Single-use product

Abstract

This invention relates to single-use products made from composite materials, processes for making single-use products, and premixes that can be used in such processes. The inventors have developed composite materials comprising a combination of a non-wood lignocellulosic material and a biodegradable and / or compostable polyester, preferably a polyhydroxyalkanoate. Such composites can be processed into molded articles such as cups, plates, straws, and cutlery, possessing functionality suitable for replacing conventional SUPs produced from petrochemical-based plastics. The lignocellulosic material can originate from by-products of agro-food production. The production of these composite materials and their processing into molded (single-use) articles is straightforward, can be carried out using conventional machinery, and consumes relatively small amounts of energy, chemicals, and / or water.

Description

Technical Field

[0001] The present invention belongs to the field of single - use products. More specifically, the present invention relates to single - use products made from composite materials that can assist in reducing the environmental impact of so - called single - use products. The present invention also relates to a new process for making single - use products, and further to premixes that can be used in such a process.

Background Art

[0002] The term single - use plastic or SUP is used to mean a product that is used once or for a short time and disposed of immediately after use. Examples of the most frequently encountered single - use plastic products include packaging, shopping bags, disposable tableware, etc. Single - use plastics are still mainly made from fossil - fuel - based chemicals (petrochemicals).

[0003] The impact of single-use plastic waste on the (global) environment and human health is substantial. The vast majority of petrochemical-based plastics do not decompose or decompose only very slowly; in other words, they simply break down. Over time, the sun and heat gradually transform the plastic into increasingly smaller pieces until they eventually become what are known as microplastics. These microscopic plastic fragments, typically less than 5 millimeters in length, are difficult to detect and are generally ubiquitous. They eventually end up in the soil, groundwater, rivers, and oceans, entering the food chain when ingested by fish and wildlife, and ultimately reaching the human body. Recent evidence suggests that this can lead to heart attacks, strokes, and even death. Plastic waste and microplastics are particularly dangerous to wildlife, as they can easily accumulate in animals' bodies when ingested, potentially causing health problems such as organ punctures and fatal bowel obstructions. The vast majority of this pollution—mostly single-use plastic waste—comes from countries lacking the infrastructure to properly manage waste.

[0004] Over the past 20 years, attempts have been made to mitigate the problems associated with the use of (petrochemical-based) SUPs. Finding / developing alternative materials for single-use products that meet all (functional) requirements, e.g., (depending on the specific type of product): strength, durability (when wet), low fluid permeability, heat resistance, surface properties, etc., has proven to be a challenging task. Some promising results have been achieved using so-called "bioplastics" composed of polymers derived from or synthesized from plant materials. For example, it is possible to process sugarcane to produce ethylene, which can then be used to manufacture polyethylene. However, despite being bio-based, such plastics are still neither biodegradable nor compostable, thus the problem of plastic waste accumulating in the environment remains. Alternatively, it is possible to process starch to produce lactic acid, followed by polylactic acid (PLA), which is biodegradable when composted under well-controlled industrial conditions. It is possible to use such bioplastics to produce single-use products that are less harmful to the environment and (human) health. These bioplastics are attractive to businesses for reasons other than reducing plastic pollution. In other words, by using bio-based plastics, the company becomes less dependent on the price fluctuations of petrochemical materials and the associated oils around the world.

[0005] Many bioplastics also have drawbacks. For example, the process of extracting and / or synthesizing polymers from plant materials is often characterized by significant energy consumption, chemical use, and / or the generation of large streams of waste. Furthermore, the use of certain bioplastics, such as starch-based ones, would compete with food availability for overall resources (or contribute to further deforestation of land). Finally, certain bioplastics are only degradable and / or compostable under properly controlled conditions in industrial composting facilities. If products made from such bioplastics are sent to landfills (or simply left in the natural environment), they would still take a very long time to degrade. Therefore, these products are not a very effective solution to the problems associated with SUP, especially in countries / regions lacking the infrastructure for proper waste management. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a novel single-use product composed of a material that possesses desirable functionality while overcoming some or all of the drawbacks associated with bioplastics (and petrochemical-based plastics). [Means for solving the problem]

[0007] To this end, the inventors have developed composite materials comprising a combination of a non-wood lignocellular material and a biodegradable and / or compostable polyester, preferably a polyhydroxyalkanoate. Such composites can be processed into molded articles such as cups, plates, straws, and cutlery, possessing suitable functionality to replace conventional SUPs produced from petrochemical-based plastics.

