TW201833236A - Carbohydrate-based polymeric materials - Google Patents

Abstract

Described herein are articles including carbohydrate-based polymeric materials, and methods for forming such articles. Such articles may exhibit improved sustainability, biodegradability, increased strength, and/or other various beneficial characteristics. The carbohydrate-based polymeric material may be formed from one or more starches, a plasticizer (e.g., glycerin), and water. The carbohydrate-based polymeric material may exhibit very low crystallinity charactersitics, so as to be substantially amorphous (e.g., having a crystallinity of no more than 20%, no more than 10%, less than 10%, etc.). The carbohydrate-based polymeric materials may be blended with non-biodegradable plastics to render those plastic materials now biodegradable, it may lend increased strength to the film or other article, it may be blended with a sustainable polymeric material (e.g., bioPE or the like) for increased sustainability (e.g., as much as 90% or more), or the like. The blend may include an organic odor-reducing agent to counteract a characteristic slightly burned carbohydrate odor associated with the carbohydrate-based polymeric material. Very small fractions of such odor-reducing agent (e.g., 1:50,000) relative to the carbohydrate-based polymeric material are surprisingly effective. When blowing films, a high blow up ratio of 2.0 or greater, and/or a narrow die gap (e.g., 500 microns or less) may be used to lend increased strength to the resulting film.

Description

   Carbohydrate-based polymer materials   

The invention relates to the field of plastic materials, in particular to polymer materials based on carbohydrates.

Traditional petrochemical plastic products demand strong, lightweight and durable. However, these plastic products are often non-biodegradable and have resulted in tens of thousands of tons of plastic products being discarded in landfills or floating in the ocean. In order to reduce the amount of plastic waste, some items typically made of petrochemical plastics are changed to biodegradable materials.

For example, a large amount of polyethylene and polypropylene, and many other plastics (polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, polycarbonate, nylon, etc.) are typically not easily biodegradable. Petrochemical plastic materials. Usually in the case of such materials known as "green" plastics, they can come from renewable or sustainable sources, rather than petrochemical raw materials.

In recent years, by adding UV and or OXO additives (for example, PDQ-M, PDQ-H, BDA, and OxoTerra ^™ from Willow Ridge Plastics, OX1014 from LifeLine; or organic additives, such as from Enso's Restore®, EcoPure® from Bio-Tec Environmental, ECM masterbatch Pellets 1M, or BioSphere® from ECM Biofilms) to increase the decomposability of these plastic materials. The use of these additives often makes the plastic industry Associations (such as SPC, APR, FPA, and / or BPI) are dissatisfied because the degree of biodegradation and the rate of biodegradation are usually too slow, and the OXO additive usually easily initiates structural fragmentation or degradation, which accelerates the physical properties of these plastic materials Degradation, becoming small fragments of the base plastic material, rather than the exact conversion of the plastic into natural materials such as carbon dioxide (CO ₂ ), water (H ₂ O), and methane (CH ₄ ).

For example, these materials simply act to accelerate the destruction of the macrostructure of the plastic product due to exposure to ultraviolet light (from sunlight) and / or oxygen. These special plastics are not truly biodegradable, and will not decompose to any estimable degree within a specific length of time (such as 5 years, 3 years, or 1 year). They simply lose strength, chip, and break into Small snippet. As a result, piles or small pieces of polyethylene or other base plastic materials are produced. As a result of the addition of the UV and / or OXO additive, bottles, cans, films or other items made of these materials are physically degraded over time. However, the weight of the polyethylene or other base plastic material fragments remained substantially the same, and no actual biodegradation occurred. When the object becomes debris, shards, and broken into small fragments, the decomposition is only physical, and many small fragments of polyethylene or other base plastic materials remain. For these plastic materials, the term "biodegradable" means a certain degree of misuse because of the complete biodegradation of the polymer material itself (i.e., the substantial fragments of the plastic will decompose into CO _2, CH _4, H ₂ O, etc.) does not actually occur.

In addition, most of the plastics used today are not made from renewable or sustainable sources (eg, starting materials are renewable in less than about 100 years). Herein, the terms renewable or sustainable are used interchangeably. More precisely, polyethylene (PE), polyethylene terephthalate (PET), and other traditional plastics used in the mass production of bottles, cans, bags, and other packaging materials are derived from petrochemical starting materials, and petrochemical products The starting materials are not renewable or sustainable.

In order to increase sustainability, some companies have recently been working to develop processes for making these plastic materials from renewable sources such as sugar cane, corn or other plants. Plant materials are sustainable. For example, these renewable materials can be used to make ethanol, glycol, or other chemical building block materials, which can then be further reacted to make polymerizable monomers. These efforts have begun to show their potential in some high-priced products. Among them, these "green" plastic resins can be mixed with conventional petrochemical base resins. For example, some materials (such as 30%) for making bottles or other packaging materials are sustainable. In fact, some products are now available in 100% "green" plastic resins.

When the mixture of this "green" material with conventional petrochemical plastics begins to become a viable product, it is still difficult to implement the replacement of the remaining conventional petrochemical plastic materials with all sustainable materials, and there are still processing, cost and other considerations. Many challenges.

In addition, even by replacing some materials with sustainable plastic materials to reduce the amount of conventional non-sustainable plastic materials, the resulting plastic packaging materials are still non-biodegradable. For example, even if a plastic packaging material is made of 100% "green" plastic or contains some "green" PE or "green" PET, it is still non-biodegradable. This lack of biodegradability shows a huge and persistent problem. In this technical field, it would be a significant advantage if biodegradable items could be provided. Increased strength is also expected. It would be even more advantageous if the whole (or almost all) of the item were made of sustainable materials.

In addition, reducing the use of such non-renewable petrochemical plastic materials has been an object of recent years. Some are intended to make plastic materials from renewable sources such as sugar cane or other plant products as the source resin. However, to achieve a certain degree of feasibility, compared with plastics made of non-renewable materials based on petrochemicals, such renewable sources of plastic are much more expensive.

In addition, the plastic material has a specific strength characteristic correlation, depending on whether the specific material is used to form a plastic film or other material, and the physical characteristics of the film or other article itself. For example, when a plastic film is formed, the use of non-renewable petrochemical plastic resin materials can be reduced by forming a thinner film, but a reduction in the amount of this material will result in a more fragile film.

For example, WO 2014/0190395, filed by Leufgens, describes the use of a mixture of polyethylene and thermoplastic starch (especially Cardia BL-F) to form a film. The control film is fragile, and because of the difficulty in processing mixtures containing conventional thermoplastic starches, the films prepared here must be very thick (e.g., 3 mils). Such extremely thick films do not cause a substantial reduction in the amount of petrochemical-based plastic resin materials, because it is impossible to implement thin films, and / or, because such thermoplastic starches weaken the overall film, so Must be thick to maintain the desired strength.

When using plastic materials of renewable origin, it is desirable to provide films with any desired film thickness that can increase strength and its related manufacturing methods, for example, by adjusting process parameters in the manufacturing process. Such a method may allow a film having a desired thickness and increased strength, or a film having a lower thickness but the same strength. At the same time, this method can actually reduce the amount of petrochemical plastic materials and replace them with plastic materials of renewable sources without increasing the overall thickness.

In addition, although the replacement of some petrochemical materials with starch or starch-based materials shows the potential for improving sustainability, one of the problems with adding such starch or starch-based materials is that the plastic composition contains a significant amount of this Seeding starch or starch-based materials can cause a significant odor in articles prepared using such mixtures. For example, the material may have a slight burnt starch flavor, popcorn-like flavor, and caramel corn flavor. Some people find this smell pleasant or even eager, but others may prefer not to express it, such as plastic products made of starch-free or starch-based materials (such as polyethylene or other polymeric materials). Resin is formed separately).

To sum up, there are still many problems in this technical field.

The present invention relates to various concepts for implementing article preparation and / or preparation methods. In one embodiment, the present invention relates to articles having increased strength and / or biodegradability. In some examples, articles can be made from a mixture of one or more polymer materials (e.g., synthetic, such as petrochemical-based, or other) and one or more carbohydrate-based polymer materials, the latter having low crystals (i.e., they (Substantially amorphous), glass transition temperature, heat distortion temperature, Fica softening temperature and other specific characteristics. In a specific example, the one or more carbohydrate-based polymer materials may include one or more starch-based polymer materials. For example, the carbohydrate-based polymer material is substantially amorphous and has no more than 20% crystals; it may have a Young's modulus of at least 1.0 GPa, and / or it may have a temperature of 70 ° C to 100 ° C. ℃ glass transition temperature or heat distortion temperature or Fica softening temperature. Other features of this carbohydrate-based material will be detailed below.

A method of preparing an article may include providing one or more polymer materials and one or more substantially amorphous carbohydrate-based polymer materials. The one or more polymer materials and the one or more carbohydrate-based polymer materials may be mixed and heated. The obtained mixture can be extruded into a plastic product using a plastic processing equipment, such as an injection molding machine, a blow molding machine, a thermoforming machine, and the like. Gas can be injected into the extruded mixture to form a film. Such films can be processed into bags or other categories of items. Other items can be extruded plastic products, injection molded plastic products, blow molded plastic products, extruded or pressed plates or films, thermoformed plastic products, etc.

The article may have increased strength and / or biodegradability. For example, in one embodiment, mixing the substantially amorphous carbohydrate-based polymer material and other polymer materials adds biodegradability to the other polymer materials, even if the other polymer materials themselves are separate Not biodegradable when present. For example, polyethylene itself is not biodegradable, which is known. The applicant in this case confirmed the ability to add biodegradability to other non-biodegradable plastic materials (such as polyethylene). Other examples may include, but are not limited to, polypropylene, other polyolefins, polyethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, nylon, and polycarbonate. For example, under simulated disposal conditions (such as under simulated burial conditions), the biodegradability of the item within 5 years or other preset time lengths is higher than the carbohydrate-based polymer contained in the item The amount of material. Such simulated disposal conditions may include simulated burial conditions (eg, under any typical ASTM standard, such as, but not limited to, D-5511 and / or D-5526), simulated industrial composting conditions (eg, ASTM D-5338), or simulated Marine conditions (eg ASTM D-6691). In other words, part of this other non-biodegradable polymer material is now biodegradable for some unknown reason, the same as carbohydrate-based materials. For example, if the article is formed from a mixture containing 25% carbohydrate-based polymer materials, the biodegradability of the article under these conditions is greater than 25% (i.e., part of the other polymer materials) Also decomposed, even if the other polymer material itself is not decomposable under similar conditions).

The applicant obtained the results of third-party testing, which shows that the decomposition can occur relatively quickly, for example, sometimes within about 180 days (6 months), within about 1 year, within about 2 years, and about 3 years Occurred within 5 years.

In addition to or instead of biodegradability, the item and method can provide increased strength (e.g., at least 5% increase in dart strength or other strength characteristics), which is related to the absence of the carbohydrate-based high Compared with molecular materials but only articles made from the other polymer materials.

Other aspects of the invention relate to articles formed from renewable or sustainable "green" plastic materials and the carbohydrate-based (eg, starch-based) polymer materials. For example, in another embodiment, the other polymer material may be a sustainable “green” polymer material, and the source is a sustainable resource (for example, a plant such as sugar cane, corn, etc.). In an embodiment, the sustainable polymer material can be processed into a polymer, which has similar but not exactly the same characteristics as petrochemical-based polymers (for example, it can be "green" polyethylene, "green" polymer Acrylic, "green" polyethylene terephthalate (PET), etc.). Such "green" polymers may have similar but not identical chemical and physical properties compared to the same polymers (such as polyethylene) made from petrochemical raw materials. The carbohydrate-based polymer material can substantially add biodegradable characteristics to the persistent polymer material by mixing or other forming methods, wherein the persistent polymer material may not have such biodegradability Features (or, if the sustainable polymer material already has some biodegradability, this feature can be enhanced).

In addition to or instead of biodegradability, the item may have increased strength, which is compared with other similar items, but its preparation is based on the carbohydrate-based polymer material. For example, an embodiment relates to an article, which comprises one or more carbohydrate-based polymer materials (such as the aforementioned materials) and one or more sustainable polymer materials, the source of which is a sustainable plant source, wherein, and Compared to articles made without the carbohydrate-based polymer material, the strength of the article is increased by at least 5%. For example, the applicant of this case found that the article containing such a carbohydrate-based polymer material (e.g., a mixture of the two polymer materials) can provide compared with those containing only the sustainable polymer material. Increased intensity.

Another aspect of the present invention relates to the use of blow-up ratios and / or die gaps during film preparation to increase the productivity of such carbohydrate-based polymer materials and other polymer materials. A method for the film strength of a film made from a mixture. In particular, the applicant of this case found that the strength of most plastic films blown from different resin materials (such as polyethylene and / or polypropylene) would not be affected by the change in inflation ratio. However, as described herein, the Renewable carbohydrate-based (e.g., starch-based) polymer materials have specific amorphous characteristics, specific glass transition temperature characteristics, Fika softening temperature characteristics, or thermal deformation temperature characteristics, and / or specific elastic modulus characteristics, and their When it is blown into a film by being contained in the resin mixture, the strength is changed depending on the inflation ratio and / or the mold gap, and the film may be blown only in an extremely narrow range of conditions. The applicant of this case has actually successfully blown a film that can be as thin as 0.1 mil and has significant strength; in the prior art, it is believed that such a film blowing with a known resin or preparation method is impossible.

Blow-up ratio means dividing the maximum diameter of the blown film by the diameter of the die of the film blowing equipment. Typically, when the molten resin material comes out of the blow mold, the diameter will partially increase, and it starts to move upwards, through the "frost line" toward the part of the blown film where the resin is blown. The material no longer melts and solidifies. Curing and crystallization typically occur at the cold line, where it can be observed that the blown film bubbles begin to appear opaque or "frosty." The applicant in this case observed that when using the specific regenerative carbohydrate-based polymer materials described herein, increased strength can be obtained, surpassing other similar blown plastic films (but without carbohydrate-based polymer materials) )Strength of. This increase in strength is achieved by choosing a high inflation ratio and / or a narrow die gap. It is believed to be the result of the alignment, orientation, and / or extension of the molecular structure of the carbohydrate-based polymer material, which is homogeneously distributed throughout the resin mixture to form a thin film. It is believed that the observed increase in strength is due at least in part to the alignment and orientation of the amorphous, renewable, carbohydrate-based polymer material in the film.

In other words, as described herein, the specific regenerative carbohydrate-based polymer material can be combined with the specific operating conditions to enhance the strength of the resulting film; not to mention, replace with the regenerative carbohydrate-based polymer material. Permanent advantages obtained by other polymer components of the film.

In particular, the typical film obtained is blown with an inflation ratio of about 1.5. The applicant of the present case found that when the resin mixture used for blown film contained a renewable carbohydrate-based polymer material such as NuPlastiQ or Eco Starch Resin (ESR) (sold by the applicant), Increasing the inflation ratio to at least 2.0, such as from 2.2 to 2.8 (eg, about 2.5), higher inflation ratios can result in significantly increased film strength. For example, compared to film strengths that do not contain NuPlastiQ or ESR but have the same rest, a mixture of NuPlastiQ or ESR and a typical polymer resin (such as polyethylene and / or polypropylene) can have a substantial inflation ratio of 1.5. Same strength characteristics.

This film (without NuPlastiQ or ESR) does not have any significant increase in strength when the inflation ratio is increased, so there is no reason to change the value of the inflation ratio when blowing this film. The applicant of this case found that when the resin mixture contains NuPlastiQ or ESR, when a high inflation ratio is applied (such as at least 2.0), the strength is significantly increased, as described above.

Furthermore, NuPlastiQ or ESR does not have many of the problems encountered with alternative thermoplastic starch materials that have made these materials useful for forming relatively thin films (such as below 2 mils, typically below 1.5 mils, such as 0.1 to 1.5 mil). The combination of these findings enables the applicant of the present case to prepare films of the desired thickness and increased strength, which is the same as using the same material but without NuPlastiQ or ESR (or compatibilizer, that is, by other polymer materials such as polyethylene alone Formed). When NuPlastiQ or ESR was used in the mixture, the discovery also produced films of the same strength, but with increased thickness. Such a result is surprising and advantageous, and it is possible to prepare a film containing a significant amount of a renewable resin while increasing the strength. This can be achieved by using an inflation ratio and / or a die gap. The applicant of this case also found that by ensuring that the mold gap applied to the blown film equipment is relatively narrow, it is also possible to increase the strength. Again, narrow mold gaps are not possible in many practical operations of conventional thermoplastic starch mixtures, as evidenced by Lovgens (with a mold gap of 1.6 to 1.8 mm). The present invention can be applied with a die gap of 1000 micrometers (micron) or less, and more typically 500 micrometers or less. Accordingly, the inflation ratio and / or die gap according to the present invention can be used to provide increased film strength.

For example, one embodiment relates to a method for providing increased strength to a blown plastic film. The method includes blowing a plastic film with a blown film device. The film is made of a first polymer material (for example, polyethylene, other polymers). Olefin, or other conventional polymer materials) and a renewable carbohydrate-based polymer material. The regenerable carbohydrate-based polymer material may be substantially amorphous, having no more than 20% crystals; it may have a Young's modulus of at least 1.0 GPa, and / or a glass transition temperature of 70 ° C to 100 ° C , Heat distortion temperature, or Fica softening temperature. The blown film equipment can be operated with a high inflation ratio and / or a narrow mold gap, such as an inflation ratio of at least 2.0 when the film is blown, or the mold gap may not exceed 500 microns. The high inflation ratio and / or narrow die gap can provide the blown plastic film with increased strength (for example, the same as other conditions, but with a lower inflation ratio and / or a larger die gap).

Another embodiment may be related to a method for increasing the strength of a blown plastic film by using the blow-up ratio. The method includes blowing a plastic film with a blown film device, the film comprising a first polymer material and a second A polymer material, which includes a mixture of renewable carbohydrate-based polymer materials. The regenerable carbohydrate-based polymer material may be substantially amorphous, having no more than 20% crystals; having a Young's modulus of at least 1.0 GPa, and having a glass transition temperature of 70 ° C to 100 ° C, Ficca Softening temperature or heat distortion temperature. The method may further include: using (ie, specifically selecting) the inflation ratio of the blown film equipment to select a high inflation ratio of at least 2.0 to increase the strength of the film (for example, the same as other conditions, but for The lower inflation ratio is compared). In addition to or instead of using the blow-up ratio, the method may include using (ie, specifically selecting) the die gap of the blown film equipment to select a narrow die gap of no more than 500 microns, so the narrow die gap and / or The inflation ratio increases the strength of the film (e.g., the same as all other conditions, but with a higher die gap and / or a lower inflation ratio).

Another embodiment of the present invention may be related to a method for reducing a unique odor caused by including a starch-based polymer material or other carbohydrate-based polymer materials, and an article including such a odor reduction. The carbohydrate-based polymer materials and other similar carbohydrate-based polymer materials described herein have a unique slightly burnt starch, popcorn, or caramel corn type odor. Although an atypical unbearable odor, the odor is still quite noticeable in some articles made from a mixture of materials containing the carbohydrate-based polymer material; especially when the finished article is relatively geometrically relatively "Closed" (e.g., in a cup), or other closed structure whose volume is bounded by the plastic material on two, three, or more sides. This unique odor may accumulate in the enclosed volume and become noticeable to consumers or in other applications (for example, if the user places his nose into such a cup and sniffs).

The applicant in this case wants to remove or minimize this unique odor, so the odor will be similar to or equivalent to the odor (typically odorless) of articles made from standard (such as petrochemical-based) polymer materials. . For example, an article according to the present invention may be formed from a mixture of such a standard "other polymer material" and the carbohydrate-based polymer material, as previously described and described herein. The applicant of this case found that by adding a very small amount of deodorant, especially an organic deodorant, the unique odor can be substantially removed or minimized.

There are some previous technologies that attempt to reduce the odor caused by distillers dried grains (DDG) materials, such as described in WO2009058426, which requires the addition of relatively high amounts of activated carbon or steam activated anthracite coal. To achieve a certain degree of effective possibility, the concentration of such materials is high, and the cost of such materials is too high, so it is not feasible for commercial implementation. In addition, adding a high amount of dark activated carbon or steam activated anthracite is not desirable, which will make them equivalent to pigments under certain conditions to make the plastic material dye; when high-definition films, high-color items or other similar items are This can cause big problems when you want.

Therefore, an embodiment of the present invention may be a sustainable plastic material, including the carbohydrate-based polymer material, other polymer materials, and also a deodorant. In the absence of the deodorant, the carbohydrate-based polymer material will give the sustainable plastic material a special carbohydrate scorching odor. In one embodiment, the deodorant may be organic and include 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 deodorant may include freeze-dried fruits or vegetables, or extracts of fruits or vegetables, such as vanilla extract. The organic deodorant may actually be extracted from fruits, vegetables, or other plants; or may include aromatic compounds that are typically found in the extract, but are artificially synthesized (e.g., synthetic vanillin or other synthetic aromatic compounds) applicable). Vanillin is an aromatic benzaldehyde compound, also known as 4-hydroxy-3-methoxybenzaldehyde.

