible article made of plastic, including but not limited to, for example, films, bags, bottles, caps, lids, sheets, boxes, plates, cups, utensils, etc., can be formed from the mixture. If the article is a film, a die can be used to form the film by injecting a gas into the heated mixture of materials to form the film (ie, blow the film). The film can be sealed and / or otherwise modified to be in the form of a bag or other article.

  If the article is a film, the film can be composed of a single layer or multiple layers. The film or any individual layer is 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, at least 0.03 mm, at least 0.05 mm, at least 0.07 mm, at least It can have a thickness of 0.10 mm, 2 mm or less, 1 mm or less, 0.5 mm or less, 0.1 mm or less, about 0.05 mm to about 0.5 mm, or 0.02 mm to 0.05 mm. Some specific examples may include films of less than 0.005 mm, for example, 0.002 mm to 0.004 mm, or 0.0025 mm (0.1 mil) to 0.25 mm (10 mil). Although there may be some overlap in the thickness values of the film and sheet articles, it will be appreciated that sheet materials thicker than such film values provided by any desired plastic manufacturing process may be provided. It will be appreciated that it is good.

  The ability to blow very thin films of 0.1 mil (0.0025 mm) has been demonstrated by applicants using blends as described herein, and such very Thin films exhibit high strength (eg, at least 40 g in a dart drop impact test on 0.1 mil film, such as a dart strength of 40 g to 110 g, or 40 g to 100 g for such a very thin film). ). Using the blends and other parameters (eg, blow-up ratio, die gap, etc.) as described herein, even the ability to blow such very thin films is likely to be unique to Applicants It is considered to be.

  For films or other articles, dart drop impact test (ASTM D-1709), tensile strength at break test (ASTM D-882), tensile elongation at break test (ASTM D-882), secant modulus test (ASTM D-882) 882), and / or strength properties characterized through tests such as the Elmendorf Tear Test (ASTM D-1922). The film weighs 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, 400 g or less, 375 g or less, 350 g or less, or 325 g or less, 140 g-425 g, 200 g-400 g, 250 g-350 g, 265 g It can have a dart drop impact test value of ３３０330 g. In one implementation, such values may be of any film thickness. In another implementation, such a value may be for a 1 mil thick film formed from a mixture of materials.

  The article is at least 3.5 kpsi, at least 3.7 kpsi, at least 3.9 kpsi, at least 4.1 kpsi, at least 4.3 kpsi, or at least 4.5 kpsi, 5.5 kpsi or less, 5.3 kpsi or less, 5.1 kpsi or less, It may have a tensile strength at break in the longitudinal direction of 4.9 kpsi or less, or 4.7 kpsi or less, 3.5 kpsi to 5.5 kpsi, or 4.1 kpsi to 4.9 kpsi.

  The article is at least 3.2 kpsi, at least 3.4 kpsi, at least 3.6 kpsi, at least 3.8 kpsi, at least 4.0 kpsi, at least 4.2 kpsi, 5.7 kps or less, 5.5 kpsi or less, 5.3 kpsi or less, 5 Have a transverse tensile strength test value of .1 kpsi or less, 4.9 kpsi or less, 4.7 kpsi or less, 4.5 kpsi or less, 3.2 kpsi to 5.7 kpsi, or 3.6 kpsi to 5.0 kpsi. it can.

  The article is at least 550%, at least 560%, at least 570%, at least 580%, at least 590%, at least 600%, at least 610%, at least 620%, 725% or less, 710% or less, 700% or less, 680% Below, it can have a tensile elongation at break in the machine direction of 665% or less, 650% or less, 635% or less, 550% to 750%, or 600% to 660%.

  The article has at least 575%, at least 590%, at least 600%, at least 615%, at least 630%, or at least 645%, 770% or less, 755% or less, 740% or less, 725% or less, 710% or less, 695% or less. %, 680% or less, 575% to 775%, or 625% to 700%.

  If applicable, the article is at least 280 g / mil, at least 300 g / mil, at least 320 g / mil, at least 340 g / mil, or at least 360 g / mil, 450 g / mil or less, 430 g / mil or less, 410 g / mil or less, 390 g / Mil or less, or 370 g / mil or less, 275 g / mil to 475 g / mil, or 325 g / mil to 410 g / mil in the longitudinal Elmendorf tear strength test value.

  If applicable, the article has at least 475 g / mil, at least 490 g / mil, at least 500 g / mil, at least 525 g / mil, at least 540 g / mil, or at least 550 g / mil, 700 g / mil or less, 680 g / mil or less, 650 g. / Mil or less, 625 g / mil or less, 600 g / mil or less, 580 g / mil or less, 570 g / mil or less, 475 g / mil to 725 g / mil, or 490 g / mil to 640 g / mil transverse Elmendorf tear force test value Can be provided.

  If applicable, the article is at least 20 kpsi, at least 22 kpsi, at least 24 kpsi, at least 26 kpsi, at least 28 kpsi, or at least 30 kpsi, 40 kpsi or less, 38 kpsi or less, 36 kpsi or less, 34 kpsi or less, or 32 kpsi or less, 20 kpsi to 40 kpsi, or 25 kpsi to 25 kpsi. It may have a longitudinal secant modulus test value of 35 kpsi.

  If applicable, the article is at least 20 kpsi, at least 22 kpsi, at least 24 kpsi, at least 26 kpsi, at least 28 kpsi, or at least 30 kpsi, 40 kpsi or less, 38 kpsi or less, 36 kpsi or less, 34 kpsi or less, or 32 kpsi or less, 20 kpsi to 40 kpsi, or 25 kpsi to 25 kpsi. It may have a transverse secant modulus test value of 35 kpsi.

  In some cases, an article comprising a carbohydrate-based polymer material formed from a mixture of two or more starches has greater strength properties than an article comprising a carbohydrate-based polymer 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 has a dart that is at least about 5% greater, or 10% greater, than a component in which the carbohydrate-based polymeric material is formed from a single starch. Have a drop impact test value (in grams or g / mil thickness) and are at least about 25% greater than the same article but comprising a carbohydrate-based polymeric material formed from a single starch; It may have a dart drop impact test value that is at least about 50% greater, at least about 75% greater, 10% greater to 150% greater, or 60% greater to 120% greater. Details of such increased strength can be found in the examples herein and in U.S. Patent Application Nos. 14 / 853,725 and 15 / 481,806, which are already incorporated by reference.

  1A, 1B, and 1C further illustrate certain examples of processes according to the present disclosure. Accordingly, these figures are generally encompassed by the more general steps of FIG. 1, and the description provided therewith, which generally applies. For example, FIG. 1A shows similar steps 102, 104, 106, and 108, but at 110 'the manufactured article is particularly a blown film and the film blow molding apparatus has a blow-up ratio of at least two. And / or operated so that the die gap is less than or equal to 500 micrometers. In other words, FIG. 1A specifically illustrates that renewable carbohydrate-based polymeric materials are included in the blend into which the plastic film is blown, and that high blow-up ratios and / or narrow die gaps are achieved. 5 illustrates an exemplary process 100 'that may be used to increase the strength of a blown plastic film by selection. At 102, the process 100 includes any plastic resin that can be blown into a film, such as, for example, polyethylene, polypropylene, other polyolefins, polyethylene terephthalate, polyester, nylon, polystyrene, ABS, polyvinyl chloride, and the like. This may include providing one or more "other" polymeric materials. The "other" polymer material can be a petrochemical-based polymer material. It can also be a "green" version of such a petrochemical-based polymeric material, such as "green" polyethylene available from Braskem. It will be apparent that a wide variety of polymers may be suitable for use as the "other" polymer material.