[0008] For example, this composite material produces products that possess the strength, rigidity, and durability typically required to hold liquids and / or wet food products, even when used at high temperatures. The composite material of the present invention can be manufactured to have a smooth, hard surface that does not immediately begin to deteriorate when wet. Drinking straws made from this composite material offer significant advantages over, for example, paper drinking straws, which are currently commonly used as a substitute for plastic straws.

[0009] Articles made from this composite material will degrade under industrial composting and even soil composting conditions, and will not themselves result in the formation of (plastic) microparticles that persist in ecosystems (and accumulate in the food chain). In a preferred embodiment, articles made from this composite material will also degrade under freshwater or marine environmental conditions.

[0010] Although the properties of the composite material and the articles produced therefrom are particularly advantageous for application in / as SUP, the present invention is not limited in any way to that application. It will be understood by those skilled in the art that the composite material can also be used to produce articles that are actually intended for multi-use, i.e., reusable products, based on this teaching, and that articles produced in accordance with this teaching may be suitable for or intended for multi-use (reusable) without departing in any way from the scope of the present invention.

[0011] The lignocellulosic materials that constitute the significant parts of the composite material of the present invention can typically be obtained from agricultural production of many food products and components, such as cereals, legumes, maize, rice, sugarcane, and soybeans, in which case the lignocellulosic plant parts are typically obtained as waste materials. Lignocellulosic agricultural waste is still quite abundant, and its use for producing the composite material according to the present invention is unlikely to interfere with food production and / or compete with other production systems.

[0012] The production of this composite material and its processing into (single-use) articles is remarkably simple and straightforward, can be done using conventional machinery, consumes relatively small amounts of energy, chemicals, and / or water, and does not itself generate a large stream of waste that is difficult to handle.

[0013] The present invention thus provides a molded article made from the composite material, a process for producing the molded article, and a composite premix that can be processed into a molded article. These and other aspects of the present invention will become apparent to those skilled in the art based on the detailed description below and the appended examples. [Modes for carrying out the invention]

[0014] In a first aspect, the present invention provides a fabricated article comprising a three-dimensional monolithic body made of a composite material comprising a non-wood lignocellulosic material and a biodegradable and / or compostable polyester, preferably a polyhydroxyalkanoate.

[0015] For the purposes of this invention, the term “molded article” should be understood to mean any three-dimensional solid article that has acquired a shape, the shape of which remains unchanged under the normal ambient conditions and / or normal conditions of use of the article.

[0016] The fabricated articles of the present invention typically include a monolithic body composed of a composite material as its main or sole part. As used herein, the term “monolithic body” is defined as an object having only one integral piece or part of material and not consisting of two or more discrete macroscopic layers or parts of material. Therefore, a “monolithic body” does not include, for example, a multi-layer laminate, but nevertheless, in principle, it can be a part of a multi-layer laminate. As will be understood by those skilled in the art, based on this teaching, the composite material of the present invention provides most or all of the functionality typically required for many single-use products, and it can be processed into substantially any shape. Therefore, many of the products currently envisioned may simply consist of a monolithic body composed entirely of the composite material, but the present invention is not necessarily limited to this association. In some embodiments of the present invention, the fabricated article may include a plurality of interconnecting or mounting parts, including at least one monolithic body composed of the composite material.

[0017] In a particularly preferred embodiment of the present invention, the molded article is a disposable article or item, preferably a disposable article or item selected from the group consisting of (drinking) straws, cutlery such as spoons, forks, knives, and chopsticks, plates, drinking cups, lollipop sticks, plant pots, cotton swaps, and the like.

[0018] The term “composite material” means a combination of at least two types of materials that, in combination, impart one or more properties that are typically not achievable by using either of the materials individually. Generally speaking, a composite material has a continuous matrix and a discrete load. While we do not wish to be bound by any particular theory, it is currently considered that the composite material of the present invention can best be observed / described as a discrete load of non-wood lignocellular particles embedded, surrounded, and / or retained and integrated by a matrix composed of biodegradable polyester, preferably polyhydroxyalkanoate.