The applicant of this case was surprised to find that a very small amount of aromatic deodorant is sufficient to substantially remove any unique odor caused by the carbohydrate-based polymer material, which is included in the preparation of the In a mixture of sustainable plastic materials. For example, in order to substantially remove the odor, the weight ratio of the deodorant to the carbohydrate-based polymer material is 1: 1000 or less. For example, as low as 100 ppm, 50 ppm, or even 20 ppm or less, is a substantial mark sufficient to remove this unique odor.

This was an amazing discovery, and the odor was removed with such a low amount of deodorant. Because the required amount is so low, and the odor does not appear to be typically replaced or masked by the taste of the deodorant, it is believed that the mechanism may not simply mask the unique carbohydrate odor. Although the mechanism is not fully understood, it may be a chemical interaction between the aromatic or other organic deodorant and the unique odorous compound that heats the carbohydrate-based compound while the thermoplastic mixture melts and forms the desired item. Polymer materials.

The deodorant may be contained in the carbohydrate-based polymer material, for example, in a master batch thereof. Therefore, an embodiment may be such a sustainable thermoplastic carbohydrate-based polymer material with reduced odor, which includes the organic deodorant premixed with the carbohydrate-based polymer material. The weight ratio of the organic deodorant to the carbohydrate-based polymer material may be not higher than 1: 1000 (that is, compared with the amount of the deodorant, the carbohydrate-based polymer material is at least 1000 times the above). In one embodiment, the ratio of the deodorant to the carbohydrate-based polymer material may be thinner, such as 1: 50,000.

The present invention obviously also includes related methods, such as a method of reducing the unique odor of a material mixture containing a carbohydrate-based polymer material, for example, by including a small amount of an organic deodorant in the mixture. Here, the carbohydrate-based polymer material is provided as a master batch, and the deodorant is provided in the master batch, and has been mixed with the carbohydrate-based polymer material. Therefore, when the master batch is then mixed with a polymer resin material (for example, any of a number of different plastic resins, such as PE, PP, other polyolefins, polyesters, polystyrene, PBAT, polycarbonate, or others) In some cases, the mixed material also contains the deodorant mixed therein.

[Summary of illustrative concepts to be requested]

1. An article comprising: one or more substantially amorphous carbohydrate-based polymer materials (such as starch-based polymer materials) having less than 20%, less than 10% crystals, and a specific glass transition temperature , Heat distortion temperature, Fika softening temperature, specific Young's modulus, and / or other characteristics of NuPlastiQ or ESR; and one or more polyolefin-based polymer materials; wherein the item has a thickness of at least 140 grams per mil. Drop weight impact test value.

2. The article according to item 1 of the patent application scope, wherein the one or more starch-based polymer materials are formed of one or more starches and one or more plasticizers.

3. The article as claimed in claim 2, wherein the one or more starches include one or more of potato starch, corn starch, and cassava starch, and the plasticizer includes glycerin.

4. The article of claim 1 in which the one or more polyolefin-based polymer materials include polyethylene.

5. The article of claim 1 in the patent application scope, wherein the article is a bag having a thickness of about 0.01 mm to 0.1 mm, and the bag includes a cavity having a volume of about 1 L to about 100 L.

6. The article according to item 1 of the patent application scope, wherein: the one or more starch-based polymer materials include about 20% to 40% by weight of the article; the one or more polyolefin-based polymer materials include the article About 60 wt% to 80 wt%; the article has a thickness of about 0.02 mm to 0.05 mm; and the article has a drop weight test value of about 265 to 330 grams per mil thickness.

7. The item in the scope of patent application, further comprising a compatibilizer, which is present in an amount not exceeding 8% by weight of the item.

8. An article comprising: a substantially amorphous carbohydrate-based polymer material (e.g., starch-based polymer material) having less than 20%, less than 10% crystals, a specific glass transition temperature, a Ficca Softening temperature, or heat distortion temperature, specific Young's modulus and / or other characteristics of NuPlastiQ or ESR, formed from a starch mixture comprising a first content of a first starch and a second content of a second starch; and A polyolefin-based polymer material; wherein the article has a drop weight impact test value that is higher than: (i) a first drop weight impact test value of a first item that includes the polyolefin-based Polymer material and a first starch-based polymer material (formed from a single starch of the first starch), and (ii) a second drop weight impact test value of a second item, the second item including the polymer based An olefin polymer material and a second starch-based polymer material (formed from a single starch of the second starch).

9. The article as claimed in claim 8 wherein the starch-based polymer material is formed of one or more plasticizers.

10. The article as claimed in claim 8 wherein the first starch comprises or is derived from potato starch, corn starch, or tapioca starch; and the second starch comprises or is derived from potato starch or corn starch , Or another kind of cassava starch or derived from it.

11. The article according to the scope of patent application, wherein the starch-based polymer material is present in an amount of about 20% to about 30% by weight of the article, and the polyolefin-based polymer material is used in the article It is present in an amount of about 65 wt% to about 75 wt%.

12. The article as claimed in claim 11, wherein in the starch mixture forming the starch-based polymer material, the first starch includes about 10% to 50% by weight, and the second starch includes about 50% to 90%.

13. The article of claim 12 in which the starch mixture forming the starch-based polymer material includes a third starch; in the starch mixture forming the starch-based polymer material, the third starch includes About 10 wt% to 35 wt%; and the drop weight test value of the item is higher than the third drop weight test value of the third item, the third item including the polyolefin-based polymer material and the third starch-based Polymer material (formed from a single starch of the third starch).

14. The article according to item 8 of the scope of patent application, wherein the article has a tensile elongation rupture value in a mechanical direction, which is higher than that formed by the polyolefin-based polymer material and no starch-based polymer material. Tensile elongation rupture value in the mechanical direction of additional items.

15. The item according to item 9 of the scope of patent application, further comprising a compatibilizer, present in an amount not exceeding 8% by weight of the item.

16. A process comprising: providing one or more petrochemical-based polymer materials; providing one or more substantially amorphous carbohydrate-based polymer materials (such as starch-based polymer materials) Has less than 20%, less than 10% crystals, specific glass transition temperature, Ficca softening temperature, or heat distortion temperature, specific Young's modulus, and / or other characteristics of NuPlastiQ or ESR; mixing the one or more petrochemicals A base polymer material and the one or more carbohydrate-based polymer materials to prepare a material mixture; heating the material mixture to a temperature of about 120 ° C to 180 ° C; and preparing a film from the material mixture, the film having Drop weight impact values of approximately 250 to 350 grams per mil thickness.

17. The process according to item 16 of the patent application, wherein preparing the film from the material mixture comprises: preparing an extruded object by extruding the material mixture; and injecting a gas into the extruded object.

18. The process of claim 16 in the scope of patent application, wherein: the one or more carbohydrate-based polymer materials are formed of the first starch and the second starch; and the film has a drop weight impact test value, which is high In: (i) the first drop weight impact test value of a first article comprising the one or more petrochemical-based polymer materials and a first carbohydrate-based polymer material (consisting of the first starch Formed from a single starch), and (ii) a second drop weight impact test value for a second article comprising the one or more petrochemical-based polymer materials and a second carbohydrate-based polymer material (from Formed of a single starch of the second starch).

19. The process of claim 16 in the patent application range, wherein: the material mixture further includes one or more compatibilizers; and the material mixture comprises: about 10% to 40% by weight of the one or more carbohydrate-based polymer materials 1, about 60 wt% to 89 wt% of one or more petrochemical-based polymer materials; and, from about 1 wt% but not more than 8 wt% of one or more compatibilizers.

20. The process of claim 16 in which the article includes a film having a thickness of about 0.02 mm to 0.05 mm. .

1. An article comprising: a polymer component comprising: a substantially amorphous carbohydrate-based polymer material (such as a starch-based polymer material) having less than 20%, less than 10% crystals, Specific glass transition temperature, Fica softening temperature, or thermal deformation temperature, specific Young's modulus, and / or other characteristics of NuPlastiQ or ESR; formed from at least the first starch; and another polymer material; wherein biomethane Based on the results of the biomethane potential test, the amount of decomposition of the polymer component was higher than the amount of the starch-based polymer material after 91 days. The test was performed at a temperature of about 52 ° C. and about 55 wt%. Water and about 45 wt% organic solids (inoculum) were performed.

2. The item in the scope of patent application, wherein substantially all starch-based polymer materials are biodegraded after 91 days, which is measured by the biomethane potential test at a temperature of about 52 ° C, Inoculation was performed with about 55 wt% water and about 45 wt% organic solids.

3. The article according to item 1 of the patent application scope, wherein the article further comprises a biodegradation assisting agent in an amount of about 0.5 wt% to 2.5 wt%.

4. If the item in the scope of patent application, the item is substantially free of biodegradation aids.

5. The article according to item 4 of the scope of patent application, wherein, based on the results of the biomethane potential test performed at a temperature of about 52 ° C, with about 55wt% water and about 45wt% organic solids, the article has a higher than About 5% to 60% of the biodegradable amount of the article after 91 days based on the amount of the starch-based polymer material.

6. The article according to the scope of patent application, wherein the starch-based polymer material is formed of a material containing one or more plasticizers.

7. The article according to the scope of patent application, wherein the starch-based polymer material is formed from a first starch and a second starch, wherein the first starch comprises or is derived from potato starch, corn starch, or One of tapioca starch; and the second starch comprises or is derived from another of potato starch, corn starch, or tapioca starch.

8. The article of claim 7 in which the first content of the first starch includes a starch mixture of about 10 wt% to 50 wt%, and the second content of the second starch includes about 50 wt% to 90 wt%. Starch mixture, which is used to form the starch-based polymer material.

9. The item according to item 1 of the scope of patent application, further comprising a compatibilizer, present at a maximum of 8% by weight of the item.

10. An article comprising: a polymer component comprising: one or more substantially amorphous carbohydrate-based polymer materials (e.g., starch-based polymer materials) having a content of less than 20% and less than 10% Crystals, specific glass transition temperatures, Fika softening temperatures, or heat distortion temperatures, specific Young's modulus and / or other characteristics of NuPlastiQ or ESR; formed from one or more carbohydrates; and one or more petrochemical substrates Molecular materials; wherein the amount of biodegradation of the polymer component after 91 days is greater than the amount of the one or more carbohydrate-based polymer materials, which is based on the results of the biomethane potential test, which is based on the temperature of about 40 ° C to 50 ° C, inoculation with about 50% to 60% by weight of water and about 40% to 50% by weight of organic solids

11. The article of claim 10, wherein the article includes about 20% to 40% by weight of the one or more carbohydrate-based polymer materials, and about 65% by weight to 85% by weight of one or more petrochemical substrates. Polymer Materials.

12. The article according to item 11 of the scope of patent application, wherein the amount of biodegradation of the polymer component after 91 days is about 30% to 50%, which is at a temperature of about 52 ° C, with about 55wt% water and about Based on the results of the biomethane potential test carried out with 45 wt% organic solid inoculation.

13. The article according to item 10 of the scope of patent application, wherein the amount of biodegradation of the polymer component after 62 days is about 25% to 35%, which is at a temperature of about 52 ° C, with about 55wt% water and about Based on the results of the biomethane potential test carried out with 45 wt% organic solid inoculation.

14. The article of claim 10, wherein the polymer material of the one or more petrochemical substrates includes the polymer material of the first petrochemical substrate and the polymer material of the second petrochemical substrate, and the second petroleum Chemically based polymer materials are compostable according to ASTM D-6400.

15. A process comprising: providing one or more petrochemical-based polymer materials; providing one or more substantially amorphous carbohydrate-based polymer materials (e.g., starch-based polymer materials) having a content of less than 20 %, Crystals below 10%, specific glass transition temperature, Fika softening temperature, or heat distortion temperature, specific Young's modulus, and / or other characteristics of NuPlastiQ or ESR; formed from one or more carbohydrates; blending this One or more petrochemical-based polymer materials and the one or more carbohydrate-based polymer materials to prepare a material mixture; heating the material mixture at a temperature ranging from about 120 ° C to 180 ° C; preparing a film from the material mixture, Wherein: the film contains a polymer component composed of the one or more petrochemical-based polymer materials and the one or more carbohydrate-based polymer materials; and the amount of the polymer components biodegraded after 91 days Is greater than the amount of the one or more carbohydrate-based polymer materials at a temperature of about 52 ° C and a temperature of about 55 ° C. Based on the results of biomethane potential tests conducted with wt% water and approximately 45wt% organic solids.

16. As claimed in claim 15, wherein: the one or more carbohydrate-based polymer materials are formed from the first starch and the second starch; and substantially all of the one or more carbohydrate-based polymer materials Biodegradation after 91 days, which is based on the results of a biomethane potential test performed at a temperature of about 52 ° C. and inoculation with about 55 wt% water and about 45 wt% organic solids.

17. The scope of claim 15, wherein the material mixture comprises: up to 8 wt% of one or more compatibilizers; about 10 wt% to 40 wt% of the one or more carbohydrate-based polymer materials; and about 60 wt % To 90% by weight of the one or more petrochemical-based polymer materials.

18. The scope of application for item 15 further comprises preparing a bag with the film.

19. The item 15 of the scope of patent application, wherein the bag has a thickness of about 0.02 mm to 0.05 mm, and the bag includes a cavity with a volume of about 5L to 20L.

20. The item 15 of the scope of patent application, wherein: the material mixture is heated in a plurality of chambers of an extruder; the first chamber of the extruder is set to a first temperature; and the first The two chambers set a second temperature different from the first temperature.

21. An article comprising: a polymer component comprising: a substantially amorphous carbohydrate-based polymer material (such as a starch-based polymer material) having less than 20%, less than 10% crystals, A specific glass transition temperature, a Feika softening temperature, or a heat distortion temperature, a specific Young's modulus, and / or other characteristics of NuPlastiQ or ESR, formed of at least a first starch; and a synthetic polymer material; Under burial conditions, simulated compost conditions, and simulated ocean conditions, the amount of biodegradation of the polymer component after about one year is greater than the amount of the starch-based polymer material.

22. The article according to the scope of patent application, wherein the synthetic polymer material is at least 25% biodegraded within about 3 years.

23. The article according to claim 21, wherein the starch-based polymer material is formed from a first starch and a second starch, wherein the first starch comprises or is derived from potato starch, corn starch, or One of tapioca starch; and the second starch comprises or is derived from another of potato starch, corn starch, or tapioca starch.

Comprises or is derived from potato starch, corn starch, or cassava starch; and the second starch comprises or is derived from potato starch, corn starch, or cassava starch

24. The article of claim 23, wherein the amount of the first starch includes about 10 to 50% by weight of the starch mixture, and the amount of the first starch includes about 50 to 90% by weight of the starch mixture. The starch mixture is Used to form the starch-based polymer material.

25. The article of claim 21 further includes a compatibilizer.

1. An article comprising: a substantially amorphous carbohydrate-based polymer material (such as a starch-based polymer material) having less than 20%, less than 10% crystals, specific glass transition temperature, phenanthrene Card softening temperature, or thermal deformation temperature, specific Young's modulus, and / or other characteristics of NuPlastiQ or ESR to provide biodegradability of other materials of the item; and a sustainable polymer material from sustainability Plant-derived; where, under simulated burial conditions, the amount of biodegradation of the item within 5 years is greater than the amount of the carbohydrate-based polymer material.

2. The article according to 1, wherein the carbohydrate-based polymer material includes a starch-based polymer material.

3. The article according to 1, wherein the sustainable polymer material comprises one or more of polyethylene, polypropylene, or polyethylene terephthalate formed from a sustainable plant source.

4. The article according to 3, wherein the sustainable polymer material is formed from one or more of sugarcane or corn.

5. The article according to 2, wherein the starch-based polymer material is formed of one or more starches, and the starch includes one or more of potato starch, corn starch, or cassava starch.

6. The article according to 5, wherein the starch-based polymer material is formed of two or more starches, the first starch including one or more of potato starch, corn starch, or cassava starch, and the second Starch includes one or more of potato starch, corn starch, or tapioca starch.

7. The article according to 6, wherein: relative to the total weight of the first starch and the second starch, the first starch includes about 50% to 90% by weight, and the second starch includes about 10% to 50% by weight And the amount of the carbohydrate-based polymer material includes about 10% to 40% by weight of the total weight of the carbohydrate-based polymer material and the sustainable polymer material, and the amount of the persistent polymer material Including about 60% to 90% by weight of the total weight of the carbohydrate-based polymer material and the sustainable polymer material.

8. The article according to 7, wherein the strength of the article is increased by at least about 5% compared to an article made of only the sustainable polymer material without the carbohydrate-based polymer material.

9. The article according to 1, wherein at least 90% of the polymer component of the article is derived from sustainable resources.

10. The article according to 1, wherein the article comprises a film.

11. The article according to 1, wherein the article comprises at least one of a bottle or a plate.

12. An article comprising: one or more substantially amorphous carbohydrate-based polymer materials (such as starch-based polymer materials) having less than 20%, less than 10% crystals, specific glass transition temperatures , Fica softening temperature, or thermal deformation temperature, specific Young's modulus, and / or other characteristics of NuPlastiQ or ESR to provide biodegradability of other materials of the item; and one or more types of persistent polymer materials From a sustainable plant source; where the strength of the item is increased by at least about 5% compared to an item made of only the sustainable polymer material without the carbohydrate-based polymer material.

13. The article of 12, wherein the article includes a film and has a drop weight impact strength of at least about 100 g / mil.

14. The article according to 12, wherein the sustainable polymer material comprises one or more of polyethylene, polypropylene, or polyethylene terephthalate formed from a sustainable plant source.

15. The article according to 14, wherein the sustainable polymer material is formed of one or more of sugarcane or corn.

16. The article according to 12, wherein the carbohydrate-based polymer material comprises a starch-based polymer material.

17. The article of claim 16, wherein the starch-based polymer material is formed from one or more starches, and the starch includes one or more of potato starch, corn starch, or cassava starch.

18. The article according to 17, wherein the starch-based polymer material is formed from two or more starches, the first starch including one or more of potato starch, corn starch, or cassava starch, and Di-starch includes one or more of potato starch, corn starch, or tapioca starch.

19. The article according to 18, wherein: relative to the total weight of the first starch and the second starch, the first starch includes about 50% to 90% by weight, and the second starch includes about 10% to 50% by weight And the amount of the carbohydrate-based polymer material includes about 10% to 40% by weight of the total weight of the carbohydrate-based polymer material and the sustainable polymer material, and the amount of the persistent polymer material Including about 60% to 90% by weight of the total weight of the carbohydrate-based polymer material and the sustainable polymer material.

20. The article according to 12, wherein the strength of the article is increased by at least about 10% compared to an article made of only the sustainable polymer material without the carbohydrate-based polymer material.

21. The article according to 12, wherein at least 90% of the polymer component of the article is derived from sustainable resources.

22. The article according to 12, wherein the article includes a film.

23. The article according to 12, wherein the article comprises at least one of a bottle or a plate.

1. A method for making a biodegradable plastic material that is not itself biodegradable, the method comprising: providing a plastic material that is not biodegradable per se; and providing one or more substantially amorphous carbohydrate-based Polymer materials (such as starch-based polymer materials) with crystals below 20%, below 10%, specific glass transition temperature, Ficca softening temperature, or heat distortion temperature, specific Young's modulus, and / or Other features of NuPlastiQ or ESR; selecting the one or more carbohydrate-based polymer materials to provide biodegradability to the plastic material that is not itself biodegradable; and mixing the carbohydrate-based polymer material and the Plastic material.

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

3. The method of claim 2 in the patent application scope, wherein the one or more starch-based polymer materials are formed of one or more starches and one or more plasticizers.

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

5. The method of claim 3, wherein the starch-based polymer material is formed from a mixture of at least two different starches.

6. The method of claim 5, wherein the two different starches forming the starch-based polymer material comprise (i) one of potato starch, corn starch, or cassava starch, and (ii) potato starch , Corn starch, or tapioca starch, wherein the choice of (ii) is different from (i).

7. The method of claim 6 in the scope of patent application, wherein the two different starches forming the starch-based polymer material are selected from the following table:

8. The method of claim 1, wherein the plastic material includes polyolefin.

9. The method of claim 1, wherein the plastic material includes polyethylene.

10. The method of claim 9 in which the plastic material includes a polyethylene film, and the film is formed of a mixture of the carbohydrate-based polymer material and polyethylene.

11. The method according to item 1 of the patent application scope, wherein the plastic material comprises one or more of polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, and polyvinyl chloride Ethylene, or polycarbonate.

12. The method according to item 1 of the patent application scope, wherein mixing 5 wt% of the carbohydrate-based polymer material with the plastic material is sufficient to make the plastic material biodegradable.

13. The method of claim 1, wherein the mixture of the carbohydrate-based polymer material and the plastic material comprises at least 5 wt% of the carbohydrate-based polymer material.