  At 104, the process 100 is specifically selected to include in the blend, for example, due to its recognized ability to increase strength when blown at high blow-up ratios and / or with a narrow die gap. And providing one or more carbohydrate-based polymeric materials. Renewable carbohydrate-based polymeric materials can be substantially amorphous and have a crystallinity of 20% or less. An exemplary NuPlastiQ available from BiologiQ as described herein, wherein various other properties relating to elastic modulus (ie, Young's modulus), glass transition temperature, heat distortion temperature, Vicat softening temperature, or other properties are described. Or may be additionally or alternatively as described for the ESR material. At 106, the materials can be mixed together at 106 to form a blend of the materials. At 108, they can be heated (eg, in the case of a thermoplastic material, melted) in preparation for blow molding the films. At 110 ', a plastic film is blown using a film blower using a mixture of materials. During such film blow molding, the blow-up ratio used may be at least 2.0. As described herein, Applicants have shown that the combination of including a carbohydrate-based polymeric material in a blend and using a blow-up ratio of 2.0 or more, especially when also with a narrow die gap, , Found that the strength is greatly improved.

  Multilayer films formed from blends of Cardia BL-F and PE are described in WO2014 / 0139095 to Leufgens, which uses different TPS materials, as well as certain blown materials. Due to the selection of the up ratio, due to the ratio and / or the selected die gap properties, it is significantly weaker than the film described in the present invention. For example, Leufgens blown films are 80 micrometers (ie, 3 mils or more) thick and actually exhibit strength less than that of 100% PE films. In contrast, certain choices described herein actually increase the strength at any given thickness compared to a 100% "other polymeric material" (eg, PE) control. Make it possible. Furthermore, the method allows for the production of films having a desired level of strength at much lower thicknesses. Such ability to achieve the desired level of strength at a significantly lower thickness also reduces the amount of material used in the film layers, resulting in further cost savings and greater sustainability.

  As described herein, a particular carbohydrate-based polymeric material described herein is blended with another polymeric material, and then with a mixture of materials at a blow-up ratio of at least 2.0 and / or narrow. Blow molding a plastic film with a film blower at a die gap (e.g., 500 micrometers or less) involves blowing only the first polymer material (e.g., PE), otherwise. Applicants have found it to provide thin films (e.g., less than 2 mils, e.g., 0.1-1.5 mils) that exhibit greater strength than similar films.

  Without being bound by any particular theory, certain renewable carbohydrate-based polymers that are substantially amorphous when blow molded with such high blow-up ratios and / or narrow die gaps The resin is believed to promote the desired alignment, orientation and / or stretching of the different polymer molecules of the blend in a manner that increases the strength of the resulting blended plastic film.

  For example, polymers are formed using both crystalline (regularly packed) and amorphous (randomly arranged) structures. While many polymers (such as polyethylene) contain a high degree of crystallinity, they can include some amorphous regions randomly arranged and entangled throughout the polymer structure. The particular renewable carbohydrate-based polymeric material used is not highly crystalline but substantially amorphous. Without being bound by a particular theory, the combination of the crystalline first polymeric material and the amorphous, renewable carbohydrate-based polymeric material is such that the components of the blend are uniformly blended with each other, but with high strength. It is believed that it undergoes orientation, alignment, and stretching in a manner that allows it to be oriented and stretched in a manner that provides for the increase. Such an increase may be observed in both the machine direction (MD) and the transverse direction (TD), so that the phenomenon observed simply trades off the intensity in one direction for another. Not something. This is evident in the dart drop impact data describing the strength in both directions.

  The selection of a particular amorphous carbohydrate-based material and the selection of a high blow-up ratio, for example, and / or the use of a narrow die gap, such an increase in strength, often results in thin films, such as Cardia BL-F. Advantageously provides an increase in strength, thinner than that achievable with other TPS-containing blends. In some cases, as described herein, the film can be blown as thin as, or even thinner than, blowing the first polymeric material alone. is there. For example, Applicants have the ability to blow films from blends of polyethylene and renewable carbohydrate-based polymeric materials that are as thin as, or even thinner than, the thinnest films that can be blown with polyethylene alone (eg, , The ability to blow-mold films below 0.1 mil).

  As described herein, a carbohydrate-based polymeric material having low crystallinity and / or other properties as described herein, and a high blow-up ratio and / or narrow die gap as described Articles comprising other polymer materials formed of may have greater strength property values than articles formed solely of "other" polymer materials. Such an increase in strength is advantageous and surprising, for example, as compared to the state of the art. For example, Leufgens describes a film blown from a blend of a starch-based polymeric material (Cardia BL-F) and polyethylene, but the resulting film is otherwise formed from polyethylene alone. It shows lower tensile strength (Leufgens FIG. 2) and lower dart drop impact strength (Leufgens FIG. 5) when compared to similar films. This is the case even when the blend of Cardia BL-F and polyethylene is blow molded at a blow-up ratio of 3: 1. This is because, at least in at least the particular conditions used in Leufgens (which also includes a relatively wide die gap of 1.6-1.8 mm), the renewable carbohydrate-based polymer material alone has increased strength. Evidence that may not occur. As the examples show, the use of the present renewable carbohydrate-based polymeric materials with low crystallinity and / or NuPlastiQ or other specific properties related to ESR results in increased strength.

  An increase in strength (eg, tensile strength, dart drop impact strength, or other strength measurement) is an article that is formed from the “other” polymeric material alone, but otherwise identical (ie, renewable) 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 15%, It can be 20%, 1% to 50%, 1% to 40%, or 10% to 40%.

  FIGS. 1B and 1C show a particular method for combating the unique odor provided by including a carbohydrate-based polymeric material in the blend. As will be apparent to those skilled in the art, any of the methods described herein can be used together (e.g., to include films with high blow-up ratios and / or narrow die gaps while also including odor reducing agents). Blow molding). FIG. 1B illustrates an exemplary method 100 "according to the present invention for manufacturing an article comprising a carbohydrate-based polymeric material, an organic odor reducing agent, and a polymeric resin. In 102, the process 100 includes one or more" others ". "Providing a polymeric resin. Such resins can be any of the vast number traditionally used in plastics manufacturing, as described herein. At 103 and 104, respectively, process 100 includes providing an organic odor reducing agent and a carbohydrate-based polymeric material.

  In one embodiment, an odor reducing agent may be included with the carbohydrate-based polymeric material (eg, included in the masterbatch). In other embodiments, the odor-reducing agent can be added with the polymer resin via another route, separately from, for example, both the polymer resin and the carbohydrate-based polymer. It will be apparent that various routes for such addition are contemplated and possible. The odor reducing agent is specifically selected for inclusion in the blend because of its ability to counteract the odor otherwise imparted to the finished product by the carbohydrate-based polymeric material. For example, carbohydrate-based polymeric materials may otherwise produce slightly burnt carbohydrate odors (e.g., slightly during the heat treatment of the blend (e.g., during injection molding, blow molding, film blow molding, etc.)). (A burnt starch odor, popcorn or caramel corn-like odor), where the mixture of components at 102, 103, and 104 is melted together and formed while in the heated state.

  The odor reducing agent at 103 can be in any such desired form (eg, pellets, powders, knurls, slurries and / or liquids). In one embodiment, the odor reducing agent may initially include a lyophilized powder that can be mixed into the masterbatch of the carbohydrate-based polymer material during or after the production of the carbohydrate-based polymer material. When formed from a mixture of powder (s), glycerin, and water, the odor reducing agent (eg, as a lyophilized powder) may be added to the mixture of starch powder (s), or to water, or to a plasticizer (eg, , Glycerin) and mixtures thereof. The carbohydrate-based polymer material can then be manufactured by the same process as is usually manufactured, wherein the odor reducing agent is dispersed in the carbohydrate-based polymer material as a dispersing component therein (e.g., uniformly dispersed therein). ) Can be incorporated.

  In another embodiment, the powdered or other odor reducing agent is prepared for combination with other components (eg, compatibilizers) that are melted and included in the masterbatch, so that the carbohydrate-based polymer and Can be mixed. It will be apparent to those skilled in the art that there are numerous possibilities for adding odor reducing agents to any of the components that will form a plastic article from a blend of a carbohydrate-based polymeric material and other polymeric resins. Would. A variety of such alternative routes for incorporating organic odor reducers may also be suitable for use.