[0019] The term "lignocellulosic material" is generally understood to mean the cell wall material that typically constitutes the majority of non-substance plant tissues, and is understood to include cellulose, hemicellulose, and lignin as its main components. The presence of substantial amounts of lignin and the absence of substantial amounts of pectin distinguish lignocellulosic (non-substance) material from cellulose material obtainable from substance plant tissue. The relative amounts of cellulose, hemicellulose, and lignin contained in lignocellulosic material can vary depending on its source. Furthermore, as is generally known to those skilled in the art, lignin found in non-wood sources, including lignin found in the hardened seed husks of such sources, is structurally different from lignin found in hardwood sources and / or softwood sources. As already suggested above in this specification, it is particularly preferable according to the present invention that lignocellulosic material is derived from non-wood material. In one embodiment of the present invention, the non-wood lignocellulosic plant material is agricultural residue from a plant or crop selected from a group of grasses. In one embodiment of the present invention, the non-wood lignocellulosic plant material is agricultural residue selected from the group consisting of flax, hemp, bagasse, wheat straw, barley straw, oat straw, rye straw, rice straw, sugarcane, maize stalk, cotton, tobacco, bamboo, and the husks or shells of grains, rice, etc. Preferably, the non-wood lignocellulosic plant material is agricultural residue selected from the group consisting of flax, hemp, wheat straw, barley straw, oat straw, rye straw, maize stalk, cotton, tobacco, bamboo, and the husks or shells of wheat, barley, oats, and rye, and more preferably, the non-wood lignocellulosic plant material is wheat straw. In relation to the present invention, it is also conceivable that two or more non-wood lignocellulosic plant materials may be used in combination.

[0020] In one embodiment of the present invention, the non-wood lignocellulosic plant material is not selected from sisal, sugarcane bagasse, coconut, pia saba, soybean, jute, ramie and krawa (Ananas lucidiis), rice straw, rice hulls, sugarcane and sugarcane bagasse, and preferably is not selected from rice straw, rice hulls, sugarcane and sugarcane bagasse.

[0021] As suggested above in this specification, the composite material includes particles of non-wood lignocellulosic plant material, for example, particles that can be obtained by grinding, milling, or granulating non-wood lignocellulosic plant material. In a preferred embodiment of the present invention, the particles of non-wood lignocellulosic plant material are ground, milled, or granulated to a specific particle size range. In a preferred embodiment of the present invention, the particles of non-wood lignocellulosic plant material are ground, sieved, milled, or granulated to a specific particle size range. In a particular preferred embodiment of the present invention, the composite material includes particles of non-wood lignocellulosic plant material characterized by fiber lengths in the range of 0.01 to 10 mm, for example, fiber lengths of at least 0.2 mm, at least 0.3 mm, at least 0.4 mm, or at least 0.5 mm, and / or fiber lengths of less than 7.5 mm, less than 5 mm, less than 4.5 mm, less than 4 mm, less than 3.5 mm, less than 3 mm, or less than 2.5 mm. In a particular preferred embodiment of the present invention, the composite material comprises particles of non-wood lignocellulosic plant material characterized by fiber lengths in the range of 0.01 to 10 mm, for example, at least 0.015 mm, at least 0.02 mm, at least 0.03 mm, at least 0.05 mm, at least 0.075 mm, at least 0.1 mm, at least 0.2 mm, at least 0.3 mm, at least 0.4 mm, or at least 0.5 mm, and / or fiber lengths less than 7.5 mm, less than 5 mm, less than 4.5 mm, less than 4 mm, less than 3.5 mm, less than 3 mm, or less than 2.5 mm.

[0022] In certain preferred embodiments of the present invention, the composite material comprises particles of non-wood lignocellulosic plant material characterized by a fiber length in the range of 0.01 to 10 mm, preferably in the range of 0.02 to 7.5 mm, more preferably in the range of 0.03 to 3.5 mm, even more preferably in the range of 0.050 to 3.5 mm, and most preferably in the range of 0.050 to 2.5 mm. The particle size of the material of the present invention can be determined using visual / microscopic determination.