14. The method of claim 1, wherein the mixture 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 mixture 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 mixture 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 mixture of the carbohydrate-based polymer material and the plastic material further comprises a compatibilizer.

18. The method of claim 17 in which the compatibilizer includes not more than 10% by weight of the mixture.

19. A method for making a biodegradable plastic material that is not itself biodegradable, the method comprising: providing a plastic material that is not itself biodegradable; providing one or more substantially amorphous carbohydrate-based materials Polymer materials (e.g. starch-based polymer materials) with less than 20%, less than 10% crystals, specific glass transition temperature, Fika softening temperature, or heat distortion temperature, specific Young's modulus and / or NuPlastiQ Or other characteristics of ESR, selecting the one or more carbohydrate-based polymer materials to provide biodegradability to the plastic material that is not itself biodegradable; and mixing the carbohydrate-based polymer material and the plastic Materials, wherein the carbohydrate-based polymer material makes the plastic material biodegradable.

1. A method for increasing the strength of a blown plastic film, the method comprising: blowing a plastic film with a film blowing device, the film being a mixture of a first polymer material and a renewable starch-based polymer material Blown, wherein the reproducible starch-based polymer material is (i) substantially amorphous, has no more than 20% crystals, (ii) has a Young's modulus of at least 1.0 GPa, and / or (iii) ) Has a glass transition temperature of 70 ° C to 100 ° C, a softening temperature of Fika, or a thermal deformation temperature of 100 ° C; of which: (A) when the plastic film is blown, the blown film equipment is operated with a high inflation ratio of at least 2.0 Wherein, the high inflation ratio provides that the obtained plastic film has improved strength; and / or (B) the mold gap of the film blowing device is a narrow mold gap of not more than 500 microns, wherein the narrow mold gap makes the The blown plastic film has increased strength.

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

3. The method of claim 1, wherein the first polymer material includes polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, and polyvinyl chloride Or one or more of polycarbonate.

4. The method of claim 1, wherein the first polymer material includes at least one of polyethylene or polypropylene.

5. The method of claim 1, wherein the blown plastic film has a thickness from 0.1 mil to 10 mils.

6. The method of claim 1, wherein the inflation ratio is from 2.2 to 2.8.

7. The method of claim 1 in the patent application range, wherein the inflation ratio is about 2.5.

8. The method of claim 1, wherein the reproducible starch-based polymer material is formed from a mixture of at least two different starches.

9. A method for increasing the strength of a blown plastic film by using an inflation ratio, the method comprising: blowing a plastic film with a blown film device, the film being composed of a first polymer material and a second polymer material The second polymer material is blown from the mixture, and the second polymer material includes a renewable starch-based polymer material, wherein the renewable starch-based polymer material is (i) substantially amorphous, having no more than 20% crystals, (ii) having a Young's modulus of at least 1.0 GPa, and (iii) having a glass transition temperature, a Feika softening temperature, or a heat distortion temperature of 70 ° C to 100 ° C; an inflation ratio using the film blowing equipment, Choose a high inflation ratio of at least 2.0 to increase the strength of the blown plastic film.

10. The method according to item 9 of the patent application scope, wherein the strength is increased by at least 1% by selecting the high inflation ratio.

11. The method according to item 9 of the patent application scope, wherein the strength is increased by at least 10% by selecting the high inflation ratio.

12. The method of claim 9 in the patent application range, wherein the inflation ratio is from 2.2 to 2.8.

13. The method of claim 9 in the patent application range, wherein the inflation ratio is about 2.5.

14. The method of claim 9 in the scope of patent application, wherein the blown plastic film has a thickness from 0.1 mils to 10 mils.

15. A method for improving the strength of a blown plastic film by using an inflation ratio and a mold gap, the method comprising: blowing a plastic film with a blown film device, the film comprising a first polymer material and a second high Blown from a mixture of molecular materials, the second polymer material includes a renewable starch-based polymer material, where the renewable starch-based polymer material is (i) substantially amorphous and has no more than 20% Crystals, (ii) having a Young's modulus of at least 1.0 GPa, and (iii) having a glass transition temperature of 70 ° C to 100 ° C, a softening temperature, or a thermal deformation temperature of 100 ° C; a mold using the film blowing device A narrow die gap of not more than 500 microns is selected; and when blowing to the plastic film, the blow-up ratio is used to a value of at least 2.0, wherein the high blow-up ratio and / or the narrow die-gap are provided for the blow The resulting plastic film has increased strength.

16. The method of claim 15 in the patent application range, wherein the inflation ratio is at least 2.0.

17. The method of claim 15 in the patent application range, wherein the inflation ratio is from 2.2 to 2.8.

18. The method of claim 15 in which the inflation ratio is about 2.5.

19. The method of claim 15 in which the die gap is from 250 microns to 500 microns.

20. The method of claim 15 in which the blown plastic film has a thickness from 0.1 mil to 10 mil.

1. A sustainable plastic material with reduced odor, comprising: a polymer resin; an organic deodorant; and a carbohydrate-based polymer material, wherein in the absence of the organic deodorant, the carbohydrate-based The polymer material makes the sustainable plastic material have a unique charred odor of carbohydrates.

2. The material as claimed in claim 1, wherein the organic deodorant comprises a lyophilized powder.

3. The material as claimed in claim 1, wherein the organic deodorant comprises a vanilla extract.

4. The material as claimed in claim 1, wherein the organic deodorant includes vanilla extract.

5. The material according to item 1 of the patent application scope, wherein the organic deodorant has the following chemical structural formula:

6. The material according to item 1 of the patent application scope, wherein the organic deodorant is mainly composed of 4-hydroxy-3-methoxybenzaldehyde.

7. The material according to item 1 of the patent application scope, wherein the organic deodorant includes not more than 1% of the plastic material.

8. The material according to item 1 of the patent application scope, wherein the organic deodorant includes not more than 0.1% of the plastic material.

9. The material according to item 1 of the patent application scope, wherein the organic deodorant includes not more than 0.01% of the plastic material.

10. The material according to item 1 of the patent application scope, wherein the organic deodorant includes not more than 1000 ppm of the plastic material.

11. The material according to item 1 of the patent application scope, wherein the organic deodorant includes not more than 100 ppm of the plastic material.

12. The material as claimed in claim 1, wherein the organic deodorant includes not more than 50 ppm of the plastic material.

13. The material according to item 1 of the patent application scope, wherein the organic deodorant includes not more than 20 ppm of the plastic material.

14. The material according to item 1 of the patent application scope, wherein the proportion of the organic deodorant is from 1: 1000 to 1: 100,000 relative to the carbohydrate-based polymer material.

15. The material according to item 1 of the patent application scope, wherein the proportion of the organic deodorant is from 1: 25,000 to 1: 75,000 relative to the carbohydrate-based polymer material.

16. The material as claimed in claim 1, wherein the organic deodorant comprises a fruit extract.

17. The material according to item 16 of the patent application, wherein the organic deodorant is a lyophilized organic fruit extract selected from vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, An extract of passion fruit, raspberry, or a combination thereof.

18. The material according to item 16 of the patent application scope, wherein the carbohydrate-based polymer material. The proportion of the freeze-dried organic fruit extract in the plastic material is relative to the carbohydrate-based polymer material , No more than 1: 1000.

19. The material according to item 1 of the patent application scope, wherein the carbohydrate-based polymer material is a starch-based polymer material.

20. A sustainable thermoplastic carbohydrate-based polymer material with reduced odor, including: organic deodorant; and a carbohydrate-based polymer material; wherein the organic deodorant The weight ratio of the polymer material is not more than 1: 1000, and accordingly, the carbohydrate-based polymer material is at least 1,000 times higher than the organic deodorant.

21. The material of claim 20, further comprising a thermoplastic polymer resin mixed with the sustainable thermoplastic carbohydrate-based polymer material, wherein the sustainable thermoplastic carbohydrate-based polymer material The hot mixing with the thermoplastic polymer resin will show a burnt odor of carbohydrates, but the organic deodorant is not present.

22. The material according to item 21 of the patent application scope, wherein the thermoplastic polymer resin comprises polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride Or one or more of polycarbonate.

23. The material of claim 22, wherein the mixture of the carbohydrate-based polymer material and the thermoplastic polymer resin comprises 5% to 50% by weight of the carbohydrate-based polymer material.

1. A process comprising: providing one or more other polymer materials (for example, a petrochemical-based polymer material); providing one or more carbohydrate-based polymer materials; mixing the one or more other polymer materials and the One or more carbohydrate-based polymer materials to prepare a mixture; heating the mixture to a temperature of about 120 ° C to 180 ° C; and preparing a film from the mixture having a thickness of about 1 to 6 microns and about 40g to 100g drop weight impact test value.

1. A process comprising: providing one or more carbohydrate-based polymer materials; providing one or more other polymer materials (for example, including PBAT or bioPE); mixing the one or more other polymer materials and the one or more A carbohydrate-based polymer material to prepare a mixture; heating the mixture to a temperature of about 120 ° C to 180 ° C; and preparing a film with the mixture having a thickness of about 10 to 100 microns and a drop of about 200g to 600g Hammer impact test value.

These and other advantages of the present invention will be fully presented in the scope of the subsequent description and patent application, or may be understood through the implementation of the present invention described herein.

100, 100 ', 100 ", 100' '' ‧‧‧ manufacturing process

102, 104, 106, 106 ", 108, 110, 110 ', 110", 110' '' ‧‧‧ steps

200‧‧‧Manufacturing System

202‧‧‧The first feed tank

204‧‧‧Second Feeding Tank

206, 208, 210, 212, 214, 216‧‧‧ chambers

218‧‧‧Mould

218a‧‧‧outer member

218b‧‧‧Inside member

220‧‧‧ tube

222‧‧‧roller

224‧‧‧ film

226‧‧‧Module gap

228‧‧‧ Cold Line

FIG. 1 shows a flowchart of an exemplary method of forming an article according to the present invention.

FIG. 1A shows a flowchart of an exemplary method for increasing the strength of a blown plastic film by using an inflation ratio.

FIG. 1B shows a flowchart of an exemplary method of including a deodorant in a material mixture including the carbohydrate-based polymer material and other polymer materials.

Figure 1C shows the formation of a carbohydrate-based polymer material that includes a deodorant that offsets the unique odor of the carbohydrate-based polymer material, and then uses the carbohydrate-based polymer material containing a deodorant. Flow chart of an exemplary method of preparing an article.

Figure 2A shows the components of an exemplary manufacturing system for preparing an article of the present invention.

Figure 2B shows a close-up view of the film blowing equipment of Figure 2A, showing the mold, the die gap, the blown film bubble with a high inflation ratio, and the cold line of the film bubble.

Fig. 2C shows a partial cross-sectional close-up view of the mold of Fig. 2B, showing the narrow die gap.

Figure 3 shows the elastic modulus and elongation at break data of different plastics. Among them, various petrochemical-based plastics (labeled as standard plastics) are typical non-biodegradable and non-compostable. More "friendly" plastics.

Figure 4 shows X-ray diffraction patterns of exemplary NuPlastiQ or "ESR" carbohydrate-based polymer materials commercially available from BiologiQ and a mixture of natural corn starch and natural potato starch used to form NuPlastiQ or ESR.

Figure 5 shows the drop weight strength of different film thicknesses based on the percentage of the carbohydrate-based polymer material in the film.

Figure 6 shows that the film formed from a mixture of 25% carbohydrate-based polymer materials, about 5% compatibilizer, and about 70% PE, and different film thicknesses from 100% PE film (from about 0.1 mils to (Up to 2 mils) drop hammer strength comparison also shows comparison with existing produce bags, carry bags and potato bags.

Figure 7 shows the drop weight strength of different film thicknesses of various mixed films including NuPlastiQ or ESR. The control film is formed of original or recycled materials.

Figures 8A-8B show that the three samples prepared according to the present invention were tested for ASTM D-5511 to measure the percentage of biodegradation for 349 days.

Figure 9 shows a potato bag made of 25% NuPlastiQ or ESR, 70% PE, and 5% compatibilizer. Under simulated burial conditions, ASTM D-5526 test was performed to measure the percentage of biodegradation in 843 days .

Figures 10A-10B show that the various samples prepared according to the present invention and the control group were tested by ASTM D-5338 to measure the percentage of biodegradation for 370 days.

FIG. 11 shows that the samples prepared according to the present invention and the control group were tested by ASTM D-6691 (i.e., simulated ocean conditions) to measure the percentage of biodegradation for 205 days.

Figure 12A shows the drop weight strength of films made from a mixture of NuPlastiQ or ESR carbohydrate-based polymer materials and bio-polyethylene or "green" PE. For films of different thicknesses, the drop weight strength is displayed as a function of NuPlastiQ or ESR percentage.

Figure 12B shows data similar to Figure 12A, but for mixtures containing NuPlastiQ or ESR at different percentages, the drop weight strength is shown as a function of film thickness.

Figure 13 shows the drop weight strength of a film with an inflation ratio of 2.5 that has been formed from a mixture of compatibilizer and polyethylene that contains 25% NuPlastiQ or ESR material, and the drop of a film formed entirely of polyethylene. Compared with the hammer strength, the strength of the polyethylene film is not dependent on the inflation ratio.

I. Definition

When separate publications, patents, or patent applications are specifically and individually alleged to be incorporated by reference, all publications, patents, and patent applications contained herein, whether previously Or later, the full text of the same degree is incorporated into the case by way of reference.

The term "comprising" is synonymous with "including", "containing" or "characterized by", is inclusive or open-ended, and does not exclude additional, undocumented Element or method step.

The term "consisting essentially of" limits the scope of the patent application to specific materials or steps of the claimed invention and "those that do not substantially affect the basic and novel features".

The term "consisting of" as used herein excludes any element, step, or ingredient not specifically indicated in the scope of the patent application.

The terms "a (an, an)", "the" and similar references in the context used to describe the inventive feature (especially the context of the scope of patent application to be described later), unless otherwise stated or clearly contradicted by context, Interpreted to cover both singular and plural. Thus, for example, a "starch" may include one, two or more starches.

As used herein, a "membrane" means a thin and continuous article that contains one or more polymer materials that can be used to separate areas or volumes, carry an article, act as a barrier, and / or as a printable surface.

As used herein, "bag" means a container made of a relatively thin, flexible film that can be used to hold and / or transport goods.

As used herein, "bottle" means a container made of the plastic disclosed herein, which is generally thicker than a film, and which generally has a relatively narrow neck and abuts the opening. Such bottles can be used to carry a wide variety of products (e.g., beverages, personal hygiene products such as shampoos, conditioners, lotions, soaps, detergents, etc.).

Unless otherwise noted, all percentages, ratios, portions, and contents used herein are by weight.

The numbers, percentages, ratios, or other values contained herein may include the value, and also include other values that are approximately and similar to the value, which is obvious to those skilled in the art. Therefore, the interpretation of the stated value should be broad enough to cover the value at least close enough to perform the desired function or achieve the desired result, and / or the value surrounding the stated value. This value contains at least the expected variation in a typical process, and can include values within 25%, 15%, 10%, 5%, 1%, and so on. Furthermore, the terms "substantially", "similarly", "approximately" or "approximately" as used herein mean an amount or an amount that is close to the amount contained or that the desired function or the desired result is still performed . For example, the terms "substantially", "about" or "approximately" may mean an amount or amount within 25%, an amount within 15%, an amount within 10%, an amount within 5% Amount, or amount within 1%.

Some scopes are revealed here. Additional ranges may be defined by ranges between any of the values disclosed herein as examples of specific parameters. All ranges are included in the scope of the present invention. It should be noted that the numerical ranges described herein are intended to be used as a brief expression, and mean each numerical value falling within the range. Unless otherwise stated, each value is incorporated into this specification when it is described separately.

By the term "about", all numbers used in this specification and the scope of the patent application to indicate raw materials, ingredients, conditions, etc. can be understood as being modifiable in all examples. Although the numerical ranges and parameters of the broad scope of the present invention are listed as approximate values, the numerical values listed in the specific examples are as accurate as possible. However, any numerical value endogenously contains a certain degree of error, which will inevitably cause the standard deviation that will be produced in its separate test measurement.

The term 'freeof' or the like as used herein means that the composition contains 0% of the contained ingredients, that is, the ingredients are not intentionally added to the composition. However, it should be noted that such ingredients may be formed accidentally under appropriate conditions, and may be accidentally present in another ingredient included, such as accidental contaminants.

As used herein, the term 'substantially free of' or similar terms means that the composition preferably contains 0% of the contained ingredients, but it should be noted that very small concentrations may exist, Such as accidental formation, accidental contamination, or even intentional addition. Such ingredients, if any, can be present in amounts less than 1%, less than 0.5%, less than 0.25%, less than 0.1%, less than 0.05%, less than 0.01%, less than 0.005%, low At 0.001% or below 0.0001%.

II. Description

The present invention relates, in particular, to articles formed from a mixture comprising a combination of a regenerative or sustainable carbohydrate-based polymer material and another polymer material. In addition to increasing sustainability, the item may have biodegradability and / or increased strength. These items can be formed by mixing one or more carbohydrate-based polymer materials and one or more other polymer materials (for example, petrochemical substrates or "green" sustainable polymer types of plastic resins), heating The mixture forms an article from it, such as by extrusion, injection molding, blow molding, blow molding, and the like. In various embodiments, the carbohydrate-based polymer material may include a starch-based polymer material that is substantially amorphous, and / or has other information about glass transition temperature, heat distortion temperature, Fica softening temperature, Special features such as Young's modulus and low crystallinity are described here.

Articles as described herein can be made in any conceivable structure, including, but not limited to, bottles, boxes, other containers, cups, plates, utensils, plates, films, bags, and the like. Film blowing equipment can be used to simply prepare films for use as bags and film coverings (for example, to cover or cover products). Other processes that can be used to form articles can include, but are not limited to, injection molding, blow molding, thermoforming, and other plastic processes.

Examples of suitable carbohydrate-based or starch-based polymer materials for forming the article are commercially available from BiologiQ under the trade name NuPlastiQ or ESR ("Eco Stach Resin"). Specific examples include, but are not limited to, GS-270, GS-300, and GS-330. Specific characteristics of NuPlastiQ or ESR materials are detailed below. Other carbohydrate- or starch-based polymer materials with similar properties are also suitable, and NuPlastiQ or ESR purchased from BiologiQ is just a non-limiting example of a suitable carbohydrate- or starch-based polymer material.

In one embodiment, the "other" polymer material (different from the carbohydrate-based polymer material) contained in the mixture may be a sustainable polymer material, such as from a plant or other renewable source (e.g., Bacterial products). According to this, all or substantially all of the polymer components of the article (for example, 90% or more, 95% or more, 97% or more, 98% or more, or 99% or more) can be polymers obtained from plants or other renewable sources. Formed. This feature is particularly advantageous in terms of sustainability. As described herein, a small amount of compatibilizer may be present outside the polymer component to increase the compatibility between the "other" polymer resin material and the carbohydrate-based polymer material. In some embodiments, this compatibilizer may be a single composition that is not derived from or derived from a sustainable resource. In other embodiments, the compatibilizer can be sustainable, that is, 100% of the article can be assumed to be a source of sustainability.

In addition to the desired sustainability characteristics, the carbohydrate-based polymer material can be used to provide its blended materials (the "green" sustainable polymer materials, such as "green" PE (or bio-polyethylene), "Green" PP, or bio-PET) is biodegradable. In other words, even if the "green" sustainable polymer material is not itself biodegradable, when it is contained in the article with the carbohydrate-based polymer material, it will actually become biodegradable . This result is also highly advantageous.

In addition, many articles (e.g., especially films) formed from conventional plastic materials (e.g., polymer materials based on petrochemical substrates) do not have particularly good strength, so it is desirable to increase the strength at a predetermined thickness. . Since "green" plastic materials have similar physical characteristics to their corresponding traditional petrochemical-based plastics, "green" plastic materials also do not have particularly good strength; therefore, it is desirable to develop means to increase strength without increasing the thickness of the article. When mixed with a carbohydrate-based polymer material as described herein, an increase in strength can be achieved. For example, when a polyethylene film (for example, one of bio-polyethylene ("green" PE) or metallocene-based petrochemical substrate PE)) has a drop weight strength of about 150 g, the thickness of the film is about 150 g. With this increase, this point has advantages. This embodiment can provide such enhanced strength. For example, by mixing a carbohydrate-based polymer material as described herein, the strength can be increased by at least 5%. Typical results for some embodiments can result in a 20% or more increase in strength.

The article can be manufactured by mixing the carbohydrate-based polymer material and the persistent polymer material, heating the mixture, and shaping (such as injection molding) the mixture, extruding the mixture, and blow molding the Mixture, blowing the mixture, thermoforming the mixture, and the like. Those skilled in the art can easily understand various other plastic manufacturing processes applicable to the present invention.

Aiming at biodegradability, the method and the article can provide plastic materials that are not biodegradable by themselves, and have biodegradability. The special characteristics of crystallinity are described here. These embodiments show particular advantages, allowing many plastic products to be quickly biodegraded in a landfill or similar environment after being discarded, rather than persisting indefinitely as a polymer, stable state.