  Whatever the route chosen to introduce the odor-reducing agent into the blend, the blending of the components at 102, 103, and 104 may be performed by any of the possible processes as described above and elsewhere herein. Can be formed.

The odor reducing agent can be organic. One skilled in the chemical arts will understand that organic compounds are carbon-based, but exclude simple carbon compounds such as carbides, carbonates, carbon oxides (eg, CO and CO ₂ ), and cyanides. There will be. In one embodiment, the organic odor-reducing agent can include a benzyl group that is an aromatic compound. Various aromatic derivatives of benzene, such as benzaldehyde and / or benzyl ketone, may be suitable for use. In one embodiment, the organic odor reducing agent can be a compound that contains only carbon, oxygen, and hydrogen atoms (eg, does not contain heteroatoms). In other embodiments, compounds containing one or more heteroatoms can prove suitable for use. In embodiments that have proven particularly effective, the odor reducing agent comprises a benzaldehyde compound, for example, 4-hydroxy-3-methoxybenzaldehyde. Such an aromatic compound is also known as vanillin and has the chemical structure shown below.

Only small amounts of organic odor reducers have been found to be sufficient to neutralize the odor associated with carbohydrate-based polymeric materials. In addition to the fact that only a small amount of odor reducing agent is required, it is also surprising that the problems associated with the addition of organic components (carbohydrate-based polymeric materials) can be solved by adding more organic components. For example, those skilled in the art will recognize that such additional organic components, especially aromatic chemical structures, may be used to increase the odor released by the blend upon heat treatment, rather than to reduce or substantially eliminate such odor. You can expect to include what you have.

  In one embodiment, no inorganic or other odor reducing agents are included in the composition. For example, in one embodiment, activated carbon, zeolites, or other components known to include active sites capable of binding odorous volatile molecules are not included in the composition. For example, including such an odor reducing agent that acts on a mechanism that depends on binding at the active site may somehow inhibit the ability of benzaldehyde or other organic odor reducing agents to perform its intended function. (Eg, such active sites merely serve to bind benzaldehyde or other organic odor reducing agents).

  The odor reducing agent is 1% or less, 0.5% or less, 0.25% or less, 0.1% or less, 0.05% or less, 0.01% or less, 1000ppm or less, 500ppm or less, 250ppm or less, 100ppm or less. , 50 ppm or less, or 20 ppm or less, including any blended plastic material, or a carbohydrate-based polymer material, including an odor reducing agent provided therein (eg, a masterbatch for blending with another polymer material). As). When such a carbohydrate-based polymer material is blended with another polymer resin, the concentration of the odor reducing agent may, of course, be further diluted. For example, the concentration of such odor reducing agents in a plastic blend article may be 15 ppm or less, 10 ppm or less, 5 ppm or less, or even 1 ppm. Applicants have found that such small proportions are surprisingly effective in counteracting and substantially eliminating odors inherent in plastics containing carbohydrate-based polymeric materials.

  In addition to vanillin, other extracts from various fruits and / or vegetables may be suitable for use as organic odor reducers. Non-limiting possible examples include lyophilized extracts from vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, passion fruit, or raspberry. Combinations may also be suitable for use.

  As described above, in one embodiment, an odor reducing agent can be added to the water and / or glycerin (eg, dissolved or dispersed therein) used to form the carbohydrate-based polymeric material; This can be particularly beneficial in ensuring uniform mixing of a very small percentage of odor reducing agents throughout the finished carbohydrate-based polymer material. For example, a powder odor reducer can be added to other powder materials (eg, starch (s)) that will produce a carbohydrate-based polymer material, but the odor reducer is added in too small an amount. For this reason (eg, 20 ppm in the masterbatch), it is more likely to ensure a uniform distribution of the odor reducing agent by mixing it with the liquid component (s) rather than combining it with the solid powder (s). Can be easy.

  The addition of an odor-reducing agent to the carbohydrate-based polymer material substantially eliminates the tendency to blend other carbohydrate-based or popcorn-type odors with blends of the carbohydrate-based polymer material with another thermoplastic polymer resin. However, such inclusion does not substantially alter any of the physical or other properties of the NuPlastiQ or ESR material, as described herein. As described above, the odor reducing agent is contained in the carbohydrate-based polymer NuPlastiQ or “ESR” material at 1000 ppm or less, 500 ppm or less, 250 pp or less, 200 ppm or less, 100 ppm or less, 50 ppm or less, 40 ppm or less, 30 ppm or less, 25 ppm or less, 20 ppm. Below, it may be present in the range 5 ppm to 50 ppm, 10 ppm to 50 ppm, or 15 ppm to 25 ppm. Applicants have found that a level of 20 ppm in NuPlastiQ or ESR materials is particularly effective. When diluted with a polymeric resinous material, the concentration of odor reducing agents in articles formed from such blends is even lower (e.g., 20 ppm levels in NuPlastiQ or ESR masterbatch, only 10 ppm in finished product, only 10 ppm) 5 ppm, or as low as 1 ppm).

  In some embodiments, NuPlastiQ or ESR may be provided in a masterbatch formulation that may include a carbohydrate-based polymeric material as described above, an odor reducing agent, and an amount of one or more compatibilizers. The masterbatch may also include one or more “other” polymer resins already contained therein (eg, the same polymer resin with which the carbohydrate-based polymer resin is blended to form the desired article). . Such masterbatch formulation pellets can be mixed with pellets of "other" polymer resin material during processing. Depending on the desired ratio of NuPlastiQ or ESR and / or compatibilizer and / or conventional polymer resin in the finished product, any conceivable proportion can be used when mixing such different pellets.

  As noted above, odor reducers are typically used at very low levels, such as 1% or less, 0.1% or less, 0.01% or less, 1000 ppm or less, 100 ppm or less, 50 ppm or less, or 20 ppm or less. , Carbohydrate-based polymeric materials. When the carbohydrate-based polymer material containing the odor-reducing agent is mixed with the polymer resin, the level of the odor-reducing agent in the resulting blended plastic article is reduced depending on the mixing ratio of the carbohydrate-based polymer material to the polymer resin material. As mentioned herein, a wide variety of mixing ratios are suitable. As an example, with a 1: 1 mixing ratio, if the initial level of odor reducing agent in the carbohydrate-based polymeric material masterbatch is 20 ppm, in the finished plastic article formed from the blend, it now drops to only 10 ppm. I have. At a mixing ratio of 25% carbohydrate-based polymer material to 75% polymer resin material, the initial 20 ppm level of odor reducing agent has now dropped to 5 ppm.

  Although the concentration of the odor-reducing agent is decreasing, it will be apparent that the ratio of odor-reducing agent to carbohydrate-based polymeric material remains unchanged due to such mixing. For example, the weight ratio of odor reducing agent to carbohydrate-based polymer may be 1: 1000, or even less. For example, the ratios are 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 may be in the range between any two such values (eg, 1: 1000 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 may be equivalent to a ratio of about 1: 50,000. Even when mixed with the polymeric resin material, this ratio can remain substantially constant because the addition of the polymeric resin material does not change the amount of odor reducing agent or carbohydrate-based polymeric material in the blend.

  The odor-reducing agent may be organic, but it may be important that this component is not volatile, so that it is simply displaced during thermal processing of the article (as residual moisture content in the carbohydrate-based polymeric material) It will be clear that nothing will happen. For example, an odor reducing agent can be solid rather than liquid at ambient temperature (eg, 25 ° C.) and ambient pressure (eg, 1 atmosphere). In the case of a liquid, the odor reducing agent may exhibit a lower volatility than the volatility of water (eg, as measured for vapor pressure at a given temperature and pressure (eg, STP as described above). )). In one embodiment, the odor reducing agent may have a boiling point above any of the temperatures associated with processing at 108 and 110 ". The odor reducing agent may have a lower melting point than the temperature associated with processing at 108 and / or 110". May be provided. For example, an odor reducing agent may be solid at ambient temperature (eg, 25 ° C.), but liquid at the elevated temperatures at which processing occurs (eg, 125 ° C.-165 ° C.). 4-hydroxy-3-methoxybenzaldehyde is an example of such an odor reducing agent.