[0023] As will be understood by those skilled in the art, based on the foregoing, the composite material of the present invention comprises particles of non-wood lignocellulosic material that have not been subjected to any further treatment other than cutting and sizing operations. Specifically, the non-wood lignocellulosic material has not been subjected to any (chemical) treatment that substantially alters the chemical composition of the material, and / or any (physical / mechanical) treatment that substantially alters the primary, secondary, and / or tertiary structure of the lignocellulosic material. Therefore, in certain embodiments of the present invention, the composite material of the present invention comprises particles of a non-wood lignocellulose material characterized by cellulose, hemicellulose, and lignin content similar to or exactly the same as that of the plant material from which it is derived, for example, a cellulose content in the range of 20-60 wt.%, 25-50 wt.%, or 30-45 wt.%, a hemicellulose content in the range of 10-35 wt.%, 15-30 wt.%, or 20-25 wt.%, and / or a lignin content in the range of 10-30 wt.%, 12.5-25 wt.%, or 15-20 wt.% (all percentages are based on the total weight of the non-wood lignocellulose material). Furthermore, in certain embodiments of the present invention, the composite material of the present invention comprises particles of a non-wood lignocellulose material characterized by the presence of a network structure of cellulose, hemicellulose, and lignin fibers similar to or identical to those found in the plant material from which it is derived.

[0024] The composite material further includes a biodegradable and / or compostable polyhydroxyalkanoate.

[0025] As used herein, the term "polyhydroxyalkanoate" (PHA) encompasses both homopolymers and copolymers and can mean a single polyhydroxyalkanoate or a mixture of polyhydroxyalkanoates. To be considered "compostable", a material must meet the following four criteria: (1) the material must be biodegradable, (2) the material must be disintegratable, (3) the material must not contain more than a maximum amount of heavy metals, and (4) the material must not be ecotoxic. As used herein, the term "biodegradable" generally means the tendency of a material to chemically decompose under certain environmental conditions. Biodegradability is an inherent property of the material itself, and the material can exhibit various degrees of biodegradability depending on the specific conditions to which it is exposed. The term "disintegratable" means the tendency of a material to physically break down into smaller fragments when exposed to certain conditions. Disintegration depends on both the material itself and the physical size and configuration of the article being tested. Ecotoxicity is a measure of the effect of a material on plant life, and the heavy metal content of the material is determined according to procedures established by standard test methods.

[0026] In an embodiment, the composite material includes a biodegradable and / or compostable polyester.

[0027] Suitable examples of biodegradable and / or compostable polyesters include polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), and mixtures thereof.

[0028] Preferable examples of the biodegradable and / or compostable polyester include polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene succinate terephthalate (PBST), and mixtures thereof.

[0029] In an embodiment, the biodegradable and / or compostable polyester is polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), or polybutylene succinate adipate (PBSA).

[0030] In an embodiment, the biodegradable and / or compostable polyester is polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), or polybutylene succinate terephthalate (PBST).

[0031] In a particularly preferred embodiment of the present invention, the biodegradable and / or compostable polyester is polybutylene adipate terephthalate (PBAT). PBAT is a biodegradable random copolymer, specifically a copolyester of adipic acid, 1,4-butanediol, and terephthalic acid. PBAT is synthesized, for example, by reacting adipic acid with 1,4-butanediol to produce their polyesters (plus water), and by reacting DMT with 1,4-butanediol to similarly form their polyesters. The polyesters are then combined and reacted using tetrabutoxytitanium (TBOT) as a transesterification catalyst to produce a copolymer of the two previously prepared polymers. This is a random copolymer because there is no control whatsoever on the dispersion or block structure of the polymer chain length in the copolymerization reaction. In other words, the repeating positions are not controlled. Products suitable for use according to the present invention are sold by BASF under the trade name ECOFLEX®.

[0032] When used in combination with one or more other polyesters such as PHA, PBS, or PBSA, PBAT typically constitutes the majority of the polyester mixture, and preferably the mixture contains PBAT and (one or more) further polyesters in a weight ratio of at least 1 / 0.75, for example, at least 1 / 0.50, at least 1 / 0.40, at least 1 / 0.30, at least 1 / 0.20, or at least 1 / 0.10, and / or in a ratio of less than 1 / 0.01, less than 1 / 0.025, less than 1 / 0.05, or less than 1 / 0.10.