Furthermore, the applicant in this case observed that when the article is stored in a typical storage and use environment (such as in a home, office, warehouse, etc.), the biological decomposition of these articles does not occur quickly; usually only in When the item is placed in a simulated or actual landfill or compost or other typical waste environment, biodegradation begins to occur. For example, these conditions typically include (i) a temperature slightly higher than the general "use" or "storage" ambient temperature, (ii) exposure to elevated humidity, and (iii) exposure to a landfill or compost And similar microbiome phases in the waste environment. Increased temperature and humidity will not cause the article to biodegrade unless the necessary microorganisms are present. The combination of these conditions causes the articles formed from this mixture of materials to begin to biodegrade. Third-party testing as described here confirms that not only the carbohydrate-based polymer material undergoes biodegradation, but also the non-biodegradable plastic material itself undergoes actual biodegradation as well.

The mechanism by which the biodegradation is made possible by mixing the carbohydrate-based polymer material is not fully understood, but it is believed that when the two plastic materials are mixed together, it may be accompanied by the carbohydrate-based polymer material The specific characteristics of the micro-degradable hygroscopic barrier of the non-biodegradable plastic material make the microorganism that can biodegrade the carbohydrate-based polymer material not only decompose the carbohydrate-based polymer material, but also the same The adjacent plastic molecules are broken down. Third-party tests have confirmed carbon bond rupture and biodegradation. The test captures and measures the escaped gases carbon dioxide and methane. This result is surprising, unexpected, and particularly advantageous.

Another aspect of the present invention relates to a method for increasing the strength of a blown plastic film. In at least some embodiments, the method uses an inflation ratio and / or a die gap. This method may include blowing a plastic film with a blown film device, the film comprising a polymer material (e.g., polyethylene, etc.) and a renewable carbohydrate-based (e.g., starch-based) polymer material as described herein The mixture is blown, wherein the renewable carbohydrate-based polymer material is substantially amorphous, such as having no more than 20% crystals, and / or contains other specific characteristics. For example, the renewable carbohydrate-based polymer material may have a Young's modulus of at least 1.0 GPa, and / or it may have a glass transition temperature of 70 ° C to 100 ° C, a softening temperature of Fica, or thermal deformation temperature. When blowing the plastic film, the film blowing device is specific to a high inflation ratio of at least 2.0, and / or operates with a narrow mold gap (eg, no more than 500 microns). The applicant in this case found that compared to the strength provided by a lower, more typical inflation ratio (e.g., 1.5) or a wider die gap, the use of these characteristics when using the carbohydrate-based polymer material can make the Surprisingly, the plastic film has increased strength. With the same material, only one of the inflation ratio or the die gap may be adjusted, and the enhanced strength shown by the comparison may be obtained. It can also be compared to blown films made using only "other" polymer materials (e.g. polyethylene) without NuPlastiQ or ESR or other renewable carbohydrate-based polymer materials with specific characteristics as defined herein It was found to have the aforementioned increased strength. When the PE is blown alone, the blow-up ratio and the die gap do not significantly affect the strength.

The method may include the step of specifically selecting the high inflation ratio and / or narrow die gap to provide the blown film with enhanced strength; rather than any other purpose that may reasonably operate the inflation ratio (for example, it may be obtained Membrane diameter).

For example, the applicant of this case found that when blowing the film with "other" polymer materials such as polyethylene alone, operating the blow-up ratio did not significantly affect the strength. Furthermore, the applicant of this case found that when using the same inflation ratio of 1.5 traditionally applied to blown film, compared with 100% polyethylene or other polymer material films, the addition of renewable carbohydrate-based polymer materials (such as NuPlastiQ or ESR) to the mixture used to blow the film, the strength of the resulting mixed film is not significantly reduced. The applicant of this case further found that when blowing a mixed film containing a renewable carbohydrate-based polymer material such as NuPlastiQ or ESR, the inflation ratio was increased to, for example, at least 2.0, preferably 2.2 to 2.5 (for example, 2.5) , Can actually achieve an increase in intensity.

Although it is not fully understood why the strength can be increased at higher inflation ratios, such strength effects do not occur when the film is formed from "other" polymer materials alone. It is believed that when the inflation ratio increases, Some types of the molecular structure of the amorphous or other mixture are aligned, oriented, extended, or arranged sequentially, resulting in an increase in strength. In any case, although it may not be fully understood, the applicant in this case has observed and measured the increased intensity under the conditions and methods described herein.

Articles are prepared by mixing renewable carbohydrate-based polymers and other polymers (e.g., polyolefins such as polyethylene, or other plastics), heating the mixture, and feeding the molten mixture into a blown film device It is operated under a specific high inflation ratio and / or narrow die gap, and the operating conditions are selected for a specific purpose, even if the strength of the resulting film is increased. The blown film can be further processed into a wide variety of conceivable structures, including, but not limited to, plastic bags, film coverings, and the like.

Another aspect of the present invention relates to the unique odor of charred carbohydrates caused during typical heating and shaping or other forming of plastic materials in embodiments, which can be achieved by including a very small amount of a deodorant (preferred) Offset for organic deodorants). In one embodiment, the deodorant may be included in the carbohydrate-based polymer material (for example, as a part of the masterbatch of the carbohydrate-based polymer material).

In one embodiment, the carbohydrate-based polymer material is present in a much higher amount than the deodorant. For example, the amount of the carbohydrate-based polymer material can be at least 1,000 times, 10,000 times, or 50,000 times higher than the deodorant. Effective control (i.e., substantially complete removal) of popcorn, caramelized corn, or slightly starch even at very small concentrations (e.g., 1 part deodorant versus 50,000 parts carbohydrate-based polymer material) Burnt smell. Surprisingly, such a small amount of deodorant is sufficient to achieve this effect.

The masterbatch containing the odor control agent and the carbohydrate-based polymer material can be mixed with any desired polymer resin material and used to prepare a desired plastic article. For example, articles can be prepared by mixing the carbohydrate-based polymer material (including deodorant) and the polymer resin, heating the mixture, and shaping (e.g., injection molding) the mixture, and extruding the mixture , Blow molding the mixture, blowing the mixture (eg, forming a blown film), thermoforming the mixture, and the like. The above list is not all of the plastic manufacturing processes, and those skilled in the art can understand various other plastic manufacturing processes.

A small amount of deodorant may be contained in the carbohydrate-based polymer material, introduced into a polymer resin, mixed with the carbohydrate-based polymer material, or introduced into the mixture by other methods. In one embodiment, a masterbatch of a carbohydrate-based polymer material that already contains a deodorant therein may be provided. In other embodiments, the deodorant may be added separately from the carbohydrate-based polymer material, and / or separately from the polymer resin, and included in the mixture used to form the article. In addition to NuPlastiQ or ESR, which are available from BiologiQ, it is clear that other carbohydrate-based or starch-based polymer materials can also benefit from the addition of small amounts of deodorants, as described herein.

III. Exemplary Articles and Methods

FIG. 1 shows an exemplary "basic" process 100 of the present invention. Obviously, various details can be added to the present invention, such as including deodorant, providing "other" polymer materials including sustainable resin itself (for example, "green" PE, bio-PET, etc.), or blowing The film is specifically selected for inflation ratio and / or die gap. At 102, the process 100 may include providing one or more "other" polymer materials, such as, typically but not necessarily, non-biodegradable materials (e.g., including but not limited to polyethylene, polypropylene, other polyolefins, polymer Ethylene terephthalate, polyester, polystyrene, ABS, polyvinyl chloride, nylon, or polycarbonate). At 104, the process 100 may include providing one or more carbohydrate-based polymer materials that are substantially amorphous and have no more than 20% crystals (eg, more typically less than 10%). Other features may alternatively or additionally exist (e.g., Young's modulus above 1.0 GPa, Young's modulus, at least 70 ° C, at least 80 ° C, or glass transition temperature from 80 ° C to 100 ° C, Fica softening temperature, or Heat deformation temperature. The one or more carbohydrate-based polymer materials may include starch-based polymer materials. The carbohydrate-based polymer materials and the other polymer materials may be provided in a desired form, such as pellets, Powder, plastic particles (nurdles), slurries, and / or liquids. In certain embodiments, the material may be particles. The method further includes mixing the other polymer materials and the carbohydrate-based polymer material.

These mixtures can be formed into the desired article through any conceivable process. One example may be an extrusion process. For example, the other polymer materials and the carbohydrate-based polymer materials can be fed into an extruder (eg, into one or more feed tanks). Different materials can be fed into the same chamber, different chambers of the extruder, at approximately the same time (e.g., via the same feed tank), or at different times (e.g., via different feed tanks, prior to one material The material is introduced into the extruder along the screw). The numerous possibilities are obvious.

In some examples, the other polymer material may include polyolefin. For example, the plastic material or polymer material may include, but is not limited to, polyethylene, polypropylene, polyethylene terephthalate, other polyolefins, polyesters, polystyrene, ABS, polyvinyl chloride, Nylon, polycarbonate, etc. The plastic material may come from petrochemical sources, or from what is referred to as "green" or sustainable sources (eg, "green" PE, bio-PET, etc.).

In some examples, the "other" polymer material may itself be sustainable, such as a sustainable polyolefin. For example, the sustainable polymer material may include, but is not limited to, "green" polyethylene (bio-PE), "green" polypropylene (bio-PP), bio-PET, or other sustainable polymers. A plastic material formed from plants. In non-limiting examples, "green" PE may be derived from ethanol, which is derived from sugar cane, other sugar crops (e.g., sugar beet) or cereals (e.g., corn, wheat, etc.). "Green" PE (also sometimes referred to as "bio-PE") has a chemical structural formula similar to that of PE from petrochemical feedstocks, but its ethanol or ethylene monosystem for polymerization is derived from sustainable resources rather than Petrochemical feedstock. Similarly, "green" PP can be formed from propylene, which can be derived from propanol (or possibly isopropanol), which can be derived from sugar cane, other sugar crops, or cereals (eg, corn). "Green" Another example of sustainable polymer materials is bio-based PET. For example, polyethylene terephthalate (e.g., typically ethylene glycol and terephthalic acid) can be derived in a similar manner from plant sources such as sugar cane, other Sugar crops, or cereals. PET is the most common thermoplastic resin in the polyester family. Another polyester that can be derived in a similar manner from sustainable plant sources is polyadipate co-butyl terephthalate (bioPBAT). PBAT can be formed from copolyesters of adipic acid, 1,4-butanediol and dimethyl terephthalate. One or more of these starting materials are derived from sustainable plant sources. One possible "green" polymer resin material is poly Acid. PLA is typically prepared from monomers of lactic acid and / or lactide esters and will be apparent to those skilled in the art. One or more of the starting materials used in the preparation of PLA can be derived from sustainable plants Source: It is well known to those skilled in the art that other "green" polymers that may be available include PBS (polybutylene succinate) or PCL (polycaprolactone).

To those skilled in the art, it is familiar with the process of synthesizing these polymers. One or more of the ingredients used to make the polymers may be derived from a suitable regenerative plant or other regenerative biological source (e.g., a bacterial product). "Green" PE is available from Braskem, bio-PET is available for use in Coca Cola ^(TM) 's Plant Bottle ^(TM) and the like can be obtained from other plastic manufacturers. When PE, PP, PET and PBAT are examples of "green" bioplastics formed from materials derived from sustainable plant sources, it should be noted that as long as they are at least partially from sustainable materials (such as plant sources), Many other "green" plastics are also suitable. In addition, it should be noted that sugar cane, other sugar crops, corn, wheat, and other grains are merely illustrative non-limiting examples of plant materials derived from "green" polymer materials, and many other plants and materials are also applicable.

The carbohydrate-based polymer material may be formed from a plurality of materials, such as a mixture, and the plurality of materials may include one or more starches. For example, the one or more starches may be prepared 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 may be used, and the applicant has found that this results in an increase in strength addition. Plasticizers may also be present in the ingredients that form the mixture of the carbohydrate-based polymer material. Water can also be used to form the carbohydrate-based polymer material, but only a slight amount of water is present in the final carbohydrate-based polymer material.

It should be noted that in some embodiments, the polymer component as a whole (or substantially the polymer component as a whole) of the article may be derived from a plant material. When the "green" polymer material is typically a polymerizable monomer or other small molecule polymerizable monomer derived from ethanol (or other) formed from a desired plant material, the carbohydrate-based (or starch-based) The polymer material may be formed from starch (and glycerin or other plasticizers), rather than processing the starch or other plant material to form smaller polymerizable monomers. Therefore, the molecular weight of the starch used to prepare the starch-based polymer material is usually orders of magnitude higher than the molecular weight of the relative small-molecule monomer prepared to make the "green" sustainable polymer material. For example, the plant-derived monomers or other polymerizable ingredients used to make the "green" sustainable polymer material can typically be less than about 500 Daltons, less than 400 Daltons, and less than 300 channels, less than 200 channels, or less than 100 channels; and the molecular weight of the starch used to make the starch-based polymer material is often significantly higher, usually greater than 500 channels, usually Or higher (eg, greater than 500 channels, at least 1000 channels, at least 10,000 channels, at least 25,000 channels, at least 40,000 channels, etc.). In other words, the starch material (e.g., natural starch) used to form the starch-based material is generally more complex than the monomers or other polymerizable ingredients used to make the "green" sustainable polymer material molecule. For example, corn starch may have a molecular weight of about 693 Daltons. Potato starch can have a wide range of molecular weights, such as from about 20,000 to 400 million Daltons (for example, amylose can range from about 20,000 Daltons to 2 million Daltons, and amylopectin can range from (Approximately 65,000 to 400 million). Tapioca starch can have a molecular weight of about 40,000 Daltons to 340,000 Daltons. The glycerol used to form the starch-based polymer material can also be derived from sustainable resources. Glycerin has a molecular weight of 92 Daltons.

Returning to the feature of the carbohydrate-based polymer material, the one or more carbohydrate-based polymer materials are mostly formed of starch. For example, at least 65%, at least 70%, at least 75%, or at least 80% by weight of the carbohydrate-based polymer material may be composed of one or more starches. In one embodiment, 65% to 90% by weight of the final carbohydrate-based polymer material may be composed of one or more starches. In addition to the negligible water content, the balance of the final carbohydrate-based polymer material is composed of a plasticizer, such as glycerin. The above percentage is the percentage of starch relative to the starting material forming the carbohydrate-based polymer material; or, the amount of the carbohydrate-based polymer material derived or composed of the plasticizer (for example, At least 65% of the carbohydrate-based polymer material can be formed (formed) from the starch as a starting material). Although some water may be used in forming the carbohydrate-based polymer material, the carbohydrate-based polymer material is substantially balanced with glycerin or other plasticizers. Very small amounts of residual water (eg, less than 2%, typically no more than about 1%) may be present in the final carbohydrate-based polymer material.

For example, the materials forming the one or more carbohydrate-based polymer materials may include at least 12%, at least 15%, at least 18%, at least 20%, at least 22%, no more than 35%, no more than 32%, No more than 30%, no more than 28%, or no more than 25% by weight of plasticizer. The percentages may represent the amount of the final carbohydrate-based polymer material derived or formed from the plasticizer (e.g., at least 12% of the carbohydrate-based polymer material may be used as the starting material by the plasticizer Constitute (form)).

Exemplary plasticizers include, but are not limited to, glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, organic compounds without hydrogen bond formation by hydroxyl groups, anhydrides of sugar alcohols, animal proteins, plant proteins, fatty acids, Phthalates, dimethyl and diethyl butyrate and related esters, glycerol triacetate, glycerol mono and diacetate, glycerol mono, di and tripropionate, butyrate, hard Tearates, lactate, citrate, adipate, stearic acid esters, oleate, other acid esters, or combinations thereof. Glycerin is preferred.

The final carbohydrate-based polymer material may contain no more than 5%, no more than 4%, no more than 3%, no more than 2%, no more than 1.5%, no more than 1.4%, no more than 1.3%, and no more than 1.2%. , Not more than 1.1%, or not more than 1wt% of water. NuPlastiQ or ESR materials available from BiologiQ are examples of this final carbohydrate-based polymer material, but it should be noted that other commercially available materials (such as in the future) may also be suitable.

In some embodiments, a mixture of different starches can be used to form the carbohydrate-based polymer material. Surprisingly, it has been found that the use of a mixture of different starches (e.g. from different plants) can result in a synergistic increase in the strength of articles containing the carbohydrate-based polymer material. In the starch mixture, the starch may be present in the mixture in an amount of at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15%, at least 20%, at least 25 %, At least 30%, at least 35%, at least 40%, no more than 95%, no more than 90%, no more than 85%, no more than 80%, no more than 75%, no more than 70%, no more than 65%, no more More than 60%, not more than 55%, not more than 50%, or from 10% to 50% by weight relative to the total weight of the plurality of starches. Some non-limiting exemplary mixtures may include 90% of the first starch and 10% of the second starch; or 30% of the first starch and 70% of the second starch; or 50% of the first starch and 50% of the first starch Second starch. Mixtures of more than two starches (e.g., using three or four different starches) can also be used.

Examples of carbohydrate-based (e.g., starch-based) polymer materials suitable for forming films and other items are purchased from BiologiQ (located in Idaho, Idaho Foss) under the trade name NuPlastiQ or ESR ("Environmentally Friendly Starch Resin (Eco Starch Resin) "). Specific examples include, but are not limited to, GS-270, GS-300, and GS-330. NuPlastiQ or ESR is available in pellet form. Table 1 below shows the physical characteristics of GS-270 and GS-300.

The characteristics of GS-270 and GS-300 shown above can be used as examples for other NuPlastiQ or ESR products, but the values may change slightly. For example, NuPlastiQ or ESR products purchased from BiologiQ typically have a glass transition temperature, Fica softening temperature or heat distortion temperature of 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 100 ° C, or from about 80 ° C to 100 ° C. Those skilled in the art can understand that the glass transition temperature, Fica softening temperature, and heat distortion temperature can indicate crystallinity. The values of melting temperature range, density, Young's modulus, and water content can be the same as or similar to those shown in Table 1. Some characteristics may be similar to the values shown for GS-270 and GS-300 but vary slightly (eg, ± 25%, or ± 10%). NuPlastiQ or ESR has an amorphous structure (for example, it is more amorphous than general raw starch). For example, generally raw starch powders mainly have a crystalline structure (for example, higher than 50%), while NuPlastiQ or ESR has mainly an amorphous structure (for example, less than 10% crystalline). Any suitable standard can be used to measure the glass transition temperature, heat distortion temperature, fecca softening temperature, or any other physical characteristic. For example, the glass transition temperature can be measured according to ASTM D-3418, the heat distortion temperature can be measured according to ASTM D-648, and the Ficca softening temperature can be measured according to ASTM D-1525.

As stated, NuPlastiQ or ESR has a low water content. When NuPlastiQ or ESR absorbs moisture, it has plasticizing properties and is flexible. When removed from a humid environment, the material dries and hardens again (e.g., again has a moisture content of less than about 1%). During the process shown in Figure 1, moisture present in NuPlastiQ or ESR (eg, granular type) can be released in a vapor form. Therefore, a film or other article prepared by mixing a starch-based polymer material such as NuPlastiQ or ESR with a non-biodegradable plastic material may have a lower water content, because the non-biodegradable plastic material usually does not Aqueous or negligible water, while water in NuPlastiQ or ESR is usually released during the manufacture of the desired item.

The low water content of the carbohydrate-based polymer material is important because significant water content can cause incompatibility with non-biodegradable plastic materials, especially when the article must form a film. For example, when water evaporates, it can cause voids and other problems within the film or other objects. When the film is blown, the carbohydrate-based polymer material preferably contains no more than about 1% water.

Although TBS materials containing relatively low water content are known in some conventional methods, the low water content of NuPlastiQ or ESR materials is not achieved through esterification. Performing this esterification is too expensive and complicated. The same is true for etherification. Furthermore, the NuPlastiQ or ESR material applicable here is an exemplary carbohydrate-based polymer material, which does not usually actually contain any identifiable starch or identifiable glycerol. This is because NuPlastiQ or ESR or The starting materials of other carbohydrate-based polymer materials have undergone chemical reactions and / or have been altered. The X-ray diffraction pattern of an exemplary carbohydrate-based polymer material (as shown in Figure 4) is as follows, confirming the chemical change, showing that the final polymer material is substantially lacking an identifiable, natural type of starch . In other words, the carbohydrate-based polymer material should not be considered simply as a mixture containing starch and glycerol. It is believed that the low water content in the carbohydrate-based polymer material is caused at least in part by the chemical conversion of starch and plasticizer materials into thermoplastic polymers, and it does not retain water like natural starch or conventional thermoplastic starch .