  For example, the odor reducing agent 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 140C, less than 135C, less than 130C, less than 125C, less than 120C, less than 115C, less than 120C, less than 115C, less than 110C, less than 100C, 50C to 180C, 50C to 50C. It can have a melting point of 150C, or 60C to 100C. The odor reducing agent is more than 150C, more than 160C, more than 170C, more than 180C, more than 200C, more than 225C, more than 250C, 150C to 500C, 200C to 400C, or 250C to 300C. It can have a boiling point of ° C. As an example, vanillin melts at 81-83 ° C and boils at 285 ° C.

  FIG. 1B shows a method of making an article from a polymer resin (102), an odor reducing agent (103), and a carbohydrate-based polymer material (104), while FIG. 1C shows that the odor reducing agent can be converted to a carbohydrate-based polymer. Shown is a process 100 "" that can be incorporated into the material. For example, an odor reducing agent may be provided at 103, a carbohydrate-based polymeric material is provided at 104, and they are mixed together at 106 ". By way of example, this may be the case if the organic odor reducing agent is mixed with the carbohydrate-based polymeric material when formulating the masterbatch (eg, when adding a compatibilizer or other components included in the masterbatch, as well). When an agent is added to the carbohydrate-based polymeric material). In another embodiment, the odor-reducing agent may be mixed with the starting material (s) from which the carbohydrate-based polymeric material is formed (e.g., the odor-reducing agent is replaced with water from which the carbohydrate-based polymeric material is formed, Glycerin, or by mixing with one or more of the starch components). In any case, the selected method will result in a carbohydrate-based polymeric material comprising an odor reducing agent dispersed therein. The concentration may be very low (eg, 20 ppm) as described herein. At 110 '' ', such carbohydrate-based polymeric materials (including odor reducing agents) are blended with a polymeric resin (e.g., typically to melt and blend thermoplastic resins together). , With the application of heat).

  Returning to standard features that may apply to any of the embodiments described herein, a biodegradation test (eg, a biomethane potential test, or ASTM D-5511, ASTM D-5526, ASTM D-5338). Or any applicable ASTM standard such as ASTM D-6691). Under such testing and within a given period of time (eg, 30, 60, 90, 180, 365 days (1 year), 2, 3, 4 or 5 years) The article may exhibit substantial biodegradation of the total polymer content and / or any non-biodegradable "other" polymer content (apart from the carbohydrate-based polymer content). The biomethane potential test is usually performed for 30 to 60 days, but sometimes for as long as 90 days. Longer term tests are more typically performed under any of the above mentioned ASTM standards. For example, an article that is free or will be substantially free of a biodegradation-enhancing additive can exhibit biodegradation greater than its carbohydrate-based polymer material content, and the other plastic material (s) also Indicates biodegradable (or shows potential for biodegradation under biomethane potential test).

  In particular, articles may be subjected to test simulated biodegradation under landfill or other disposal and / or degradation conditions (eg, composting or marine conditions) for 180 days, 200 days, 365 days (1 year), 2 years, When served for years, or five years, biodegradation can be greater than the weight percent of the carbohydrate-based polymeric material in the article. In other words, inclusion of the described carbohydrate-based polymeric material may result in at least some biodegradation of the otherwise non-biodegradable "other" polymeric material.

  For example, an article formed from a blend of a carbohydrate-based polymeric material and PE may exhibit biodegradation after such a period of time, which is greater than the weight fraction of the carbohydrate-based polymeric material in the film, and the PE ( Until now it was not considered biodegradable), but shows that it is in fact biodegradable with carbohydrate-based polymeric materials. Such a result is surprising and particularly advantageous.

  The biomethane potential test determines the potential for anaerobic biodegradation based on methanogenesis as a percentage of total methanogenic potential. The biomethane potential test can be used to predict the biodegradability of a test sample according to the ASTM D-5511 standard, and the biomethane potential test uses one or more conditions from the ASTM D-5511 standard. Can be implemented. For example, a biomethane potential test can be performed at a temperature of about 52 ° C. In addition, the biomethane potential test has several conditions that differ from those of ASTM D-5511, for example, to accelerate the test to completion within a typical period of 30, 60, or even 90 days. be able to. The biomethane potential test can use an inoculum having 50% to 60% water and 40% to 50% organic solids by weight. For example, the inoculum used in the biomethane potential test can have 55% water by weight and 45% organic solids by weight. Biomethane potential testing can be performed at other temperatures, such as 35 ° C to 55 ° C or 40 ° C to 50 ° C.

  When subjected to a biodegradation test, the carbohydrate-based polymeric material has (or preferably does not include) about 2% by weight or less of the biodegradation-promoting additive, and the amount of carbohydrate-based polymeric material and "other" Articles having a polymeric material can exhibit increased degradation as a result of the introduction of the carbohydrate-based polymeric material into 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%, of a non-carbohydrate-based polymeric material (eg, an "other" polymeric material). 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% and even at least 95% landfill, compost And / or can be biodegraded for at least about 1 year, at least about 2 years, at least about 3 years, or at least about 5 years when exposed to marine conditions (or conditions that mimic such conditions) . Such biodegradation is particularly noteworthy and advantageous. Thus, not only are carbohydrate-based polymeric materials biodegradable, but "other" polymeric materials are biodegraded as well, even if such materials are otherwise not biodegradable by themselves.

  Examples show that over time the amount of biodegradation can be very large, such that in at least some implementations, substantially the entire article biodegrades (eg, at least about 85%, Biodegradation of at least about 90%, or at least about 95%, within 180 days, within 200 days, or within 365 days (within 1 year), within 2 years, within 3 years, within 5 years, or other time period) .

  FIG. 2A illustrates components of an exemplary manufacturing system 200 for manufacturing an article according to the present disclosure. In some cases, the manufacturing system 200 can be used in the process 100 of FIG. 1 or any of the processes 100 of FIGS. 1A-1C. In the illustrative example, manufacturing system 200 is an extruder, such as a single or twin screw extruder.

  In one implementation, one or more non-biodegradable plastic materials and one or more carbohydrate-based polymer materials are provided via a first hopper 202 and a second hopper 204. The compatibilizer may be included in one or both materials (eg, in its masterbatch).

  One or more carbohydrate-based polymeric materials and one or more non-biodegradable plastic materials can be mixed in first chamber 206 to produce a mixture of materials. In some cases, the mixture of materials comprises 5% to 40% by weight of one or more carbohydrate-based polymeric materials, 60% to 94% by weight of one or more non-biodegradable plastic materials, and 1% to It may contain 9% by weight of one or more compatibilizers. As described herein, small amounts of odor reducing agents may also be present. Of course, depending on the desired characteristics, the range may vary outside of the above range.

  In the exemplary implementation shown in FIG. 2A, a mixture of materials is provided in first chamber 206, second chamber 208, third chamber 210, fourth chamber 212, fifth chamber 214, and optional second chamber. A number of chambers, such as six chambers 216, can be passed. The mixture of materials can be heated in chambers 206,208,210,212,214,216. In some cases, the temperature of one chamber may be different from the temperature of another chamber of the chamber. In the illustrative example, the first chamber 206 is heated to a temperature between 120 ° C. and 140 ° C., the second chamber 208 is heated to a temperature between 130 ° C. and 160 ° C., and the third chamber 210 is heated to 135 ° 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 an optional sixth Chamber 216 is heated to a temperature of 145 ° C to 180 ° C.