[0033] When used in combination with one or more other polyesters such as PHA, PBS, or PBSA, PBST, PBAT typically constitutes the majority of the polyester mixture, and preferably the mixture contains PBAT and (one or more) further polyesters in a weight ratio of at least 1 / 0.75, for example, at least 1 / 0.50, at least 1 / 0.40, at least 1 / 0.30, at least 1 / 0.20, or at least 1 / 0.10, and / or in a ratio of less than 1 / 0.01, less than 1 / 0.025, less than 1 / 0.05, or less than 1 / 0.10.

[0034] In preferred embodiments, when the polyester is PHA, the admixture contains less than 15 wt.% of the total (dry) weight of the composite material, one or more other polyesters or combinations thereof selected from PBAT, polycaprolactone, and polylactic acid, and preferably less than 10 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, or less than 1 wt.%.

[0035] In preferred embodiments, the biodegradable and / or compostable polyhydroxyalkanoate is of formula (I) [ka] (In the formula, R is independently of hydrogen and C1-C in each case. 16 From the group consisting of alkyl groups, preferably selected from the group consisting of hydrogen and C1-C9 alkyl groups, m is independently selected from 1 to 16 in each case, preferably from 1 to 2. It is a homopolymer or copolymer represented by [the specified symbol].

[0036] In a preferred embodiment, the total number of carbon atoms in each monomer present in the polyhydroxyalkanoate represented by formula (I) is 4 to 16.

[0037] In preferred embodiments, the biodegradable and / or compostable polyhydroxyalkanoate is a homopolymer or copolymer of one or more monomers selected from the group consisting of 3-hydroxybutyrate (3HB), 4-hydroxybutyrate (4HB), 3-hydroxyvalerate (3HV), 3-hydroxyhexanoate (3HHx), 3-hydroxyheptanoate (3HH), 3-hydroxyoctanoate (3HO), 3-hydroxynonanoate (3HN), 3-hydroxydecanoate (3HD), 3-hydroxyundecanoate (3HUD), and 3-hydroxydodecanoate (3HDD).

[0038] In preferred embodiments, the biodegradable and / or compostable polyhydroxyalkanoate is a homopolymer of 3-hydroxybutyrate or 4-hydroxybutyrate or a copolymer containing 3-hydroxybutyrate and / or 4-hydroxybutyrate, preferably a homopolymer of 3-hydroxybutyrate or 4-hydroxybutyrate or a copolymer containing 3-hydroxybutyrate and 4-hydroxybutyrate, more preferably a homopolymer of 3-hydroxybutyrate or 4-hydroxybutyrate or a copolymer containing 3-hydroxybutyrate and 4-hydroxybutyrate, and even more preferably a copolymer containing 3-hydroxybutyrate and 4-hydroxybutyrate.

[0039] In a particularly preferred embodiment, the biodegradable and / or compostable polyhydroxyalkanoate is a copolymer of 3-hydroxybutyrate and 4-hydroxybutyrate having a 4-hydroxybutyrate content of at least 5 mol%, preferably at least 10 mol%, more preferably at least 15 mol%, even more preferably at least 25 mol%, and most preferably at least 30 mol%.

[0040] In a particularly preferred embodiment, the biodegradable and / or compostable polyhydroxyalkanoate is a copolymer of 3-hydroxybutyrate and 4-hydroxybutyrate having a 4-hydroxybutyrate content of at most 99 mol%, preferably at most 95 mol%, and more preferably at most 90 mol%.