Returning to Figure 1, processing at relatively high temperatures will cause some glycerol to volatilize and release (for example, smoke can be seen). If necessary (for example, the stored particles may absorb additional moisture), the particles can be dried by simply introducing a drying heater such as 60 ° C for 1-4 hours, which is sufficient to exclude any absorbed moisture. Prior to processing, and especially to form a film, the particles should be dried to a moisture content below about 1%. NuPlastiQ or ESR particles can be easily stored in a sealed container with a desiccant, placed in a dry place away from heat sources to minimize water absorption and prevent unwanted decomposition.

In addition to NuPlastiQ or ESR being thermoplastic, NuPlastiQ or ESR can also be thixotropic, meaning that the material is solid at ambient temperature, but flows in a liquid state under heat, pressure, and / or frictional motion. Beneficially, particles of NuPlastiQ or ESR can be used in standard plastic manufacturing processes like particles that are petrochemical-based (any typical non-biodegradable plastic resin particles). NuPlastiQ or ESR materials and products made from them may have air-blocking characteristics. Products made of, for example, NuPlastiQ or ESR particles (such as membranes) have oxygen barrier properties (for example, see the examples previously requested by the applicant, which have been incorporated into the case by reference). NuPlastiQ or ESR materials are non-toxic and edible, and are made from all edible materials. NuPlastiQ or ESR and the products made from it may be water resistant, but water soluble. For example, under humid heating conditions, NuPlastiQ or ESR can resist swelling until its particles (such as size 3-4mm) will not completely dissolve in boiling water for 5 minutes, but the particles will dissolve in the mouth in about 10 minutes . NuPlastiQ or ESR can be stable, and it has no significant retrogradation, even in relatively high humidity conditions; this feature is different from many other thermoplastic starch materials. Of course, products made with NuPlastiQ or ESR can also have these characteristics. If NuPlastiQ or ESR is stored under humid conditions, excess absorbed water can simply be evaporated, and as long as its water content does not exceed about 1%, it can be used to form films or other items.

NuPlastiQ or ESR materials generally do not biodegrade under normal storage conditions, even under relatively humid conditions, because there are no other typical conditions in landfills, composts, or similar waste environments that contain specific essential microorganisms . Of course, when these conditions exist, not only NuPlastiQ or ESR biodegradable, but also other non-biodegradable plastic materials mixed with it are surprisingly biodegradable. This surprising result is demonstrated by the examples contained herein.

NuPlastiQ or ESR is cost competitive and can compete with the manufacturing costs of 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 copolymer (ABS), polyvinyl chloride, nylon ,and others. When the above non-biodegradable polymers are made biodegradable by mixing NuPlastiQ or ESR, it should be noted that NuPlastiQ or ESR can also be mixed with polymers that are biodegradable and / or compostable. Molecules such as polylactic acid (PLA), polyadipate cobutylene terephthalate (PBAT), polybutylene succinate (PBS), polycaprolactone (PCL), polyhydroxyalkanoate ( PHA), other known as thermoplastic starch, and various other polymers. PBS, PCL and PHA are polyesters. EcoFLEX ^TM is another example of a plastic material that can be mixed with NuPlastiQ or ESR carbohydrate-based polymer materials. For example, the method is not limited to mixing the carbohydrate-based polymer material (for example, NuPlastiQ or ESR) with only non-biodegradable plastic materials. It should be noted that, if desired, bio-based Decomposed plastic (other than NuPlastiQ or ESR) can also be incorporated into the mixture.

To further explain, PLA is compostable, which means that it can be decomposed under heating conditions (ie, composting conditions), but it is not technically "biodegradable". Some of the materials listed above are both biodegradable and compostable, such as PBS, PCL, and PHA. EcoFLEX ^TM is certified as compostable. The FTC Green guidelines stipulate that plastic cannot be declared "decomposable" unless it can be decomposed within a "reasonable short time" (recently defined within 5 years) after "usual disposal".

In some embodiments, NuPlastiQ or ESR may be provided in a masterbatch formulation, which may include the carbohydrate-based polymer material as described above, and one or more compatibilizers. The master batch may also include one or more non-biodegradable plastic materials. The masterbatch formula particles can be mixed with particles of non-biodegradable plastic materials at the time of processing. The different particles can be mixed in any desired ratio, depending on the desired ratio of NuPlastiQ or ESR and / or compatibilizer and / or conventional non-biodegradable plastic material in the final article.

NuPlastiQ or ESR contains a very low water content. For example, although raw starch (e.g., used to form an ESR) can typically contain about 13% by weight water, the final NuPlastiQ or ESR granule line available from BiologiQ contains less than about 1% water. NuPlastiQ or ESR materials are biodegradable, and, as described here, not only starch-based NuPlastiQ or ESR materials are biodegradable, when combined with other polymers such as non-biodegradable PE, PP, PET, polyester, When polystyrene, ABS, polyvinyl chloride, nylon, and other non-biodegradable plastic materials are mixed, the mixed materials become substantially completely biodegradable. This result is really surprising and very advantageous. The examples provided here confirm this surprising result. Typical thermoplastic starch materials, when mixed with other plastic materials, do not claim or have these characteristics.

NuPlastiQ or ESR material may have some elasticity, but its elasticity will be less than other polymers (for example, especially "green" sustainable polymers that simulate the corresponding petrochemical base polymers). Films and other articles can be formed from a mixture of NuPlastiQ or ESR and any other desired polymer. Compared with those formed only by other polymers, the former can provide elastic results with increased strength under specified article thickness. The membranes described and commonly used in the examples herein are generally quite strong in strength; however, it is clear that items other than membranes (for example, bottles, plates, boxes, cups, plates, utensils, or other types) also May have increased strength. Table 2 below shows a comparison of the values of elongation at break and modulus of elasticity of different standard plastic ("SP") materials, different "environmentally friendly" plastic materials, and NuPlastiQ or ESR. In "environmentally friendly", the material may have one or more environmentally desirable characteristics, such as being at least partially derived from sustainable materials, compostable, and / or biodegradable. In Table 2, NuPlastiQ or ESR has an elongation strength of 40 MPa.

Figure 3 shows data similar to Table 2 in the form of a graph. Of course, some of the products listed in this table and shown in Figure 3 are listed as standard plastics, which have corresponding "green" products derived from sustainable resources, such as, but not limited to, bio-PET, "green" PP , "Green" PE, and biomass PBAT. PLA is compostable, meaning that it can be decomposed under warming conditions (ie, composting conditions), but is not technically "biodegradable". The other exemplary materials listed above such as EcoFlex, PBS, PCL, and PHA are both biodegradable and compostable. The FTC Green Guidelines stipulate that plastic cannot be declared "decomposable" unless it can be decomposed within a "reasonable short time" (recently defined within 5 years) after "usual disposal".

NuPlastiQ or ESR materials described as suitable for this carbohydrate-based (eg, starch-based) polymer material are substantially amorphous. For example, raw starch powders (such as those used to prepare NuPlastiQ or ESR and other various thermoplastic starch materials) have about 50% crystalline structure. In terms of crystalline and amorphous features, NuPlastiQ or ESR materials purchased from BiologiQ can be distinguished from many other commercially available thermoplastic starch (TPS) materials. For example, pages 62-63 of the PhD dissertation "Thermoplastic Starch Composites and Mixtures" by the author Kris Frost (September 2010) stated "Special interest in TPS during processing Complete gelatinization, and any subsequent tendency to set back to form V-type amylose crystals. " Forster further states that "gelatinization involves the loss of granular and crystalline structures, which can be achieved by heating with water, and often contains other plasticizers or modified polymers. The retrocoagulation system is spirally coiled by amylose. Caused by re-coiling. During the gelatinization period, starch molecules were destroyed and slowly re-coiled into their natural spiral arrangement or a new single spiral configuration (called V-shape), causing the TPS film to rapidly embrittle and lose optics. Sharpness. " Therefore, after the conventional TPS is made from raw starch in a gelatinization process, TPS tends to reshape into a crystalline structure. In contrast, NuPlastiQ or ESR materials purchased from BiologiQ do not return to the main crystalline structure. In addition, it maintains a stable and relatively high optical clarity, which is advantageous for forming relatively optically clear films (for example, especially a film containing NuPlastiQ or ESR sandwiched between polyethylene or other polyolefin layers).

In contrast to typical TPS materials, a suitable example of a starch-based polymer material that can be used to form articles as described herein is a NuPlastiQ or ESR material that has an amorphous microstructure and physical characteristics as shown in Table 1. Differences in molecular structure between conventional TPS and NuPlastiQ or ESR materials have been demonstrated, as shown by X-ray scattering in Figure 4, comparing NuPlastiQ or ESR materials (sample 1) purchased from BiologiQ with natural raw corn starch and natural As a result of the scattering pattern of a raw potato starch mixture (from which NuPlastiQ or ESR can be formed), NuPlastiQ or ESR materials have lower crystallinity than conventional thermoplastic starch-based materials. As can be seen in Figure 4, the scattering pattern of NuPlastiQ or ESR shows lower crystallinity (eg, less than about 10% crystals) compared to a natural starch mixture (about 50% crystals). The differences in the scattering patterns confirmed the substantial chemical change in the material due to the processing of the natural starch into NuPlastiQ or ESR. For example, natural starch has a significant scattering peak between 20-25 °, but NuPlastiQ or ESR does not have this peak. Natural starch further showed strong peaks (intensities of 0.5 to 0.6) at about 45 °, but the peaks of NuPlastiQ or ESR weakened significantly (only about 0.25 to 0.3). As shown, the scattering intensity of natural starch is higher than NuPlastiQ or ESR across almost the entire spectrum, except at about 18 ° to about 22 °. Compared to NuPlastiQ or ESR, the higher scattering intensity seen across a broad spectrum suggests the high crystallinity of natural starch. As shown, there are many other differences.

For example, the carbohydrate-based (e.g., starch-based) polymer materials used to make films according to the present invention may have less than about 40%, less than about 35%, less than about 30%, and 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% of crystals. Any suitable testing mechanism may be used to determine the crystal, including, but not limited to, FTIR analysis, X-ray scattering, symmetrical reflection and transmission techniques. To those skilled in the art, various suitable test methods are obvious.

In addition to comparing the microstructure differences between the final NuPlastiQ or ESR and the starting material, films, bottles, plates, disposable vessels, dishes, cups, or other materials made from a mixture of carbohydrate-based polymer materials Articles are different from other similar articles formed by conventional TPS and starch powder, or non-biodegradable plastic materials alone. For example, an item formed by mixing the carbohydrate-based polymer material (such as NuPlastiQ or ESR as described here) and a non-biodegradable plastic material does not have an "island" feature, which is commonly found in blending habits. Known TPS materials and polymer materials such as polyethylene. For the properties of the different films, see the physical properties of the films compared in Table 11 of Example 5 of US Patent Application No. 15 / 481,806, which has been incorporated by reference. In particular, this table compares films made by mixing carbohydrate-based polymer materials and non-biodegradable polyethylene covered here with films made by mixing conventional TPS and PE (Cardia BL-F) Physical properties. Except for the membrane physical properties shown in Table 11 of Example 5 of the applicant's U.S. Patent Application No. 15 / 481,806, the membranes prepared based on the conventional TPS material (such as Cardia BL-F) and PE are non-biological Decomposable and non-compostable.

As described here, the carbohydrate-based polymer material and the non-biodegradable plastic material described herein are mixed, so that not only the carbohydrate-based material is biodegradable, but also the non-biodegradable plastic The material actually becomes biodegradable (ie, the non-biodegradable plastic material is non-biodegradable when it exists alone). This result does not occur in a mixture of typical TPS materials. The difference in biodegradability clearly illustrates the significant differences in structure and / or chemistry of the resulting membrane and other items, because the overall structure of the composite (i.e. the membrane or other structure) can now be biodegraded, as detailed in the following formulas Examples.

Without being bound by any particular theory, it is believed that the carbohydrate-based polymer resin can reduce the crystals of the mixed product, and in some way interrupt the crystals and / or moisture absorption barriers of the polyethylene or other non-biodegradable plastic material Characteristics, while allowing water and bacteria to decompose the arrangement and connection of other non-biodegradable plastic molecules in the mixture containing the carbohydrate-based polymer resin material. In other words, when mixed with a carbohydrate-based polymer material as covered herein, chemical or mechanical forces present in a bacterial and microbial-rich environment are more likely to disrupt the polyethylene or other non-biodegradable plastic material Long polymer chains. Then, the microorganisms that naturally exist in the waste environment (such as a landfill) can consume the remaining small molecules, so they can be converted back to natural components (such as CO ₂ , CH ₄ , and H ₂ O).

For example, real biodegradable plastics are broken down into natural elements or compounds, such as carbon dioxide, methane, water, inorganic compounds, or biomass absorbed by microorganisms (for example, the enzyme action of microorganisms on plastic molecules) . It is possible to make the biodegradation of plastics by chemically or mechanically breaking one of the polymer chains initially, but it is still necessary to decompose the molecules by microbial absorption to fully reach the goal.

Plastics made from petrochemical raw materials or derived from plants have their lives started with monomers (such as a single small molecule that can chemically react with other small molecules). When the monomers come together, they become polymers ("many parts"), called plastics. Before the combination, many monomers can be easily biodegraded, but after being linked together by polymerization, the molecule becomes so large and combined in such an arrangement and bond that the microbial absorption by the microorganism cannot be effected in any way. Achieved within a reasonable time frame.

Polymers can be formed from both crystalline structures (regular stacks) and amorphous structures (random arrangements). Many polymers contain highly crystalline and some amorphous regions are randomly arranged and entangled in the overall structure of the polymer.

NuPlastiQ or ESR materials purchased from BiologiQ are formed from highly crystalline starting starch materials, but the final NuPlastiQ or ESR plastic resin materials have low crystallinity (substantially amorphous). The starch-based polymer material is used as a starting material for the preparation of articles as described herein. Therefore, NuPlastiQ or ESR is a plastic made from starch. Due to its nature, starch-based origin, and carefully controlled bond types, the molecules (size and bond) of the plastic made by NuPlastiQ or ESR are highly sensitive to biodegradation, which is induced by the introduction of wet It is produced by the action of enzymes caused by gas (water) and bacteria or other microorganisms, as confirmed by the experimental test results contained herein.

The rigid forms of polyolefins such as polyethylene and polypropylene are highly crystalline and produce long chain heights by converting monomer molecules (whether petroleum-derived or ethanol-derived or other small building block molecules derived from plants) molecule. The resulting bonds are strong and difficult to break when connecting monomers to form long polymer chains. Films and other articles formed from this polymer material are non-biodegradable. Even if the intended article is formed of a mixture of conventional non-biodegradable plastic materials and conventional TPS, the article does not normally and suddenly acquire biodegradable characteristics (except that the starch portion of the mixture may sometimes be Biodegradation).

The applicant of this case has established a method for making a non-biodegradable plastic material biodegradable by mixing the plastic material with a low-crystalline carbohydrate-based polymer material (such as NuPlastiQ or ESR). Typically, the non-biodegradable plastic material has a high crystallinity (for example, especially in the case of PE or PP).

In addition to biodegradability, the resulting mixture may additionally or alternatively have a higher modulus of elasticity (hardness, or strength) than polyethylene or other non-biodegradable plastic materials; and may be used in the preparation Plastic film or other articles are stronger than the same articles made of pure polyethylene or other pure non-biodegradable plastic materials. This enhanced strength feature is described in U.S. Patent Application No. 15 / 481,806, which has been incorporated into the present application by reference.

Returning to FIG. 1, at 106, the process 100 includes mixing one or more other polymer materials and one or more carbohydrate-based polymer materials to prepare a material mixture. In some examples, mixing of the one or more other polymer materials and the one or more carbohydrate-based materials may be performed using one or more mixing devices. In a specific implementation, a mechanical mixing device may be used to mix the one or more other polymer materials and the one or more carbohydrate-based polymer materials. In an implementation, at least part of the components of the material mixture may be combined with a device such as an extruder, an injection molding machine, and the like. In other implementations, at least part of the ingredients of the mixture of materials can be combined before feeding into the device.

Depending on the desired characteristics, there may be a wide variety of the one or more carbohydrate-based polymer materials in the material mixture. In one embodiment, this is sufficient to make other non-biodegradable "other" polymer materials contained in the mixture biodegradable, increase strength to a desired level, provide "persistent" ingredients to a predetermined level, Or other purpose. For example, the content of the carbohydrate-based polymer material may be 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% of the material mixture. %, At least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, no more than 99%, no more than 95%, no more than 90%, no more than 80%, no more than 70% , No more than 60%, no more than 50%, 2% to 98%, 20% to 40%, 10% to 40%, 20% to 30%, 50% to 80%, or 40% to 60wt%. If desired, more than one carbohydrate-based polymer material and / or more than one other plastic material may be included.

The amount of other polymer materials present in the material mixture is 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% of the material mixture , At least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, no more than 99%, no more than 95%, no more than 90%, no more than 85%, no more More than 80%, no more than 75%, no more than 70%, no more than 65%, or no more than 60%, 2% to 98%, 50% to 90%, 65% to 75%, 20% to 50%, or40 % To 60wt%.

A compatibilizer may be present in the material mixture. The compatibilizer can be mixed with the other polymer materials, the carbohydrate-based polymer materials, mixed with the two at the same time, or provided separately. Generally, the compatibilizer is provided with at least one of the polymer materials, for example, included in a masterbatch formulation. The compatibilizer can be modified polyolefin or other modified plastics, such as maleic anhydride-grafted polypropylene, maleic anhydride-grafted polyethylene, maleic anhydride-grafted polymer Butene, or a combination thereof. The compatibilizer may also include acrylate-based copolymers. For example, the compatibilizer may include an ethylene methacrylate copolymer, an ethylene butyl acrylate copolymer, or an ethylene ethyl acrylate copolymer. Additionally, the compatibilizer may include a poly (vinyl acetate) -based compatibilizer. In one embodiment, the compatibilizer may be a grafting type of other polymer materials (for example, maleic anhydride-grafted polyethylene, and here other polymer materials are polyethylene), or a copolymer (for example, , Block copolymer), where one of the blocks is the same monomer as other polymer materials (for example, styrene copolymer, where other polymer materials are polystyrene or ABS).

The material mixture may contain at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, no more than 50%, no more than 45%, no more than 40%, no more than 35%, no more More than 30%, no more than 25%, no more than 20%, no more than 15%, no more than 10%, no more than 9%, no more than 8%, no more than 7%, no more than 6%, 0.5wt% to 12% , 2% to 7%, or 4% to 6wt% of a compatibilizer.

Although not necessary, and it is best to avoid such contents in at least some embodiments, any different UV and OXO degradable additives such as PDQ-M, PDQ-H, BDA, and OxoTerra ^TM from Willow Ridge Plastics, OX1014 from LifeLine, or organic additives such as Restore® from Enso, EcoPure® from Bio-Tec Environmental, ECM Masterbatch Pellets 1M from ECM Biofilms, or Biodegradable 201 And / or Biodegradable 302 BioSphere®. Other additives may be included, for example, to increase strength (e.g., Biomax® Strong from Dupont) or others.

The material mixture may include one or more additives in an amount of at least 0.5%, at least 1%, at least 1.5%, at least 2%, at least 2.5%, at least 3%, at least 4%, no more than 10%, no more than More than 9%, no more than 8%, no more than 7%, no more than 6%, no more than 5%, 0.2% to 12%, 1% to 10%, 0.5% to 4%., Or 2wt% to 6wt%.

Although it is mainly described that a mixture of thermoplastic plastic materials can be melted together to form a desired mixture, in some embodiments, the carbohydrate-based polymer material and other non-thermoplastic polymer materials (for example, they are thermosetting, such as silicon oxide) Resin) is possible. For example, the resin component of the non-thermoplastic "other" polymer material precursor can be mixed with the carbohydrate-based polymer material, wherein polymerization or other thermoplastic "other" polymer material formation effect can be applied to the carbohydrate-based polymer material It occurs in the presence of polymer materials, resulting in a final article that is a mixture of the carbohydrate-based polymer material and thermosetting or other non-thermoplastic plastic materials. The carbohydrate-based high molecular material can, as described herein, achieve the same benefits (e.g., improved sustainability, biodegradability, increased strength, etc.) as the non-thermoplastic material due to co-mixing.

Referring to Figure 1, at 108, the process 100 may include heating the material mixture, especially when the material is thermoplastic. In one embodiment, the material mixture can be heated to a temperature of at least 100 ° C, at least 110 ° C, at least 115 ° C, at least 120 ° C, at least 125 ° C, at least 130 ° C, at least 135 ° C, at least 140 ° C, and not more than 200 ° C. No more than 190 ° C, no more than 180 ° C, no more than 175 ° C, no more than 170 ° C, no more than 165 ° C, no more than 160 ° C, no more than 155 ° C, no more than 150 ° C, 95 ° C to 205 ° C, 120 ° C to 180 ° C, or 125 ° C to 165 ° C.

The material mixture containing other polymer materials and the carbohydrate-based polymer material may be heated in one or more chambers of an extruder. In some examples, one or more chambers of the extruder can be heated to different temperatures. The speed of one or more screws of the extruder can be any desired rate.