  The heated mixture can then be extruded using a die 218 to form extrudates, such as films, sheets, and the like. Various articles such as cooking utensils, plates, cups, bottles, their caps or lids, and the like can be manufactured using injection molding, thermoforming, or other plastic manufacturing processes. In film blow molding, gas can be injected into the extrudate to expand it at a pressure of 105-140 bar. The resulting tube 220 can be aligned through rollers 222 to create a film 224 typically between about 0.8 mil and about 2 mil thick. The blends described herein can be used to produce thinner films, for example, having a thickness on the order of 0.1 mil (0.0025 mm). Of course, thicknesses in excess of 2 mils can also be achieved. In some cases, film 224 may be comprised of a single layer. In other cases, the film 224 can be composed of multiple layers. If multiple layers are present, at least one of the layers may include a 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 the inner layer. If the carbohydrate-based polymer material is not included in the outer layer (s), biodegradation of the outer layer may not occur.

  FIGS. 2B and 2C show further details regarding the blown film apparatus of FIG. 2, and particularly show how the properties of the blow-up ratio and die gap can be selected for increased strength. And the formation of bubbles 220 is schematically illustrated. As shown in FIGS. 2B and 2C, die 218 may include an outer member 218a and an inner member 218b with a die gap 226 defined therebetween. As described herein, the die 218 may have a narrow die gap, for example, less than 1000 micrometers, less than 900 micrometers, less than 800 micrometers, less than 700 micrometers, less than 600 micrometers, or less than 500 micrometers ( (E.g., 200-500 micrometers). This narrow die gap is in sharp contrast to the wide die gaps used (and possibly necessary) in the state of the art when blowing films containing other thermoplastic starch components. For example, Leufgens describes a die gap of 1.6-1.8 mm (i.e., 1600-1800 micrometers). Even with a high blow-up ratio, using such a large die gap may not be able to achieve the increased strength described herein.

FIG. 2B further illustrates a relatively high blow-up ratio, which is defined as the ratio of the maximum diameter of the bubble (D _B ) to the diameter of the die gap (D _D ). In other words, with respect to lay flat width of the film, the blow up ratio is equal to 0.637 * (lay flat width) / _{D D.} The frost line 228 is also shown in FIG. 2B, where the previously melted bubble material begins to crystallize to have a more transparent appearance over such crystallized regions in the frost line 228. As described herein, the blow-up 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, 2.2-2.8, or about 2.5. Applicants have observed an increase in film strength by simply increasing the blow-up ratio from a typical blow-molded blow-up ratio of, for example, 1.5 to a value of at least 2, such as 2.5. The intensity was observed to increase at values up to about 3, after which no significant further increase in intensity was observed, so that 2-3, 2.2-2.8, or about 2.5 The values are particularly appropriate. As described herein, the die gap can be maintained at a narrow value, which also contributes to the described increase in strength, when blow-blending blends containing the described renewable carbohydrate-based polymeric materials. can do.

  By way of example, a die gap of less than 500 micrometers and a blow-up ratio of at least 2 (eg, 2.2-2.8, or about 2.5) may be up to 1.5 mil (eg, 0.1 mil to 1 mil). It is particularly well suited for blow molding films from such blends having a thickness of 0.5 mils. In order to blow thicker films (where thicker films are needed), the die gap may need to be increased to accommodate the flow of molten material therethrough. For example, to blow a very thick film of 10 mils or even 5 mils, the die gap may need to be somewhat larger (although the value is still less than 1000 micrometers, or even 500 micrometers). Less than a micrometer).

  The concepts described herein will be further described in the following examples.

Example 1
Eleven starch-based polymers were formed from 27% tallow glycerin (99% pure glycerin) and 73% starch (excluding water). Each finished starch-based polymer showed less than about 1% water and was mixed with LLDPE and anhydride-modified LLDPE in proportions of 25%, 70%, and 5% by weight, respectively. The resulting mixture was then extruded and blown into a film. 70% of each film was LLDPE, 25% was a starch-based polymer, and 5% of each film was anhydride-modified LLDPE. The film was then tested using the drop dart impact test according to ASTM D-1709. The combinations of the starches tested and the strength test results (grams) are shown in Table 3. The results in Table 3 show that the sample formed from the mixture of starches has a dart drop impact test value greater than the dart drop impact test value of the sample formed from a single starch.

FIG. 5 charts impact test strengths for films of different thicknesses (0.5 mil, 1 mil, 1.5 mil, 2.0 mil) based on the percentage of starch-based NuPlastiQ or “ESR” in the film. I have to. The NuPlastiQ or ESR used in the formed film shown in FIG. 5 was formed from a blend of starch containing 90% corn starch and 10% potato starch. FIG. 5 shows how the strength of the film increases as the percentage of NuPlastiQ or ESR increases, up to a maximum strength at about 20% to about 25% NuPlastiQ or ESR. The remainder of the blend contained polyethylene and a suitable compatibilizer, as described herein.

  FIG. 6A shows a film comprising 25% carbohydrate-based polymeric material with the balance comprising a very small amount (eg, about 5%) of a compatibilizer and PE (about 70%) door as described herein. 2 shows the dart impact test strength for films of different thicknesses (from about 0.1 mil up to 2 mils). FIG. 6 also shows the comparative strength for the 100% PE film, which is lower in all respects than for the blend according to the present disclosure. FIG. 6 shows various "carry" bags (e.g., grocery products provided for transportation) for produce bags (e.g., bags provided to consumers to hold produce in the produce section of a supermarket). And other plastic bags), and various other test criteria for potato bags (plastic bags used to hold 5, 10, or 20 pounds of potatoes in the supermarket produce sector). Points are further shown. Example 8 is similar, but shows results for a blend where the "other" polymeric material is biopolyethylene rather than synthetic LLDPE derived from a petroleum source.

  FIG. 7 shows films of different thicknesses (from less than 0.5 mil up to about 2 mils) for various blend films according to the present disclosure, as well as comparative films (eg, 100% LLDPE, 100% recycled LLDPE (rLLDPE)). The chart shows the dart impact test strength for ()). In addition to showing strength properties for films formed from virgin materials (25% NuPlastiQ or ESR, 70% LLDPE, 5% compatibilizer (designated 25% NuPlastiQ or ESR / 75% LLDPE)) 7 recycle LLDPE (rLLDPE) when such recycled material (rLDESR) is then blended with virgin material (designated 25% NuPlastiQ or ESR / 25% rLDESR / 50% LLDPE) or during blending (Indicated as 25% NuPlastiQ or ESR / 25% rLLDPE / 50% LLDPE). As shown, in addition to the aforementioned features of increased renewability and biodegradability, strength results are improved compared to the use of PE polymer materials.

Example 2
Three samples were tested for 349 days to determine biodegradability characteristics according to ASTM D-5511. This test was intended to replicate the conditions of a full-fledged anaerobic digester (landfill). The results for the three samples (designated 1342, 1343, and 1344) are shown in FIGS. FIG. 8A shows the results for all of samples 1343, 1343, and 1344 when compared to the control. FIG. 8B shows the results of sample 1344 alone compared to the control. Sample 1342 is formed from 30% NuPlastiQ or ESR (substantially amorphous carbohydrate-based polymeric material with less than 10% crystallinity), 67% PBAT, and 3% compatibilizer. It had a thickness of 1 mil. Sample 1343 was formed from 27.5% NuPlastiQ or ESR, 70% PBAT and 2.5% compatibilizer and had a thickness of 1.0 mil. Sample 1344 was formed from 40% NuPlastiQ or ESR, 56% LLDPE and 4% compatibilizer and had a thickness of 1.0 mil.

8A-8B show that after 204 days, the negative control shows 2.5% degradation, the positive control shows 86.5% degradation, sample 1342 shows 43.3% degradation, and sample 1343 shows 53.3% degradation. It shows 9% degradation, indicating that sample 1344 shows 77.2% degradation. The decomposition values at 349 days are as shown in Table 4.

  Biodegradation after 349 days is particularly excellent. For example, samples containing PBAT (1342 and 1343) show very good biodegradation, with biodegradation rates far greater than the percentage of carbohydrate-based polymer material contained in the film, while sample 1344 (see FIG. 8B) further Surprisingly high, when the non-biodegradable plastic material is polyethylene, it shows a biodegradation of almost 96% (even higher than the positive control), which, under normal circumstances, is of course not biodegradable (See, for example, the negative control reference in Table 4 which was 100% polyethylene). The results of such biodegradation are noteworthy and particularly advantageous.

Example 3
Potato packaging bags made with a blend of 25% NuPlastiQ or ESR, 70% LLDPE and 5% compatibilizer were used according to ASTM D-5526 for 60 days, 107 days, 202 days, 317 days, 439 days, 573 days. , And 834 days later for anaerobic biodegradation. This test was intended to replicate the conditions of a full-fledged anaerobic digester (landfill). The test was performed under various conditions, and the inoculum had about 35%, 45%, and 60% organic solids with the balance being water. The results for the inoculum containing 35% organic solids (and 65% water) are shown in FIG. 9 and Table 5A. Table 5B shows other inoculum values and results for other samples. The potato bag had a thickness of 1.35 mil. These bags are referred to as sample 1072.

Potato bags made with 25% NuPlastiQ or ESR and 70% LLDPE showed a remarkable 81% biodegradation over 834 days under simulated landfill conditions. NuPlastiQ or ESR is homogeneously blended with polyethylene, which advantageously results in the long carbon chains of the polyethylene being broken down and digested by the same microorganism that consumes the carbohydrate-based polymer NuPlastiQ or ESR material. These results indicate that the entire bag containing polyethylene has been biodegraded into carbon dioxide, methane, and water. Such a result is surprising and particularly advantageous.

  Tests performed at 45% organic solids and 60% organic solids also showed that the biodegradation rate exceeded the percentage of NuPlastiQ or ESR contained in the potato bag. Using a similar potato bag containing 1% biodegradation enhancing additive (sample 1073), and another similar potato bag containing EcoFLEX ™ compostable resin and metallocene LLDPE (sample 1075). Testing was also performed.

Example 4
Films made using NuPlastiQ or a blend of ESR and LLDPE were tested for anaerobic biodegradation after 201 and 370 days according to ASTM D-5338. The conditions were intended to simulate aerobic digestion and / or industrial compost conditions. The tested films are labeled 1345 and 1346 in Table 6 and FIGS. 10A-10B, which show the results after 370 days. At day 201, samples 1345 and 1346 showed adjusted biodegradation values of 74.2% and 72.4%, respectively, while the negative control showed -3.3% and the positive control showed 100%. showed that. 10A-10B plot actual biodegradation rates. Sample 1345 contained 25% NuPlastiQ or ESR, 72.5% LLDPE, and 2.5% compatibilizer. Sample 1346 contained 40% NuPlastiQ or ESR, 56% LLDPE, and 4% compatibilizer. Both films had a thickness of 1.0 mil.

In particular, the biodegradation of sample 1345 after 370 days is particularly excellent. This sample (see FIG. 10B) shows greater than 97% biodegradation when the non-biodegradable plastic material is polyethylene, which is, of course, under normal circumstances, not biodegradable (eg, , 100% polyethylene (see negative control in Table 6). The consequences of such biodegradation are noteworthy and particularly advantageous.

Example 5
Films made using NuPlastiQ or a blend of ESR and PBAT were tested for anaerobic biodegradation after 205 days according to ASTM D-6691, meaning simulating marine conditions. The films tested are labeled 1439 and 1440 in Table 7 and FIG. At day 205, samples 1439 and 1440 exhibited adjusted biodegradation values of 49.6% and 53.6%, respectively. Sample 1439 contained 30% NuPlastiQ or ESR, 67% PBAT, and 3% compatibilizer. Sample 1440 contained 27% NuPlastiQ or ESR, 70% PBAT, and 2.5% compatibilizer. Sample film 1439 had a thickness of 1.1 mil and sample film 1440 had a thickness of 1.0 mil.

Example 6
Additional manufactured films were tested for biodegradability. Table 8 below summarizes the results of such tests, some of which are described in detail above. Such tests show excellent biodegradability results under a variety of simulated conditions (eg, landfills, composting, marine environments) over a wide range of carbohydrate-based polymeric materials and various polymeric materials. .

Example 7
In accordance with the present invention, additional tests were performed to evaluate biodegradability for different loading levels of carbohydrate-based polymeric materials. Testing was in accordance with ASTM D5511. The levels of carbohydrate-based polymeric material in the test samples were 0% (control), 1%, 5%, 10%, and 20% by weight of the blend. Table 9 below summarizes the results of such a test. Even at the 1% loading, the biodegradation rate (2.7%) after 65 days was greater than the loading (1% only), indicating that the polyethylene contained in the blend was also degraded. This trend continues with data at day 95 where the rate of biodegradation continues to increase (eg, 5% at day 95). Higher loadings of 5%, 10%, and 20% of the carbohydrate-based polymer material show further accelerated results. In all samples loaded with a biodegradable carbohydrate-based polymeric material, the total non-biodegradable plastic content may be, for example, within a reasonable time period (eg, 1, 2, 3, 4, or 5 years). ) Is expected to be degraded under such disposal conditions.

Example 8
Films were made from a blend of biopolyethylene (supplied by Braskem), NuPlastiQ or ESR, and Bynel® compatibilizer. Once formed, the resulting films were tested for dart strength (eg, according to ASTM D-1709). The films were blown in various thicknesses from 0.5 mil up to 2 mils and in various proportions ranging from 0% to 35% by weight of the starch-based polymeric material (NuPlastiQ or ESR). The results are shown in FIGS. 12A and 12B.

  As can be seen from FIG. 12A, biopolyethylene alone (without NuPlastiq or ESR) has a dart strength of about 120 g at 0.5 mil thickness, a dart strength of about 155 g at 1 mil thickness, 1.5 mil dart strength. It provides a dart strength of about 200 g for thickness and about 270 g for 2 mil thickness. The approximate dart strength is shown in Table 10A. Table 10B shows the percentage increase in strength when compared to pure biopolyethylene film. It is readily apparent that there is an increase in the percentage of all thicknesses in the film, and all NuPlastiQ or ESR tested. The increase in strength is particularly large as the film becomes thicker (ie, the rate of increase is more dramatic for thicker films as compared to thinner films).

In forming and testing such films, Applicants have observed that the results of the increase in strength generally agree well with the results seen using synthetic petrochemical polyethylene. As noted above, it was observed that the strength increase increased more rapidly with increasing thickness when using the biopolyethylene material in the blend (i.e., the rate of increase was greater as compared to thinner films). Most dramatic in film).

  It was also observed that the sweet spot for starch-based NuPlastiQ or ESR with biopolyethylene could be about 15% instead of the about 25% observed with petrochemical feed polyethylene. Nevertheless, when NuPlastiQ or ESR was blended with either base resin, an increase in strength was observed as well.

  Finally, the film formed according to Example 8 contains a biomaterial content of well over 40%, and the base resin (eg, any “green” sustainable polymer such as those described herein) Materials) and NuPlastiQ or ESR materials based on carbohydrates or starches are derived from sustainable materials. The only component in the film not counted as biomaterial content is the compatibilizer (and, if available, a sustainable compatibilizer can be used). Thus, the biomaterial content is 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% of the film or other product. It can be at least 85%, at least 90%, or even at least 95% by weight. The films of Example 8 consisted of a biomaterial content other than Bynel® compatibilizer such that they contained a biomaterial content of greater than 90% by weight.

  Finally, the film of Example 8 is substantially completely biodegradable in a manner similar to that described for the various other test polyethylenes tested in the above examples. Thus, the present invention provides polymer films and other products with very high biomaterial content that are not only sustainable but also biodegradable.