At 110, an article is prepared from the material mixture. In some examples, the article may include a film. In other examples, the article may be formed from a film. In other embodiments, the article may be shaped based on a design, such as a mold (eg, an injection mold). Any desired plastic-formed article may be formed from the mixture, including, but not limited to, films, bags, bottles, covers, lids, plates, boxes, trays, cups, utensils, and the like. When the article is a film, the film can be formed using a mold, which is formed by ejecting a gas into a heated material mixture (ie, blowing the film). The film may be sealed and / or otherwise modified to form a bag or other item.

When the article is a film, the film may be composed of a single layer or multiple layers. The thickness of the film or any individual layer can be at least 0.001mm, at least 0.002mm, at least 0.004mm, at least 0.01mm, at least 0.02mm, at least 0.03mm, at least 0.05mm, at least 0.07mm, at least 0.10mm, not more than 2mm, No more than 1mm, no more than 0.5mm, no more than 0.1mm, 0.05mm to about 0.5mm, or 0.02mm to 0.05mm. Some specific examples may include films below 0.005 mm, such as 0.002 mm to 0.004 mm, or 0.0025 mm (0.1 mil) to 0.25 mm (10 mil). For films and plate items, the thickness values may partially overlap; it should be noted that, of course, plate materials with a larger thickness than the film thickness values can be provided, and can be prepared by any desired plastic manufacturing process.

The applicant in this case has demonstrated the ability to blow a 0.0025 mm (0.1 mil) ultra-thin film using a mixture as described herein, which has significant strength (for example, a drop weight test of 0.1 mil film of at least 40 g , Such as 40g to 110g, or 40g to 100g drop weight strength for this ultra-thin film). It is believed that the ability to blow such ultra-thin films is unique to the applicant of this case, and uses mixtures and other parameters (such as blow-up ratio, die gap, etc.) as described herein.

Films or other items can have strength characteristics that have been tested, such as the drop weight strength test (ASTM D-1709), the elongation at break test (ASTM D-882), and the elongation at break test (ASTM D-882) , Secant module test (ASTM D-882), and / or Emmendorf shear test (ASTM D-1922). Film drop weight test value can be at least 150g, at least 175g, at least 200g, at least 225g, at least 250g, at least 275g, at least 300g, not more than 400g, not more than 375g, not more than 350g, or not more than 325g, 140g to 425g , 200g to 400g, 250g to 350g, 265g to 330g. In one embodiment, the value is for a film regardless of thickness. In another implementation, the value is for a 1 mil film formed from the material mixture.

The article may have a fracture elongation strength value in the mechanical direction of at least 3.5kpsi, at least 3.7kpsi, at least 3.9kpsi, at least 4.1kpsi, at least 4.3kpsi, or at least 4.5kpsi, no more than 5.5kpsi, no more than 5.3kpsi, no More than 5.1kpsi, no more than 4.9kpsi, or no more than 4.7kpsi, 3.5kpsi to 5.5kpsi, or 4.1kpsi to 4.9kpsi.

The article may have a fracture elongation strength value in the transverse axis direction of at least 3.2kpsi, at least 3.4kpsi, at least 3.6kpsi, at least 3.8kpsi, at least 4.0kpsi, at least 4.2kpsi, not more than 5.7kpsi, not more than 5.5kpsi, not more than More than 5.3kpsi, no more than 5.1kpsi, no more than 4.9kpsi, no more than 4.7kpsi, no more than 4.5kpsi, 3.2kpsi to 5.7kpsi, or 3.6kpsi to 5.0kpsi.

The article may have a tensile elongation at break value in the mechanical direction of at least 550%, at least 560%, at least 570%, at least 580%, at least 590%, at least 600%, at least 610%, at least 620%, not exceeding 725%, no more than 710%, no more than 700%, no more than 680%, no more than 665%, no more than 655%, no more than 635%, 550% to 750%, or 600% to 660%.

The article may have a tensile elongation at break value in the transverse axis direction of at least 575%, at least 590%, at least 600%, at least 615%, at least 630%, or at least 645%, not more than 770%, and not more than 755 %, Not more than 740%, not more than 725%, not more than 710%, not more than 695%, not more than 685%, 575% to 775%, or 625% to 700%.

When testable, the item may have an Emmendorf shear test value in the mechanical direction of 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. More than 450g / mil, not more than 430g / mil, not more than 410g / mil, not more than 390g / mil, or not more than 370g / mil, 275g / mil to 475g / mil, or 325g / mil to 410g / mil.

When testable, the item may have an Emmendorf shear test value in the horizontal axis direction of 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 550g / mil, no more than 700g / mil, no more than 680g / mil, no more than 650g / mil, no more than 625g / mil, no more than 600g / mil, no more than 580g / mil, or no more than 570g / mil, 475g / mil to 725g / mil, or 490g / mil to 640g / mil.

When testable, the item may have a secant module test value in the mechanical direction of at least 20kpsi, at least 22kpsi, at least 24kpsi, at least 26kpsi, at least 28kpsi, or at least 30kpsi, not more than 40kpsi, not more than 38kpsi, not more than 36kpsi , No more than 34kpsi, or no more than 32kpsi, 20kpsi to 40kpsi, or 25kpsi to 35kpsi.

When testable, the item may have a secant module test value in the horizontal axis direction of at least 20kpsi, at least 22kpsi, at least 24kpsi, at least 26kpsi, at least 28kpsi, or at least 30kpsi, not more than 40kpsi, not more than 38kpsi, not more than 36kpsi, no more than 34kpsi, or no more than 32kpsi, 20kpsi to 40kpsi, or 25kpsi to 35kpsi.

In some examples, an article containing a carbohydrate-based polymer material formed from a mixture of two or more starches has a higher strength property than a carbohydrate-based polymer material formed from a single starch Items. For example, an article containing a carbohydrate-based polymer material formed from a mixture of two or more starches has a drop weight test value (in grams or grams per mil thickness) than a single starch The carbohydrate-based polymer material formed is high, at least higher than about 5%, or 10%; compared to the same article, but containing only carbohydrate-based polymer materials formed from a single starch, at least higher than about 25%, at least above about 50%, at least above about 75%, above 10% to 150%, or above 60% to 120%. Details of this enhanced strength can be found in the examples provided herein, as well as in U.S. patent applications 14 / 853,725 and 15 / 481,806, which are incorporated herein by reference.

Figures 1A, 1B and 1C further illustrate specific examples of the method according to the present invention. These diagrams are generally covered by the more general steps in Figure 1 and the descriptions provided herein, which are generally applicable. For example, Figure 1A shows similar steps 102, 104, 106, and 108, but the article produced at 110 'is specifically a blown film, and the blown film equipment is operated so that the inflation ratio is at least 2.0, And / or the mold gap is not more than 500 microns. In other words, Figure 1A illustrates an exemplary method 100 'that can be used to increase the strength of a blown plastic film by ensuring that the mixture of the blown plastic film contains a renewable carbohydrate-based polymer material, and Choose a high inflation ratio and / or narrow die gap. At 102, the process 100 may include providing one or more "other" polymer materials, such as any plastic resin that can be blown into a film, such as polyethylene, polypropylene, other polyolefins, and polyethylene terephthalate. Ester, polyester, nylon, polystyrene, ABS, polyvinyl chloride, etc. The "other" polymer material may be a polymer material based on a petrochemical. It may also be a "green" version of these petrochemical-based polymer materials (eg, "green" polyethylene available from Braskeem, etc.). A wide range of polymers suitable for "other" polymers is readily apparent.

At 104, the process 100 may include providing the one or more carbohydrate-based polymer materials, for example, because of their identifiable ability to increase strength when blowing at high inflation ratios and / or narrow die gaps, It is specifically selected to be included in the mixture. The regenerative carbohydrate-based polymer material may be substantially amorphous and have no more than 20% crystals. Exemplary materials regarding NuPlastiQ or ESR purchased from BiologiQ, as described herein, may additionally or alternatively exist in various other aspects regarding elastic modulus (i.e. Young's modulus), glass transition temperature, heat distortion temperature, Ficca softening Characteristics of temperature or other characteristics. At 106, the materials can be co-mixed at 106 to form a mixture of the materials. At 108, they can be heated (e.g., in the case of a thermoplastic material) to prepare the film for blowing. At 110 ', a plastic film is blown with the material mixture using a film blowing device. During the blown film, the blow-up ratio used was at least 2.0. As described herein, the applicant of this case found that the combination of including the carbohydrate-based polymer material in the mixture and the use of an inflation ratio of 2.0 or higher resulted in a significant increase in the strength of the film. Achieved by narrow die gap.

WO 2014/0190395 filed by Lovgens describes a multilayer film formed of a mixture of Cardia BL-F and PE. This film is significantly weaker than the film in this case because of the use of different TPS materials and the specific selected Selection of inflation ratio and / or die gap characteristics. For example, the film blown in Lovgens is 80 microns thick (that is, more than 3 mils) and its strength is actually less than 100% PE film. In contrast, compared to a 100% "other polymer material" (such as PE) control group, the specific choices described herein actually increase the strength of any predetermined thickness. Furthermore, the method can produce a film having a desired strength and a lower thickness. The ability of such a film to achieve a desired strength with a significantly lower thickness also reduces the amount of material used to prepare the film layer, which can save costs and produce better durability.

As described herein, a specific carbohydrate-based polymer material and other polymer materials as described herein are mixed, and then the material mixture is used to blow film equipment at an inflation ratio of at least 2.0 and / or have a narrow mold Blown plastic film at a gap (for example, not more than 500 microns); the applicant of this case found that this provides a film (for example, less than 2 mils, such as 0.1 to 1.5 mils) which actually has higher strength, when similar to other but A film blown only with the first polymer material (for example, PE).

Without being bound by any particular theory, it is believed that when blown at high inflation ratios and / or narrow die gaps, the specific regenerative properties that are essentially amorphous are based on the carbohydrate polymer resin system to promote the difference in the mixture The molecules of the polymer are arranged, oriented, and / or extended in a manner that enhances the strength of the resulting mixed plastic film.

For example, a polymer can be formed of both a crystalline structure (regular stack) and an amorphous structure (random arrangement). Many polymers (such as polyethylene) contain a high degree of crystallinity, but they may include some amorphous regions arranged randomly and entangled in the overall structure of the polymer. The specific regenerative carbohydrate-based polymer materials used are not highly crystalline, but are substantially amorphous. Without being bound by any particular theory, it is believed that the combination of the crystalline first polymer material and the amorphous renewable carbohydrate-based polymer material is such that the components of the mixture are homogeneously mixed together The components are oriented, aligned, and extended, and the oriented alignment and extension results in increased strength. These strength enhancements can be seen in both the machine direction (MD) and the transverse axis direction (TD). Therefore, the observed phenomenon is not just a matter of simply giving up the strength in one direction to improve the other direction. This can be demonstrated by drop weight test data, which shows the strength in both directions at the same time.

Increasing strength through the selection of this particular amorphous carbohydrate-based material, and the choice of high inflation ratios, such as, and / or the use of narrow mold gaps, advantageously provides increased strength in the film, typically compared to other Mixtures containing TPS (such as Cardia BL-F) are thinner. In some examples, as described herein, the film can be blown as thin or even thinner than when blown from the first polymer material alone. For example, the applicant in this case observed that, compared to the thinnest film blown from polyethylene alone, it can be blown as thin or even thinner from a mixture of polyethylene and the renewable carbohydrate-based polymer material. The ability of the film (for example, the ability to blow a 0.1 mil film).

As described herein, it includes a carbohydrate-based polymer material having low crystallinity and / or other characteristics as described herein, and other polymer materials, with the high inflation ratio and / or narrow modulus. The formed article may have a numerical value of strength properties, which is larger than an article formed by "other" polymer materials alone. This increase in strength is, for example, advantageous and surprising compared to the state of the art. For example, Lovgens describes blowing films from a mixture of starch-based polymer materials (Cardia BL-F) and polyethylene. The resulting films have lower tensile strength (Lofgens Figure 2), and Low drop weight impact strength (Lofgens Figure 5), which is a result of comparison with similar films formed from polyethylene alone. This is also because the mixture of Cardia BL-F and polyethylene is blown at a 3: 1 blow ratio. This confirms that at least under the specific conditions of Lovgens (including a relatively wide mold gap of 1.6 to 1.8 mm), not all regenerative carbohydrate-based polymer materials can have an increase in strength. As shown in the examples, the use of the regenerable carbohydrate-based polymer material of the present invention, which has low crystallinity and / or other specific characteristics related to NuPlastiQ or ESR, will result in enhanced strength.

Compared with other items that are the same but formed of "other" polymer materials (ie, no regenerating carbohydrate-based polymer materials or compatibilizers), it can increase by at least about 1%, at least about 2%, at least about 3 %, At least about 5%, at least about 10%, at least about 15%, at least about 20%, 1% to 50%, 1% to 40%, or 10% to 40% strength (such as whether it is tensile strength, Drop hammer impact strength, or other strength measurement).

Figures 1B and 1C illustrate a specific method to offset the unique odor caused by the carbohydrate-based polymer material in the mixture. Those skilled in the art can easily understand that any of the methods described herein can be used in common (for example, film is blown at a high inflation ratio and / or a narrow mold gap, also including a deodorant). FIG. 1B illustrates the preparation of an article comprising a carbohydrate-based polymer material, an organic deodorant, and a polymer resin according to an exemplary method 100 "of the present invention. At 102, the process 100 may include providing one or more" other "Polymer resin. As described here, these resins can be any of many traditionally used in plastic manufacturing. At 103 and 104, respectively, the process 100 includes the provision of organic deodorants and the carbohydrate-based polymer materials. .

In one embodiment, the deodorant may be included in the carbohydrate-based polymer material (eg, included in its master batch). In other embodiments, the deodorant may be added in other ways, such as in the polymer resin, separately from the polymer resin and the carbohydrate-based polymer. The different and possible ways of addition are obvious. The particular choice of deodorant contained in the mixture is based on its ability to offset the odor of the final article due to the carbohydrate-based polymer material. For example, the carbohydrate-based polymer material may cause a slight burnt odor of carbohydrates (for example, a slight burnt starch smell, popcorn or caramel corn-like smell), which occurs during the heating process of the mixture ( For example, during injection molding, blow molding, film blowing, etc.), here, at 102, 103, and 104, the components are melted together under heating conditions to form the mixture.

At 103, the deodorant may be of any desired type (e.g., granules, powder, plastic particles, slurry, and / or liquid). In one embodiment, the deodorant may include a lyophilized powder initially, and be mixed with the masterbatch of the carbohydrate-based polymer material during manufacturing, or after the carbohydrate-based polymer material is manufactured. . For example, when the carbohydrate-based polymer material is formed from a mixture of starch powder, glycerin, and water, the deodorant (such as a lyophilized powder) can be simply mixed with starch powder, or with water, or with plastic. A chemical agent such as glycerin is added to the mixture, and then mixed with it. The carbohydrate-based polymer material can then be manufactured by the same process that is generally prepared, and the deodorant is incorporated into the carbohydrate-based polymer material to become dispersed components (for example, homogeneously dispersed therein ).

In other embodiments, since the powder or other deodorant is melted and prepared to be combined with other ingredients (such as compatibilizer) contained in the master batch, it can be simply mixed with the carbohydrate-based polymer. The many possibilities of adding the deodorant to any ingredient will be apparent to those skilled in the art, which is used to form plastic articles from a mixture of a carbohydrate-based polymer material and another polymer resin. Different alternatives incorporating the organic deodorant are also applicable.

Regardless of how the organic deodorant is incorporated into the mixture, the mixture of ingredients at 102, 103, and 104 can be formed by any desired process, such as described above or elsewhere in this specification.

The deodorant may be organic. Those skilled in the chemical arts can easily understand that organic compounds are based on carbon, but exclude simple carbon compounds such as carbides, carbonates, carbon oxides (for example, CO and CO ₂ ), and cyanide. In one embodiment, the organic deodorant may include a phenyl group and is an aromatic compound. Different aromatic derivatives of benzene are also suitable, such as benzaldehyde and / or benzyl ketone. In one embodiment, the organic deodorant may be a compound containing carbon, oxygen, and hydrogen atoms (eg, no heteroatoms). In other embodiments, compounds containing one or more heteroatoms may also be suitable. In one embodiment which has proven to be particularly effective, the deodorant system includes a benzaldehyde compound, such as 4-hydroxy-3-methoxybenzaldehyde. This aromatic compound is also called vanillin and has the following chemical structural formula.

It was found here that very small portions of the organic deodorant offset the odor associated with the carbohydrate-based polymer material. In addition to only such a small amount of deodorant, it is also surprising that the problems associated with adding organic ingredients (the carbohydrate-based polymer material) can also be solved by adding even more organic ingredients. For example, those skilled in the art would expect that the inclusion of additional organic ingredients, especially those with an aromatic chemical structure, would increase the odor release of the mixture during the heating process, rather than reduce or substantially eliminate the odor.

In one embodiment, the composition does not include inorganic or other deodorants. For example, in one embodiment, the composition does not include activated carbon, zeolite, or other known ingredients including active sites capable of bonding with volatile odor molecules. For example, the inclusion of such deodorants activates a mechanism that can inhibit the ability of benzaldehyde or other organic deodorants to perform their intended function in a manner that is bound by the active site (for example, the active site may only be Used to bond with benzaldehyde or other organic deodorants).

The deodorant may include the mixed plastic material, or a carbohydrate-based polymer material containing the deodorant (for example, as a masterbatch for mixing with another polymer resin), one of which does not exceed 1% , No more than 0.5%, no more than 0.25%, no more than 0.1%, no more than 0.05%, no more than 0.01%, no more than 1000ppm, no more than 500ppm, no more than 250ppm, no more than 100ppm, no more than 50ppm, or no more than 20ppm Of, of either the blended. By mixing the carbohydrate-based polymer material and another polymer resin, the concentration of the deodorant is of course further diluted. For example, in the plastic mixed article, the concentration of the deodorant may be no more than 15 ppm, no more than 10 ppm, no more than 5 ppm, or even 1 ppm. The applicant of this case was surprised to find that such a small amount can effectively offset or substantially remove the odor characteristics of a plastic containing a carbohydrate-based polymer material.

In addition to vanilla extract, other extracts from various fruits and / or vegetables are also suitable as organic deodorants. Non-limiting possible examples include lyophilized extracts of vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, passion fruit, or raspberry. The composition is also applicable.

As noted above, in one embodiment, the deodorant may be added to the water and / or glycerin (eg, dissolved or dispersed therein) used to form the carbohydrate-based polymer material, which is particularly beneficial to ensure that Very small portions of the deodorant can be homogeneously mixed throughout the final carbohydrate-based polymer material. For example, when a powdery deodorant is added to other powdery materials (such as starch) used to make the carbohydrate-based polymer material, the amount of the deodorant is so small (for example, in a master batch) 20ppm), and it is easier to ensure a homogeneous distribution of the deodorant by mixing with liquid components rather than solid powders.

When the deodorant is added to the carbohydrate-based polymer material, the odor characteristic can be changed. By removing the mixture of the carbohydrate-based polymer material and another thermoplastic polymer resin, it has other unique caramel. The tendency of corn or popcorn-type odors to include the deodorant does not substantially alter any physical or other properties of the NuPlastiQ or ESR material as described herein. If noted, the deodorant may be present in the carbohydrate-based polymerizable NuPlastiQ or "ESR" material, with a range of no more than 1000ppm, 500ppm, 250pp, 200ppm, 100ppm, 50ppm, 40ppm, 30ppm, 25ppm, 20ppm, 5ppm To 50 ppm, 10 to 50 ppm, or 15 to 25 ppm. The applicant in this case found that in NuPlastiQ or ESR materials, it was particularly effective at a level of 20 ppm. Obviously, after dilution with the polymer resin material, the deodorant concentration of the articles formed from the mixture will be even lower (for example, a level in the 20 ppm in NuPlastiQ or ESR masterbatch, may be In the final article, it drops to only 10 ppm, only 5 ppm, or only 1 ppm).

In some embodiments, the NuPlastiQ or ESR can be provided in a master batch formulation, which can include the carbohydrate-based polymer material, the deodorant, and one or more compatibilizers in the amounts described above. The masterbatch may also contain one or more of the "other" polymer resins (for example, the same polymer resin as the carbohydrate-based polymer resin to be mixed to form the target article). Such master batch formula particles can be mixed with particles of "other" polymer resin materials at the time of processing. Depending on the desired percentage of NuPlastiQ or ESR and / or compatibilizer and / or conventional polymer resin in the final article, the different particles can be mixed in any desired ratio.