Example 9
This example illustrates the effect of blow-up ratio and / or die gap. The dart impact test strength is measured on a variety of films, including films formed from polyethylene alone, and films formed from NuPlastiQ or a blend of ESR, polyethylene, and a compatibilizer. The film formed from the blend contains 25% renewable carbohydrate-based polymer material, 5% compatibilizer, and 70% polyethylene. All films are blow molded at a blow-up ratio of about 2.5. Applicants have observed that when blowing a film with an increased blow-up ratio using a blend, an increase in strength is observed, but when blowing a film from polyethylene alone, any blow-up ratio It was observed that it had no significant effect. In other words, polyethylene alone has substantially the same strength at a blow-up ratio of 1.5, 3, or anywhere in between. Table 11 below shows the approximate dart impact strength values (in grams) for films of various thicknesses of the invention compared to the control, as well as the percentage increase in strength for the various blends when compared to the control. .

FIG. 13 shows 100% polyethylene at various film thicknesses compared to a film formed from a blend of polyethylene and 25% NuPlastiQ or ESR renewable carbohydrate-based polymeric material, for example, with a blow-up ratio of about 2.5. Figure 3 shows additional comparative dart impact data for the film. FIG. 13 shows the ability to produce films having a thickness of only 0.1 mil. As described herein, forming such thin films from polyethylene material alone can be quite difficult. As shown by FIG. 13, the strength of the 100% polyethylene film is substantially independent of the blow-up ratio (ie, the strength is a blow-up ratio of 1.5, or 2.0, or 2.5 or 2.5 or Substantially the same at a blow-up ratio of 3.0). In all respects, the strength of films formed from 25% NuPlastiQ or ESR renewable carbohydrate-based polymer material blends is greater than the strength of films formed from polyethylene alone.

Example 10
Examples 10 to 14 are examples of the addition of an odor reducing agent. Example 10 is a comparative example. Samples are prepared from a blend of a carbohydrate-based polymer material and another polymer resin (selected as polyethylene), as well as a maleic anhydride-modified PE compatibilizer. The compatibilizer is included in an amount of 5% by weight. The amount of carbohydrate-based polymer material varies from 5% by weight to a maximum of 50% by weight, with the balance being a polyethylene polymer resin. These samples do not contain any odor reducing agents and exhibit a slight odor characteristic of carbohydrate-based polymeric materials, which can be described as a popcorn-like odor, a caramel corn-like odor, or a slightly burnt starchy odor . When the geometry of the article is relatively open (eg, a flat sheet or film of material), little odor is observable, but when the geometry is relatively closed (eg, The odor becomes more pronounced (in the form of a cup or when the film is wound on a roll).

Example 11
A sample is prepared that is identical to that of Example 10, but with a small amount of 4-hydroxy-3-methoxybenzaldehyde (vanillin) as an odor reducing agent. The odor reducing agent is provided as a powder, for example, as a lyophilized powder. The powder is mixed with a liquid component (eg, water and / or glycerin) used to make the carbohydrate-based polymeric material to provide a uniform dispersion of the odor reducing agent therein. Thereafter, the carbohydrate-based polymer material is formed from water, glycerin, and starch in the same manner as in Example 10 (and Example 1), so that the finished carbohydrate-based polymer material has 20 ppm (0.002%) by weight. It contains a level of odor reducing agent dispersed therein at a level. In each sample, the ratio of carbohydrate-based polymeric material to odor reducing agent (NuPlastiQ or ESR to ORA) is 50,000: 1.

  The characteristics of the sample are as shown in Table 12.

In contrast to the otherwise identical samples of Example 10, these samples no longer show the slight characteristic odor described in Example 10. The difference in odor is particularly pronounced in relatively closed shapes, such as when the blend is molded in the form of a cup. As a comparison, cups formed from blends as shown in Table 12 show no discernable odor, as do cups formed from 100% polyethylene. It is surprising that only small amounts of odor reducing agents are sufficient to counteract other characteristic odors typically associated with carbohydrate-based polymer content.

Example 12
A sample is prepared that is identical to that of Example 10, but contains a small amount of lyophilized strawberry powder as an odor reducing agent. The powder odor reducer is dispersed in the carbohydrate-based polymer material at a level of 20 ppm (0.002%) by weight.

  The article is formed in the same manner as in Example 10, but with a small amount of odor reducing agent dispersed therein.

In contrast to the otherwise identical samples of Example 10, these samples no longer show the slight characteristic odor described in Example 10. Odor differences are particularly pronounced in relatively closed shapes, such as when the blend is molded into a cup shape. By comparison, cups formed from blends as shown in Table 13 show no discernable odor, as do cups formed from 100% polyethylene. It is surprising that only small amounts of odor reducing agents are sufficient to counteract other characteristic odors typically associated with carbohydrate-based polymer content.

Example 13
A sample is prepared that is identical to that of Example 10, but with a small amount of lyophilized blueberry powder as an odor reducing agent. The powder odor reducer is dispersed in the carbohydrate-based polymer material at a level of 20 ppm (0.002%) by weight.

  The article is formed in the same manner as in Example 10, but with a small amount of odor reducing agent dispersed therein.

In contrast to the otherwise identical samples of Example 10, these samples no longer show the slight characteristic odor described in Example 10. Odor differences are particularly pronounced in relatively closed shapes, such as when the blend is molded into a cup shape. As a comparison, cups formed from blends as shown in Table 14 show no discernable odor, as do cups formed from 100% polyethylene. It is surprising that only small amounts of odor reducing agents are sufficient to counteract other characteristic odors typically associated with carbohydrate-based polymer content.

Example 14
A sample is prepared which is identical to that of Example 10, but contains only a small amount of lyophilized bubaniline powder as odor reducing agent. The powder odor reducing agent is dispersed in the carbohydrate-based polymer material at a level of 5 ppm (0.0005%) to 100 ppm (0.01%) by weight.
The article is formed in the same manner as in Example 10, but with a small amount of odor reducing agent dispersed therein.

In contrast to the otherwise identical samples of Example 10, these samples no longer show the slight characteristic odor described in Example 10. Odor differences are particularly pronounced in relatively closed shapes, such as when the blend is molded into a cup shape. By comparison, cups formed from blends as shown in Table 15 show no discernable odor, as do cups formed from 100% polyethylene. It is surprising that only small amounts of odor reducing agents are sufficient to counteract other characteristic odors typically associated with carbohydrate-based polymer content. Relatively high levels of vanillin (e.g., 100 ppm or more) can begin to contain the characteristic favorable vanilla odor.

IV. Conclusion Finally, while various implementations are described in a language specific to structural features and / or methodological acts, the subject matter defined in the accompanying language is not necessarily limited to the particular features or acts described. Shall be understood. Rather, the specific features and acts are disclosed as example forms of implementing the claimed subject matter.

  Finally, it is to be understood that the embodiments of the features of the invention disclosed herein are illustrative of the principles of the features of the invention. Other modifications that can be employed are within the features of the invention. Thus, by way of example, and not limitation, alternative features of the invention may be utilized in accordance with the teachings herein. Thus, the features of the present invention are not strictly limited to those shown and described.

  The scope of the present disclosure may rewrite any claim as dependent on any other claim, include multiple dependencies from any combination of the other claims, and / or include multiple claims. It will be appreciated that the combination extends. Such extends to the “summary of exemplary concepts that may be claimed” as described in the Summary of the Invention section. The scope of the present disclosure also includes the insertion and / or removal of any combination of features from any claim for insertion into another claim, or the use of such features from any other claim. It covers the drafting of new claims, including any combination.

Claims (51)

An article,
A substantially amorphous carbohydrate-based polymer material having a crystallinity of 20% or less;
Another polymer material blended with the substantially amorphous carbohydrate-based polymer material;
The strength of the article is at least 5% greater than the strength that the article would have if it were made solely from other polymer materials without the carbohydrate-based polymer material, or under simulated landfill conditions The article wherein the amount of the article that biodegrades within 5 years is at least one of greater than the amount of the carbohydrate-based polymeric material.   The article of claim 1, wherein the other polymeric material comprises a polyolefin.   Article according to claim 1, wherein the substantially amorphous carbohydrate-based polymer material has a crystallinity of less than 20%, preferably less than 15%, more preferably less than 10%.   The substantially amorphous carbohydrate-based polymer material has a glass transition temperature, heat distortion temperature, or Vicat softening of more than 70 ° C, more than 75 ° C, more than 80 ° C, 70 ° C to 100 ° C, or 80 ° C to 100 ° C. The article of claim 1, wherein the article has a temperature.   The article of claim 1, wherein the substantially amorphous carbohydrate-based polymeric material has a Young's modulus of at least 1.0 GPa.   The article of claim 1, wherein the other polymeric material comprises polyethylene.   The article of claim 6, wherein the article comprises a film, wherein the film is formed from a blend of the carbohydrate-based polymeric material and polyethylene.   The article of claim 1, wherein the other polymeric material comprises a petrochemical-based polymeric material that is not biodegradable by itself.   The article of claim 1, wherein the other polymeric material comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride, PBAT, or polycarbonate.   5% by weight of the carbohydrate-based polymer material is sufficient to make the other polymer material biodegradable, such that the amount of the article that biodegrades within 5 years under simulated landfill conditions The article of claim 1, wherein the amount is greater than the amount of carbohydrate-based polymeric material.   The article of claim 1, wherein the blend of the carbohydrate-based polymer material and the other polymer material comprises at least 5% by weight of the carbohydrate-based polymer material.   The article of claim 1, wherein the blend of the carbohydrate-based polymer material with another polymer material comprises 5% to 50% by weight of the carbohydrate-based polymer material.   The article of claim 1, wherein the blend of the carbohydrate-based polymer material with another polymer material comprises 10% to 50% by weight of the carbohydrate-based polymer material.   The article according to claim 1, wherein the article comprises a film, the film having a thickness of less than 0.005 mm, preferably 0.002 mm to 0.004 mm.   The article of claim 1, wherein the article comprises a film, wherein the film has a thickness of between 0.1 mil and 10 mil.   The article of claim 1, wherein the carbohydrate-based polymer material comprises a starch-based polymer material.   17. The article of claim 16, wherein the starch-based polymeric material is formed from starch and a plasticizer.   18. The article of claim 17, wherein the starch comprises one or more of potato starch, corn starch, or tapioca starch, and wherein the plasticizer comprises glycerin.   17. The article of claim 16, wherein the starch-based polymeric material is formed from a blend of at least two different starches.   The article according to claim 1, wherein the article comprises a film, the film having a dart strength of at least 100 g / mil (0.0254 mm) thickness, preferably at least 140 g / mil (0.0254 mm) thickness. Goods.   2. The article of claim 1, wherein the strength of the article is at least 10% greater than the strength that the article would have if it were made solely of the other polymer material without the carbohydrate-based polymer material. .   The article of claim 1, wherein the other polymeric material comprises a sustainable polymeric material.   23. The article of claim 22, wherein the other polymeric material comprises a sustainable polymeric material formed from one or more of sugarcane or corn.   23. The article of claim 22, wherein at least 90% of the polymer content of the article is provided from a sustainable source.   23. The article of claim 22, wherein the article comprises at least one of a film, sheet, bottle, or other container.   23. The article of claim 22, wherein the sustainable polymeric material comprises one or more of polyethylene, polypropylene, or polyethylene terephthalate formed from a sustainable source.   Wherein the blend of the substantially amorphous carbohydrate-based polymer material and the other polymer material further comprises an odor reducing agent, wherein the odor reducing agent is preferably an organic odor reducing agent; The article of claim 1 wherein, in the absence of, the carbohydrate-based polymeric material imparts a characteristic burnt carbohydrate odor to the article.   28. The article of claim 27, wherein the organic odor reducing agent comprises a lyophilized powder.   28. The article of claim 27, wherein the organic odor reducing agent comprises a vanilla extract.   28. The article of claim 27, wherein the organic odor reducing agent comprises vanillin. The organic odor reducing agent has the following chemical structure:
28. The article of claim 27, comprising:   28. The article of claim 27, wherein the organic odor reducing agent consists essentially of 4-hydroxy-3-methoxybenzaldehyde.   The organic odor reducing agent is 1% or less, preferably 0.1% or less, more preferably 0.01% or less, more preferably 1000 ppm or less, more preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 20 ppm or less. 28. The article of claim 27, comprising the following blend:   28. The organic odor reducing agent according to claim 27, wherein the organic odor reducing agent is present in a ratio of 1: 1000 to 1: 100,000, preferably 1: 25,000 to 1: 75,000 relative to the carbohydrate-based polymeric material. Goods.   28. The article of claim 27, wherein the organic odor reducing agent comprises a fruit extract.   The organic odor reducing agent comprises a lyophilized organic fruit extract selected from an extract of vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, passion fruit, raspberry, or a combination thereof. An article according to claim 35.   37. The article of claim 36, wherein the lyophilized organic fruit extract is present in a plastic material in a ratio of 1: 1000 or less to the carbohydrate-based polymer material.   28. The article of claim 27, wherein the organic odor reducing agent is included within the carbohydrate-based polymeric material. A method of providing a plastic article with increased sustainability while also providing the plastic article with at least one of increased strength or biodegradability, said method comprising:
Providing a polymer material;
Mixing a substantially amorphous carbohydrate-based polymer material having a crystallinity of 20% or less with the polymer material;
Heating the mixture to a temperature in the range of 120 ° C. to 180 ° C. so as to melt mix the polymer material with the substantially amorphous carbohydrate-based polymer material;
Forming a plastic article from a blend of the polymeric material and the substantially amorphous carbohydrate-based polymeric material;
The strength of the article is at least 5% greater than the article would have if the article were made from the polymer material alone without the carbohydrate-based polymer material, or 5 under simulated landfill conditions Wherein the amount of the article that biodegrades within a year is greater than the amount of the carbohydrate-based polymeric material.   Although the polymer material itself is not biodegradable by itself, blending it with the carbohydrate-based polymer material imparts biodegradability to the polymer material, thereby resulting from the carbohydrate-based polymer material. The claim that the difference in the amount of the article that biodegrades within 5 years under simulated landfill conditions when compared to the amount is due to the biodegradation of the polymeric material that is not, by itself, biodegradable. 39. The method of claim 39.   41. The method of claim 40, wherein at least 25% of the polymeric material that is not itself biodegradable biodegrades within three years.   40. The article of claim 39, wherein the article comprises a film, the film having a dart strength of at least 100 g / mil (0.0254 mm) thick, preferably at least 140 g / mil (0.0254 mm) thick. the method of.   40. The article of claim 39, wherein the strength of the article is at least 10% greater than the strength that the article would have if made from the other polymer material alone, without the carbohydrate-based polymer material. Method. Forming the plastic article comprises blowing a plastic film in a film blow molding apparatus, wherein the film comprises the blend of the polymeric material and the substantially amorphous carbohydrate-based polymeric material. Blow molded from
(A) the film blow molding apparatus operates at a high blow-up ratio of at least 2.0 when blow-molding a plastic film, and the high blow-up ratio increases in the blow-molded plastic film; And / or (B) the die gap of the film blow molding apparatus is selected to be a narrow die gap of 500 micrometers or less, wherein the narrow die gap is blown plastic film 40. The method of claim 39, wherein said method provides increased strength.   46. The method of claim 44, wherein the film has a thickness of between 0.1 mil and 10 mils.   The method according to claim 45, wherein the film has a thickness of less than 0.005 mm, preferably 0.002 mm to 0.004 mm.   The method of claim 44, wherein the blow-up ratio is between 2.2 and 2.8.   The method of claim 44, wherein the blow-up ratio is 2.5.   The method of claim 44, wherein the strength of the plastic film is increased by selecting the high blow-up ratio.   45. The method of claim 44, wherein the blow-up ratio is selected to be at least a value of 2.0 and the die gap is selected to be no greater than 500 micrometers.   The method of claim 44, wherein the die gap is selected to be between 250 micrometers and 500 micrometers.