As noted above, the deodorant can generally be present in the carbohydrate-based polymer material in very low amounts, such as no more than 1%, no more than 0.1%, no more than 0.01%, no more than 1000ppm, no more than 100ppm, Not more than 50 ppm, or not more than 20 ppm. By mixing a carbohydrate-based polymer material containing the deodorant and the polymer resin, the amount of the deodorant in the resulting mixed plastic article is reduced, and the polymer is based on the carbohydrate-based polymer material to the polymer. Mixing ratio of resin materials. As noted here, a wide variety of mixing ratios can be applied. For example, the initial amount of deodorant in the carbohydrate-based polymer material master batch is 20 ppm, and when the mixing ratio is 1: 1, it is reduced to only 10 ppm in the final plastic article formed from the mixture. When the mixing ratio is 25% of the carbohydrate-based polymer material and 75% of the polymer resin material, the initial amount of the deodorant is reduced to 5 ppm when it is 20 ppm.

Obviously, although the deodorant concentration is reduced, the ratio of the deodorant to the carbohydrate-based polymer material due to the mixing remains unchanged. For example, the weight ratio of the deodorant to the carbohydrate-based polymer may be 1: 1000, or even more diluted. For example, the ratio can be 1: 1000, 1: 2000, 1: 5000, 1: 10,000, 1: 15,000, 1: 20,000, 1: 25,000, 1: 30,000, 1: 35,000, 1: 40,000, 1: 45,000, 1: 50,000, 1: 60,000, 1: 70,000, 1: 80,000, 1: 90,000, or 1: 100,000. The ratio can be a value between any two of the above values (eg, 1: 1000 to 1: 100,000, or 1: 10,000 to 1: 80,000, or about 1: 50,000). The amount of deodorant in the carbohydrate-based polymer material is 20 ppm, which can be equivalent to a ratio of about 1: 50,000. Even if the polymer resin material is mixed, this ratio can be maintained substantially unchanged because the addition of the polymer resin material does not change the amount of the deodorant or the carbohydrate-based polymer material in the mixture.

It is also obvious that when the deodorant is organic, it is important that this component is not volatile because it will not be easily lost during the thermal processing of the article (the residual content of the carbohydrate-based polymer material Water volume may). For example, the deodorant may be solid rather than liquid at ambient temperature (eg, 25 ° C.) and pressure (eg, 1 atm). If liquid, the deodorant may have less volatility than water (for example, measure the relevant vapor pressure at a predetermined temperature and pressure (such as the STP described above). In one embodiment, the deodorant may have a boiling point higher than any temperature related to 108 and 110 "processing. The deodorant may have a melting point lower than any temperature related to 108 and 110" processing. For example, the deodorant may be solid at ambient temperature (eg, 25 ° C), but liquid at elevated temperatures (eg, 125 ° C to 165 ° C) during processing. An example of such a deodorant is 4-hydroxy-3-methoxybenzaldehyde.

For example, the deodorant may have a melting point of at least 30 ° C, at least 50 ° C, below 200 ° C, below 190 ° C, below 180 ° C, below 175 ° C, below 170 ° C, below 165 ° C, Below 160 ℃, below 150 ℃, below 145 ℃, below 140 ℃, below 135 ℃, than 130 ℃, below 125 ℃, below 120 ℃, below 115 ℃, below 120 ℃, low At 115 ° C, below 110 ° C, below 100 ° C, 50 ° C to 180 ° C, 50 ° C to 150 ° C, or 60 ° C to 100 ° C. The deodorant may have a boiling point higher than 150 ° C, higher than 160 ° C, higher than 170 ° C, higher than 180 ° C, higher than 200 ° C, higher than 225 ° C, higher than 250 ° C, 150 ° C to 500 ° C, 200 ° C to 400 ° C, or 250 ° C to 300 ° C. For example, vanilla extract melts at 81 ° C to 83 ° C and boils at 285 ° C.

Figure 1B illustrates how to prepare an article from a polymer resin (at 102) and a deodorant (at 103) and a carbohydrate-based polymer material (at 104). Figure 1C illustrates a process 100 '' ', The deodorant may be incorporated into the carbohydrate-based polymer material. For example, the deodorant can be provided at 103, the carbohydrate-based polymer material can be provided at 104, and they can be mixed together at 106 ". For example, when preparing a masterbatch, the organic A odorant is mixed into the carbohydrate-based polymer material (for example, when the deodorant is added to the carbohydrate-based polymer material, a compatibilizer or other ingredients are also included in the master batch). In other implementations For example, the deodorant may be mixed with a starting material that forms the carbohydrate-based polymer material (for example, by mixing the deodorant with one or more of water, glycerin, or a starch component, forming the Carbohydrate-based polymer materials). In either case, the method chosen is to include a carbohydrate-based polymer material with the deodorant dispersed therein. As described herein, its concentration can be very low (e.g., , 20ppm). At 110 '' ', by mixing with polymer resins (for example, generally about applying heat to melt and blend thermoplastic materials), this carbohydrate-based polymer material (including The deodorant) used to prepare an article.

Returning to standard features that can be implemented in any of the embodiments herein, they can be characterized by biodegradation testing (for example, whether it is a biomethane potential test, or any applicable ASTM standard, such as ASTM D-55511, ASTM D-5526 , ASTM D-5338, or ASTM D-6691). Under this test, for a predetermined length of time (for example, 30 days, 60 days, 90 days, 180 days, 365 days (1 year), 2 years, 3 years, 4 years, or 5 years, the item can display the total Macromolecular component, and / or any non-biodegradable "other" macromolecular component (different from the carbohydrate-based polymer component) for substantial biodegradation. The biomethane potential test is typically performed for 30 or 60 days, Although sometimes it can be as long as 90 days. In any of the above ASTM standards, the test is typically performed over a longer period of time. For example, an article may be free of or substantially free of biodegradation aids, showing The biodegradation effect higher than the content of the carbohydrate-based polymer material implies that the other plastic material is also biodegradable (or has the potential of biodegradation under the biomethane potential test).

Especially when the article is tested for a simulated landfill or other waste and / or decomposition environment (such as compost conditions, or marine conditions) for 180 days, 200 days, 365 days (1 year), 2 years, 3 years, Or 5 years, its biodegradation effect can be greater than the weight percentage of carbohydrate-based polymer materials in the article. In other words, the inclusion of the carbohydrate-based polymer material may cause at least partial biodegradation of other non-biodegradable "other" polymer materials.

For example, after the length of time, the article formed from the mixture of the carbohydrate-based polymer material and PE may have a biodegradation effect, which is higher than the weight of the film of the carbohydrate-based polymer material. , Implying that PE (previously considered non-biodegradable) was actually biodegraded, together with the carbohydrate-based polymer material. These results are surprising and particularly advantageous.

Biomethane potential test is based on methanogenesis as a percentage of total methanogenesis potential to determine the potential of anaerobic biodegradation. According to the ASTM D-5511 standard, the biomethane potential test can be used to predict the biodegradability of the test sample, and the biomethane potential test can be performed under one or more conditions of the ASTM D-5511 standard. For example, the biomethane potential test can be performed at a temperature of about 52 ° C. Accordingly, the biomethane potential test may have conditions different from those of ASTM D-5511, such as being completed within 30, 60, or sometimes up to 90 days in order to accelerate the test. Biomethane potential test can be inoculated with 50% to 60wt% water and 40% to 50wt% organic solids. For example, an inoculation for a biomethane potential test may have 55 wt% water and 45 wt% organic solids. The biomethane potential test can also be performed at other temperatures, such as 35 ° C to 55 ° C, or 40 ° C to 50 ° C.

When carrying out biodegradation, the content of biodegradation promoter (or preferably not containing) of not more than about 2% by weight and the content of carbohydrate-based polymer materials and "other" polymer materials as described herein The article may have an enhanced decomposition effect as a result of introducing the carbohydrate-based polymer material to the article. For example, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60 %, At least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or even at least 95% of non-carbohydrate-based polymer materials (such as the "other" polymer material) , Under landfill, compost, and / or marine conditions (or simulated conditions), it can be biodegraded over a period of at least about one year, at least about two years, at least about three years, or at least about five years. This type of biodegradation is particularly noteworthy and advantageous. Therefore, it is not only the carbohydrate-based polymer material that is biodegraded, but the "other" polymer material is also decomposed, even if the material itself is not biodegradable.

Examples show that as time increases, the amount of biodegradation can be very high; in at least some embodiments, the item is substantially biodegraded overall (e.g., on 180 days, or 200 days, or 365 days (1 At least about 85%, at least about 90%, or at least about 95% biodegradable) within 2 years, within 3 years, within 5 years, or other lengths of time).

Figure 2A illustrates the components of an exemplary manufacturing system 200 for preparing articles in accordance with the present invention. In some examples, the manufacturing system 200 may be used in any one of the process 100 in FIG. 1 or in FIGS. 1A-1C. In an illustrative embodiment, the manufacturing system 200 is an extruder, such as a single screw extruder or a twin screw extruder.

In one embodiment, one or more non-biodegradable plastic materials and one or more carbohydrate-based polymer materials may be provided through the first supply tank 202 and the second supply tank 204. One or both of the materials may include a compatibilizer (eg, in its masterbatch).

The one or more carbohydrate-based polymer materials and the one or more non-biodegradable plastic materials can be mixed in the first chamber 206 to prepare a material mixture. In some examples, the material mixture may include 5 wt% to 40 wt% of one or more carbohydrate-based polymer materials, 60 wt% to 94 wt% of one or more non-biodegradable plastic materials, and 1 wt% to 9 wt% One or more compatibilizers. As described herein, small amounts of deodorants may also be present. Depending on the desired characteristics, this range can of course be changed beyond the above range.

As shown in FIG. 2A, the material mixture can pass through a series of chambers, such as the first chamber 206, the second chamber 208, the third chamber 210, the fourth chamber 212, and the fifth chamber 214. ， And the selected sixth chamber 216. The material mixture can be heated in the chambers 206, 208, 210, 212, 214, 216. In some examples, one of the chambers may have a different temperature than the other chamber. In the illustrative embodiment, the first chamber 206 is heated to a temperature of 120 ° C to 140 ° C; the second chamber 208 is heated to a temperature of 130 ° C to 160 ° C; the third chamber 210 is heated to A temperature of 135 ° C to 165 ° C; the fourth chamber 212 is heated to a temperature of 140 ° C to 170 ° C; the fifth chamber 214 is heated to a temperature of 145 ° C to 180 ° C; and the sixth chamber selected 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 an extruded article, such as a film, plate, or the like. Injection molding, thermoforming, or other plastic manufacturing methods can be used to make a variety of different items, such as utensils, plates, cups, bottles, their covers or covers. In the blown film, air can be injected into the extruded article to expand it at a pressure of 105 bar to 140 bar. The resulting tube 220 can be stretched via a roller 222 to produce a film 224, typically having a thickness of 0.02 mm (about 0.8 mils) to 0.05 mm (about 2 mils). Mixtures as described herein can be used to make even thinner films, such as having a thickness as thin as 0.1 mil (0.0025 mm). Of course, thicknesses higher than 2 mils can also be achieved. In some examples, the film 224 may be composed of a single layer. In other examples, the film 224 may be composed of multiple layers. When multiple layers are present, at least one layer may contain the carbohydrate-based polymer material. In some embodiments, the carbohydrate-based polymer material may be present in one or more outer layers. In other embodiments, the carbohydrate-based polymer material may be present in the inner layer. If the outer layer does not contain a carbohydrate-based polymer material, the biodegradation of the outer layer may not occur.

Figures 2B and 2C illustrate the formation of the die 218 and the bubble 220, showing additional details about the film blowing equipment of Figure 2, and specifically showing how to select the inflation ratio and die gap characteristics to increase strength. As shown in FIGS. 2B and 2C, the mold 218 may include an outer member 218a and an inner member 218b, and a mold gap 226 is defined therebetween. As described herein, the mold 218 may be specifically used to provide a narrow mold gap, such as below 1000 microns, below 900 microns, below 800 microns, below 700 microns, below 600 microns, or below 500 microns (e.g., 200 to 500 microns). On a blown film containing other thermoplastic starch ingredients, this narrow mold gap is in stark contrast to the wide mold gap (and possibly necessary) used in conventional techniques. For example, the Lovgens system describes a mold gap of 1.6 to 1.8 mm (ie, 1600 to 1800 microns). Even at high inflation ratios, it is not possible to achieve the strength enhancements described herein with such large die gaps.

Figure 2B further illustrates the relatively high inflation ratio, which is defined as the ratio of the maximum diameter (D _B ) of the bubble divided by the die gap diameter (D _D ). In another way, it is about the flat folding width of the film, and the inflation ratio is equivalent to 0.637 * (flat folding width) / D _D. Figure 2B also shows the cold line 228, where the previously melted material of the bubble begins to crystallize, so the crystalline area of the cold line 228 has a more translucent appearance. As described herein, the inflation ratio is at least 2.0, such as 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 2.2 to 2.8, or about 2.5. The applicant of this case has observed that the strength of the film can be simply increased by increasing the inflation ratio, which is increased from the inflation ratio of 1.5 to at least 2, such as 2.5, in a typical blowing method. When the value rises to about 3, an increase in intensity can be observed; however, there is no significant increase in strength after that, so values of 2-3, 2.2 to 2.8, or about 2.5 are particularly preferred. As described herein, the strength increase can also be achieved by blowing a mixture containing a specific said regenerative carbohydrate-based polymer material while maintaining a narrow gap.

For example, a mold gap below 500 microns and an inflation ratio of at least 2 (e.g., 2.2 to 2.8, or about 2.5) are particularly suitable for blowing from the mixture with a maximum of 1.5 mils (e.g., 0.1 mil to 1.5 mil). To blow thicker films (when thicker films are needed), the die gap can be increased to accommodate the flow of molten material. For example, to blow a very thick film of 10 mils, or even 5 mils, the mold gap can be increased slightly (although the value may still be below 1000 microns, or even below 500 microns).

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

Examples

Example 1

Eleven kinds of starch-based polymers are formed from 27% animal fat glycerin (99% pure glycerin) and 73% starch without water. Individual final starch-based polymers have <about 1% water, and are mixed with LLDPE and anhydride-modified LLDPE at 25%, 70%, and 5% by weight, respectively. Next, the resulting mixture was extruded and blown into a film. 70% of each film is LLDPE, 25% is starch-based polymer, and 5% of each film is acid-modified LLDPE. The films were then subjected to a drop weight test in accordance with ASTM D-1709. The combination of starch test and strength test results (in grams) is shown in Table 3. The results in Table 3 show that the samples with a starch mixture have a drop weight impact test value that is higher than the samples with a single starch sample.

Figure 5 shows the drop weight impact tests of films of different thicknesses based on the percentage of NuPlastiQ or "ESR" based on starch in the film (thickness of 0.5 mil, 1 mil, 1.5 mil, 2.0 mil). NuPlastiQ or ESR forming these films as shown in Figure 5 is formed from a starch mixture containing 90% corn starch and 10% potato starch. Figure 5 shows how the film strength increases as the percentage of NuPlastiQ or ESR increases, with NuPlastiQ or ESR of about 20% to about 25% being the highest strength. The balance of the mixture includes polyethylene and a suitable compatibilizer, as described herein.

Figure 6A shows a film containing 25% of a carbohydrate-based polymer material and balanced with a small amount of a compatibilizer (for example, about 5%) and PE (about 70%) as described herein. Hammer impact test (0.1 mil thickness to 2 mils maximum). Figure 6 also shows the control strength of a 100% PE film, all of which are lower than the mixture according to the invention. Figure 6 further shows a variety of other test reference points, for fresh packaging bags (for example, bags for fresh products provided to consumers in the supermarket fresh food area), various "haul out" bags (for example, for takeaway) Groceries and other plastic bags), and potato bags (in the supermarket fresh food area, usually used for plastic bags containing 5, 10 or 20 pounds of potatoes). Example 8 is similar data, but the results shown are for a "other" polymer material that is a mixture of biomass polyethylene, rather than synthetic LLDPE derived from petroleum sources.

Figure 7 shows the drop weight impact strength of films of different thicknesses (thickness below 0.5 mils up to about 2 mils) for different mixed films and control films according to the present invention (e.g., 100% LLDPE, 100 % Recycled LLDPE (rLLDPE)). In addition to showing the strength characteristics of the film formed from the initial material (25% NuPlastiQ or ESR, 70% LLDPE, 5% compatibilizer (labeled as 25% NuPlastiQ or ESR / 75% LLDPE)), Figure 7 also shows the This recycled material (rLDESR) is then mixed with the original material (labeled 25% NuPlastiQ or ESR / 25% rLDESR / 50% LLDPE), or recycled LLDPE (rLLDPE) is used in the mixture (labeled 25% NuPlastiQ or ESR / 25% rLLDPE / 50% LLDPE). In addition to the previously mentioned features of improving regenerative and biodegradable properties, as shown, this strength result is improved compared to the use of PE polymer materials.

Example 2

Three samples were tested for 349 days in accordance with ASTM D-5511 to determine biodegradability characteristics. This test is intended to repeat conditions for large-scale anaerobic digestion (landfill). The results of the three samples (labeled 1342, 1343, and 1344) are shown in Figures 8A-8B and Table 4. Figure 8A shows the results of all samples 1342, 1343, and 1344 compared with the control group. Figure 8B shows the results of sample 1344 alone compared with the control group. Sample 1342 is formed of 30% NuPlastiQ or ESR (the substantially amorphous carbohydrate-based polymer material with less than 10% crystals), 67% PBAT, and 3% compatibilizer, and has a thickness of 1.1 Mil. Sample 1343 was formed from 27.5% NuPlastiQ or ESR, 70% PBAT, and 2.5% compatibilizer, and had a thickness of 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.

Figures 8A-8B show that after 204 days, the negative control group showed 2.5% decomposition, the positive control group showed 86.5% decomposition, sample 1342 showed 43.3% decomposition, sample 1343 showed 53.9% decomposition, and sample 1344 showed 77.2% decomposition. At 349 days, the decomposition value is shown in Table 4.

Biodegradation is particularly excellent after 349 days. For example, the samples containing PBAT (1342 and 1343) show very good biodegradation, the percentage of biodegradation is much larger than the amount of the carbohydrate-based polymer material contained in the membrane; and sample 1344 (see Figure 8B) ) Is even more surprising, showing nearly 96% biodegradation (even higher than the positive control group), where the non-biodegradable plastic material is polyethylene, which is of course non-biodegradable under normal conditions (for example, see The negative control group of Table 4, which is 100% polyethylene). The result of this biodegradation is extremely valuable and extremely advantageous.

Example 3

Anaerobic biodegradation testing of potato packaging bags prepared with a mixture of 25% NuPlastiQ or ESR, 70% LLDPE, and 5% compatibilizer in accordance with ASTM D-5526 for 60 days, 107 days, 202 days, 317 days, 439 Days, 573 days, and 834 days. The test is intended to repeat conditions for large-scale anaerobic digestion (landfill). The test was performed under various conditions using a water-balanced inoculation with approximately 35%, 45%, and 60% organic solids. The results of inoculations containing 35% organic solids (and 65% water) are shown in Figure 9 and Table 5A. Table 5B shows the results of other inoculation values and other samples. The potato bag has a thickness of 1.35 mils. These bags are labeled Sample 1072.

Under simulated burial conditions for more than 834 days, potato packaging bags made with 25% NuPlastiQ or ESR and 70% LLDPE showed excellent biodegradability of 81%. NuPlastiQ or ESR is homogeneously mixed with polyethylene, which is beneficial to cause the long carbon chain of polyethylene to break and be digested by the same microorganisms that can consume the carbohydrate-based polymerizable NuPlastiQ or ESR material. These results show that the entire bag containing polyethylene can be biodegraded into carbon dioxide, methane, and water. This result is surprising and highly advantageous.

The test results with 45% organic solids and 60% organic solids also show that the percentage of biodegradation exceeds the percentage of NuPlastiQ or ESR contained in the potato packaging bag. Similar potato packaging bags (Sample 1073) containing 1% biodegradation booster and other similar potato packaging bags (Sample 1075) containing EcoFLEX ^™ compostable resin and metallocene LLDPE were also tested.

Example 4

Anaerobic biodegradation of films prepared from NuPlastiQ or a mixture of ESR and LLDPE was tested in accordance with ASTM D-5338 after 201 and 370 days. The conditions are simulated aerobic digestion and / or industrial composting conditions. In Table 6 and Figures 10A-10B, the test films are labeled 1345 and 1346, which show the results after 370 days. On 201, samples 1345 and 1346 showed calibrated values of 74.2% and 72.4%, respectively, while the negative control group showed -3.3% and the positive control group showed 100%. Figures 10A-10B show the actual% biodegradation. Sample 1345 contains 25% NuPlastiQ or ESR, 72.5% LLDPE, and 2.5% compatibilizer. Sample 1346 contains 40% NuPlastiQ or ESR, 56% LLDPE, and 4% compatibilizer. Both films had a thickness of 1.0 mil.

Biodegradation after 370 days, especially sample 1345 is particularly good. This sample (see Figure 10B) shows more than 97% biodegradability. When the non-biodegradable plastic material is polyethylene, it is of course non-biodegradable under normal circumstances (for example, see the negative control group in Table 6, which is 100% polyethylene). The result of this biodegradation is extremely valuable and particularly advantageous.

Example 5

According to ASTM D-6691, the anaerobic biodegradation of films prepared from NuPlastiQ or a mixture of ESR and PBAT was tested after 205 days, which simulates marine conditions. In Tables 7 and 11, the test films are labeled 1439 and 1440. On day 205, samples 1439 and 1440 showed that the calibrated biodegradation percentage values were 49.6% and 53.6%, respectively. Sample 1439 contains 30% NuPlastiQ or ESR, 67% PBAT, and 3% compatibilizer. Sample 1440 contains 27% NuPlastiQ or ESR, 70% PBAT, and 2.5% compatibilizer. Sample 1439 has a thickness of 1.1 mils, and sample 1440 has a thickness of 1.0 mils.

Example 6

Test the biodegradability of additional manufactured membranes. Table 8 below summarizes the results of this test, some of which are described in detail below. The test shows that under different simulated conditions (such as landfill, compost, marine environment), the amount of carbohydrate-based polymer materials spanning a wide range, and the excellent biodegradability results of different polymer materials.

Example 7

Additional tests were performed on the carbohydrate-based polymer material with different loadings according to the present invention to assess biodegradability. The test is performed according to ASTM D5511. The amount of the carbohydrate-based polymer material in the test sample was 0% (control group), 1%, 5%, 10%, and 20% by weight of the mixture. Table 9 below summarizes the results of this test. Even with only 1% filling, the biodegradation percentage (2.7%) after 65 days is higher than the filling amount (only 1%), suggesting that the polyethylene contained in the mixture is also decomposed. This tendency was consistently seen in the 95-day data, while the percentage of biodegradation continued to increase (for example, 5% on the 95th day). The results of further acceleration can be seen in higher loadings of 5%, 10%, and 20% of the carbohydrate-based polymer material. It is expected that in all samples filled with biodegradable carbohydrate-based polymer materials, all non-biodegradable plastic components will be within such a reasonable time frame under such waste conditions (for example, 1 Years, 2 years, 3 years, 4 years, or 5 years).

Example 8

Films were prepared from a mixture of bio-based polyethylene (purchased from Braskem), NuPlastiQ or ESR, and Bynel® compatibilizer. Once formed, the resulting film is tested for drop weight (for example, according to ASTM D-1709). Blown films with different thicknesses from 0.5 mils up to 2 mils and different percentages of starch-based polymer materials (NuPlastiQ or ESR) from 0wt% to 35wt% of NuPlastiQ or ESR. The results are shown in Figures 12A and 12B.

As shown in Figure 12A, the biopolyethylene alone (without NuPlastiQ or ESR) has a drop weight strength of 0.5 mil and a thickness of about 120 g, a drop weight strength of 1 mil and a thickness of about 155 g, and 1.5 mils. A drop weight strength of about 200 g and a 2 mil drop weight strength of about 270 g. The approximate drop weight strength is shown in Table 10A. Table 10B shows the percentage increase in strength compared to pure bio-polyethylene film. It can easily be seen that it increases in the test percentage of NuPlastiQ or ESR in all thicknesses and in all films. This increase in strength is particularly high when the film changes thickness (i.e., the increase in the percentage of thicker films is even more dramatic compared to thinner films).

In forming and testing such a film, the applicant of the present application observed that the results of the improved strength were roughly consistent with those using synthetic petrochemical polyethylene. As noted above, it has been observed that when using a bio-polyethylene material in a mixture, the improvement in strength increases more rapidly as the thickness increases (i.e., the percentage increase in thicker films is even greater than in thinner films). dramatic).

It has also been observed that the optimal point for starch based NuPlastiQ or ESR for biomass polyethylene is about 15%, rather than about 25% for petrochemically derived polyethylene. However, when NuPlastiQ or ESR was mixed with one of the two base resins, a similar increase in strength was observed.

Finally, the film formed according to Example 8 contains a biomass content much higher than 40%, which is particularly advantageous because the base resin (for example, any "green" sustainable polymer material as described herein) Both the carbohydrate-based or starch-based NuPlastiQ or ESR materials are derived from sustainable materials. In these films, the only component that is not considered a biomass component is a compatibilizer (if available, a permanent compatibilizer can be used). Accordingly, the biomass component may be at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, and at least 80% of the film or other products. , At least 85%, at least 90%, or even at least 95% by weight. In addition to the Bynel® compatibilizer, the films of Example 8 are composed of biomass components, so they contain more than 90% by weight of biomass components.

Finally, the film of Example 8 was substantially completely biodegradable and decomposed in a manner similar to the various other test polyethylenes tested in the above examples. Accordingly, the present invention provides polymer membranes and other products with very high biomass, which are not only sustainable, but also biodegradable.

Example 9

This example illustrates the effectiveness of the blow-up ratio and / or die gap. Various films were tested with drop weight test strength, including films formed of polyethylene alone and films formed of a mixture of NuPlastiQ or ESR, polyethylene, and a compatibilizer. Film formed from a mixture of 25% renewable carbohydrate-based polymer materials, 5% compatibilizer, and 70% polyethylene. All films were blown with an inflation ratio of about 2.5. The applicant has observed that when the film is blown with the mixture at an increased inflation ratio, an increase in strength is seen; but when the film is blown from polyethylene alone, the inflation ratio does not have any significant effect on strength. In other words, when the polyethylene is used alone, the strength is substantially the same whether the inflation ratio is 1.5, 3, or any value in between. The following Table 11 shows that the drop weight impact strength (in grams) of the films with different thicknesses of the present invention compared with the control group is larger, and the percentage of strength improvement of different mixtures compared with the control group.

Figure 13 shows additional comparative data on the impact strength of the drop weight, for films formed from a mixture of 100% polyethylene film with polyethylene and 25% NuPlastiQ or ESR renewable carbohydrate-based polymer materials with different film thicknesses, For example, at an inflation ratio of about 2.5. Figure 13 shows the ability to make films with thicknesses as thin as 0.1 mils. As described herein, it is quite difficult to form such a thin film system from a polyethylene material alone. As indicated in Figure 13, the strength of a 100% polyethylene film is substantially independent of the inflation ratio (that is, the strength is substantially the same at an inflation ratio of 1.5, or an inflation ratio of 2.0, or 2.5, or 3.0) . At all points, films formed from a mixture of 25% NuPlastiQ or ESR-renewable carbohydrate-based polymers are stronger than films formed from polyethylene alone

Example 10

Examples 10-14 illustrate the addition of a deodorant. Example 10 is a comparative example. The samples were prepared from a mixture of a carbohydrate-based polymer material and another polymer resin (selected as polyethylene), and maleic anhydride modified PE compatibilizer. The compatibilizer content was 5 wt%. The content of the carbohydrate-based polymer material varies from 5% to up to 50% by weight, and is balanced by a polyethylene polymer resin. These samples did not contain any deodorant and had the slight odor characteristics of the carbohydrate-based polymer material, which was described as popcorn-like odor, caramel corn-like odor, or slightly charred starch odor. When the geometry of the item is relatively open (such as a plate or film of the material) the odor is hardly noticeable, but when the geometry is relatively closed (such as a cup type or the film is wound on a roll), The smell becomes more pronounced.

Example 11

The same sample was prepared as in Example 10, but contained a small amount of 4-hydroxy-3-methoxybenzaldehyde (vanillin) as a deodorant. The deodorant is provided as a powder, such as a lyophilized powder. The powder is mixed with liquid ingredients (e.g., water and / or glycerin) used to prepare the carbohydrate-based polymer material to obtain the deodorant homogeneously dispersed therein. Next, in the same manner as in Example 10 (and Example 1), the carbohydrate-based polymer material is formed from water, glycerin, and starch, so the final carbohydrate-based polymer material includes deodorant dispersed therein. Agent in 20 ppm (0.002%) by weight. In each sample, the ratio of the carbohydrate-based polymer material to the deodorant (NuPlastiQ or ESR to ORA) was 50,000: 1.

The characteristics of this sample are shown in Table 12.

In contrast to the samples with the same remaining ingredients of Example 10, these samples no longer have a slightly unique odor as described in Example 10. This difference in odor is particularly noticeable in relatively closed geometric configurations, such as when the mixture is shaped into a cup shape. For comparison, the cups formed from the mixture shown in Table 12 did not have a recognizable odor, similar to cups made from 100% polyethylene. It is surprising that such a small amount of the deodorant is enough to offset the typical unique odors associated with the carbohydrate polymer composition.

Example 12

The same sample was prepared as in Example 10, but contained a small amount of lyophilized strawberry powder as a deodorant. The powdery deodorant is dispersed in the carbohydrate-based polymer material, and the amount is 20 ppm (0.002%) by weight.

An article was formed in the same manner as in Example 10, but contained a small amount of a deodorant dispersed therein.

In contrast to the samples with the same remaining ingredients of Example 10, these samples no longer have a slightly unique odor as described in Example 10. This difference in odor is particularly noticeable in relatively closed geometric configurations, such as when the mixture is shaped into a cup shape. For comparison, the cups formed from the mixture shown in Table 13 did not have a recognizable odor, similar to cups made from 100% polyethylene. It is surprising that such a small amount of the deodorant is enough to offset the typical unique odors associated with the carbohydrate polymer composition.

Example 13

The same sample was prepared as in Example 10, but contained a small amount of lyophilized blueberry powder as a deodorant. The powdery deodorant is dispersed in the carbohydrate-based polymer material, and the amount is 20 ppm (0.002%) by weight.

An article was formed in the same manner as in Example 10, but contained a small amount of a deodorant dispersed therein.

In contrast to the samples with the same remaining ingredients of Example 10, these samples no longer have a slightly unique odor as described in Example 10. This difference in odor is particularly noticeable in relatively closed geometric configurations, such as when the mixture is shaped into a cup shape. For comparison, the cups formed from the mixture shown in Table 14 did not have a recognizable odor, similar to cups made from 100% polyethylene. It is surprising that such a small amount of the deodorant is enough to offset the typical unique odors associated with the carbohydrate polymer composition.

Example 14

Samples were prepared in a similar manner as in Example 10, but containing lyophilized vanilla extract powder in different small portions as a deodorant. The powdery deodorant is dispersed in the carbohydrate-based polymer material, and the amount is from 5 ppm (0.0005%) to 100 ppm (0.01%) by weight.

An article was formed in the same manner as in Example 10, but contained a small amount of a deodorant dispersed therein.

In contrast to the samples with the same remaining ingredients of Example 10, these samples no longer have a slightly unique odor as described in Example 10. This difference in odor is particularly noticeable in relatively closed geometric configurations, such as when the mixture is shaped into a cup shape. For comparison, the cups formed from the mixture shown in Table 15 did not have a recognizable odor, similar to cups made from 100% polyethylene. It is surprising that such a small amount of the deodorant is enough to offset the typical unique odors associated with the carbohydrate polymer composition. A relatively high amount of vanilla extract (e.g., 100 ppm or higher) will begin to contain a pleasant vanilla odor.

IV. Conclusion

As a conclusion, although various embodiments describe structural features and / or methodological behaviors with specific words, it is understood that the subject matter defined in the accompanying statements is not necessarily limited to the specific characteristics or behaviors described. What's more, these specific features and behaviors are disclosed in the form of embodiments for implementing the requested subject matter.

As a conclusion, it should be understood that the embodiments of the inventive features disclosed herein are only used to illustrate the principles of the inventive features. Other modifications are possible within the scope of this creative feature. Therefore, by way of example and not limitation, alternative configurations of this inventive feature may be used in accordance with the teachings herein. Accordingly, the inventive feature is not limited to those shown and described.

It should be noted that the scope of the present invention covers any patent application scope rewritten in accordance with any other patent application scope, including plural subsidiary items from any combination of other patent application scopes, and / or a common combination of multiple patent application scopes. It also covers the "Summary of Exemplary Concepts to Request" as described in the abstract paragraph. The scope of the present invention also covers the insertion and / or removal of any combination of features from any patented scope, the insertion into other patented scopes, or the writing of a new patented scope containing a combination of features from any other patented scope.

Claims (51)

    An article comprising: a substantially amorphous carbohydrate-based polymer material having no more than 20% crystals; and another polymer material and the substantially amorphous carbohydrate-based polymer material Mixing; of which there is at least one of the following: Compared with an article made of the other polymer material without the carbohydrate-based polymer material, the strength of the item is increased by at least 5%; or in a simulated landfill Under these conditions, the biodegradable amount of the article within 5 years is higher than that of the carbohydrate-based polymer material.         For example, the article in the scope of patent application, wherein the other polymer material includes polyolefin.         For example, the item in the scope of patent application, wherein the substantially amorphous carbohydrate-based polymer material has less than 20% crystals, preferably less than 15%, more preferably less than 10% .         For example, the item in the scope of patent application, wherein the substantially amorphous carbohydrate-based polymer material has a glass transition temperature, heat distortion temperature, or Ficca softening temperature higher than 70 ° C, preferably Above 75 ° C, preferably above 80 ° C, from 70 ° C to 100 ° C, or from 80 ° C to 100 ° C.         For example, the article in the scope of patent application, wherein the substantially amorphous carbohydrate-based polymer material has a Young's modulus of at least 1.0 GPa.         For example, the article in the scope of patent application, wherein the other polymer material includes polyethylene.         For example, the article in the patent application scope item 6, wherein the article includes a film formed by the mixture of the carbohydrate-based polymer material and polyethylene.         For example, the item in the scope of patent application, wherein the other polymer material is a polymer material including a petrochemical substrate, which itself is not biodegradable.         For example, the item in the scope of patent application, wherein the other polymer material includes polyethylene, polypropylene, polyethylene terephthalate, polyester, polystyrene, ABS, nylon, polyvinyl chloride, One or more of PBAT, or polycarbonate.         For example, the item in the scope of patent application, in which 5wt% of the carbohydrate-based polymer material is sufficient to make the other polymer material biodegradable, so that under simulated burial conditions, the item can be used within 5 years. The amount of biodegradation is higher than that of the carbohydrate-based polymer material.         For example, the item in the scope of patent application, wherein the mixture of the carbohydrate-based polymer material and the other polymer material contains at least 5 wt% of the carbohydrate-based polymer material.         For example, the article in the scope of patent application, wherein the mixture of the carbohydrate-based polymer material and the other polymer material comprises from 5wt% to 50wt% of the carbohydrate-based polymer material.         For example, the item in the scope of the patent application, wherein the mixture of the carbohydrate-based polymer material and the other polymer material comprises a carbohydrate-based polymer material from 10 wt% to 50 wt%.         For example, the article of the scope of patent application, wherein the article includes a film, the film has a thickness of less than 0.005mm, preferably from 0.002mm to 0.004mm.         For example, the article in the scope of patent application, wherein the article includes a film having a thickness from 0.0025 mm (0.1 mil) to 0.25 mm (10 mils).         For example, the item in the scope of patent application, wherein the carbohydrate-based polymer material includes a starch-based polymer material.         For example, the article under the scope of patent application No. 16, wherein the starch-based polymer material is formed of starch and plasticizer.         For example, the article under the scope of patent application No. 17, wherein the starch includes one or more of potato starch, corn starch, and cassava starch, and the plasticizer includes glycerin.         For example, the article under the scope of patent application No. 16, wherein the starch-based polymer material is formed by a mixture of at least two different starches.         For example, the article in the scope of patent application, wherein the article includes a film, the film has a drop weight strength of at least 100 grams (g) per mil (0.0254mm) thickness, preferably at least 140 per mil thickness G.         For example, the article of the scope of patent application, the strength of the article is increased by at least 10% compared with the article made of only the other polymer materials without the carbohydrate-based polymer material.         For example, the article in the scope of patent application, wherein the other polymer material includes a sustainable polymer material.         For example, the item in the scope of patent application No. 22, wherein the other polymer materials include a sustainable polymer material formed of one or more of sugar cane or corn.         For example, the item in the scope of application for patent No. 22, in which the source of at least 90% of the polymer content of the item is a sustainable resource.         For example, the article in the scope of patent application No. 22, wherein the article includes at least one of a film, a plate, a bottle, or other containers.         For example, the item in the scope of patent application No. 22, wherein the sustainable polymer material includes one or more of polyethylene, polypropylene, or polyethylene terephthalate formed from sustainable resources.         For example, the item in the scope of patent application, wherein the mixture of the substantially amorphous carbohydrate-based polymer material and the other polymer material further includes a deodorant, and the deodorant is preferably an organic deodorant Among them, in the absence of the deodorant, the carbohydrate-based polymer material makes the article have a unique charred odor of carbohydrates.         For example, the item in the scope of patent application No. 27, wherein the organic deodorant comprises a lyophilized powder.         For example, the article in the scope of patent application No. 27, wherein the organic deodorant includes vanilla extract.         For example, the article in the scope of patent application No. 27, wherein the organic deodorant includes vanilla extract.     For example, the article in the scope of patent application No. 27, wherein the organic deodorant has the following chemical structure:     For example, the article in the scope of patent application No. 27, wherein the organic deodorant is mainly composed of 4-hydroxy-3-methoxybenzaldehyde.         For example, the item in the scope of patent application No. 27, wherein the organic deodorant includes not more than 1% of the mixture, preferably not more than 0.1%, more preferably not more than 0.01%, more preferably not more than 1000ppm, It is more preferably not more than 100 ppm, more preferably not more than 50 ppm, and most preferably not more than 20 ppm.         For example, the item in the scope of patent application No. 27, wherein the proportion of the organic deodorant is from 1: 1000 to 1: 100,000, preferably not more than 1: 25,000, relative to the carbohydrate-based polymer material. To 1: 75,000.         For example, the article in the scope of patent application No. 27, wherein the organic deodorant comprises a fruit extract.         For example, the item in the scope of patent application No. 35, wherein the organic deodorant is a lyophilized organic fruit extract selected from vanilla, strawberry, blueberry, banana, apple, peach, pear, kiwi, mango, passion fruit An extract of fruit, raspberry or a composition thereof.         For example, the item in the scope of application for patent No. 36, wherein the proportion of the freeze-dried organic fruit extract in the plastic material is not more than 1: 1000 relative to the carbohydrate-based polymer material.         For example, the article under the scope of patent application No. 27, wherein the organic deodorant is contained in the carbohydrate-based polymer material.         A method for increasing the sustainability of a plastic article, and also increasing at least one of the strength or biodegradability of the plastic article, the method includes: providing a polymer material; mixing the polymer material with a substantially amorphous material Type of carbohydrate-based polymer material having no more than 20% crystals; heating the mixture to a temperature of 120 ° C to 180 ° C to melt-mix the polymer material with the substantially amorphous carbohydrate-based high Molecular material; and a plastic article formed from a mixture of the polymer material and the substantially amorphous carbohydrate-based polymer material, which has at least one of the following: and does not contain the carbohydrate-based polymer material Compared with an item made of the polymer material alone, the strength of the item is increased by at least 5%; or under simulated burial conditions, the biodegradability of the item within 5 years is higher than the carbohydrate-based polymer The amount of material.         For example, the method of claim 39 of the patent scope, wherein the polymer material itself is not biodegradable, but after being mixed with the carbohydrate-based polymer material, the polymer material is provided with biodegradability. Therefore, in Under simulated burial conditions, compared with the content of the carbohydrate-based polymer material, the difference in the biodegradability of the article within 5 years is due to the biodegradation of the polymer material.         For example, in the method of applying for the scope of patent No. 40, in which the polymer material is not biodegradable, at least 25% cannot be biodegraded within 3 years.         For example, the method of claim 39, wherein the article comprises a film having a drop weight strength of at least 100 grams per mil, preferably at least 140 grams per mil.         For example, the method of claim 39, wherein the strength of the article is increased by at least 10% compared with an article made of only the other polymer material without the carbohydrate-based polymer material.         For example, the method of claim 39, wherein forming the plastic article includes blowing a plastic film with a film blowing device, and the film is composed of the polymer material and the substantially amorphous carbohydrate-based polymer material. The mixture is blown, wherein: (A) when the plastic film is blown, the film blowing device operates at a high inflation ratio of at least 2.0, wherein the high inflation ratio provides the resulting plastic film with increased strength ; And / or (B) the die gap of the film blowing device is a narrow die gap of not more than 500 micrometers, wherein the narrow die gap enables the blown plastic film to have enhanced strength.         For example, the method of claim 44 in which the film has a thickness from 0.0025 mm (0.1 mil) to 0.25 mm (10 mils).         For example, the method of claim 45, wherein the film has a thickness of less than 0.005 mm, preferably from 0.002 mm to 0.004 mm.         For example, the method according to item 44 of the patent application range, wherein the inflation ratio is from 2.2 to 2.8.         For example, the method according to item 44 of the patent application scope, wherein the inflation ratio is 2.5.         For example, the method according to item 44 of the patent application range, wherein the strength of the plastic film is increased by the high inflation ratio.         For example, the method according to item 44 of the patent application range, wherein the inflation ratio is at least 2.0, and the mold gap is not more than 500 microns.         For example, the method according to item 44 of the patent application, wherein the mold gap is from 250 microns to 500 microns.