[0041] In preferred embodiments, the biodegradable and / or compostable polyhydroxyalkanoates are poly(3-hydroxybutyrate) (P3HB), poly(4-hydroxybutyrate) (P4HB), poly(3-hydroxyvalerate) (P3HV), poly(3-hydroxyhexanoate) (P3HHx), poly(3-hydroxyheptanoate) (P3HH), poly(3-hydroxyoctanoate) (P3HO), poly(3-hydroxynonanoate) (P3HN), poly(3-hydroxydecanoate) (P3HD), poly(3- Poly(hydroxyundecanoate)(P3HUD), poly(3-hydroxydodecanoate)(P3HDD), poly(3-hydroxybutyrate-co-3-hydroxyvalerate)(P3HB3HV), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxyvalerate)(P3HB3HV4HV or P3HB3HV), poly(3-hydroxybutyrate-co-3-hydroxybutyrate)(P3HB4HB), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(P3HB3HH (x), poly(3-hydroxyoctanoate-co-3-hydroxyhexanoate)(P3HO3HHx), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate)(P3HB3HO), poly(3-hydroxybutyrate-co-3-hydroxydecanoate)(P3HB3HD) are selected from the group, preferably poly(4-hydroxybutyrate)(P4HB), poly(3-hydroxyvalerate)(P3HV), poly(3-hydroxyhexanoate)(P3HHx), poly(3-hydroxyheptanoate)( P3HH), poly(3-hydroxyoctanoate)(P3HO), poly(3-hydroxynonanoate)(P3HN), poly(3-hydroxydecanoate)(P3HD), poly(3-hydroxyundecanoate)(P3HUD), poly(3-hydroxydodecanoate)(P3HDD), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxyvalerate)(P3HB3HV4HV) or P3HB3HV), poly(3-hydroxybutyrate-co-3-hydroxybutyrate)(P3HB4HB),This is a homopolymer or copolymer selected from the group consisting of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HHx), poly(3-hydroxyoctanoate-co-3-hydroxyhexanoate) (P3HO3HHx), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (P3HB3HO), and poly(3-hydroxybutyrate-co-3-hydroxydecanoate) (P3HB3HD).

[0042] In preferred embodiments, the biodegradable and / or compostable polyhydroxyalkanoate is selected from the group consisting of poly(3-hydroxybutyrate)(P3HB), poly(4-hydroxybutyrate)(P4HB), and poly(3-hydroxybutyrate-co-3-hydroxybutyrate)(P3HB4HB), and preferably the biodegradable and / or compostable polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxybutyrate)(P3HB4HB).

[0043] In a particularly preferred embodiment, the biodegradable and / or compostable polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxybutyrate)(P3HB4HB) having a 4-hydroxybutyrate content of at least 5 mol%, preferably at least 10 mol%, more preferably at least 15 mol%, even more preferably at least 25 mol%, and most preferably at least 30 mol%.

[0044] In a particularly preferred embodiment, the biodegradable and / or compostable polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxybutyrate)(P3HB4HB) having a 4-hydroxybutyrate content of at least 99 mol%, preferably at least 95 mol%, and more preferably at least 90 mol%.

[0045] In embodiments, a composite material according to the present invention is provided, comprising a biodegradable and / or compostable polyhydroxyalkanoate and other polyesters, specifically other polyesters selected from PBAT, polycaprolactone, and polylactic acid, in amounts of less than 15 wt.%, preferably less than 10 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, or less than 1 wt.%, based on the total (dry) weight of the composite material.

[0046] In embodiments, the present invention provides a composite material comprising a biodegradable and / or compostable polyhydroxyalkanoate and other polyesters, specifically other polyesters selected from PBAT, PBST, polycaprolactone, and polylactic acid, in amounts of less than 15 wt.%, preferably less than 10 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, or less than 1 wt.%, based on the total (dry) weight of the composite material.

[0047] Some monomers that can be used to produce polyhydroxyalkanoates contain a chiral center and therefore exist as enantiomers. According to the present invention, the chemical structures described herein, and therefore the compounds of the present invention, encompass all enantiomers of the corresponding compounds. However, since polyhydroxyalkanoates and the monomers incorporated therein are also generally produced by microorganisms from naturally occurring resources, including sugars, lipids, or amino acids, the preferred enantiomers are those obtained from their respective naturally occurring resources.

[0048] When used in combination with one or more other polyesters, the polyhydroxyalkanoate constitutes the majority of the polyester mixture, preferably the mixture comprising the polyhydroxyalkanoate and (one or more) further polyesters in a weight ratio of at least 1 / 0.75, for example, at least 1 / 0.50, at least 1 / 0.40, at least 1 / 0.30, at least 1 / 0.20, or at least 1 / 0.10, and / or in a ratio of less than 1 / 0.01, less than 1 / 0.025, less than 1 / 0.05, or less than 1 / 0.10.

[0049] In preferred embodiments of the present invention, biodegradable polyesters, preferably polyhydroxyalkanoates having a melting point in the range of 60 to 200°C, preferably 80 to 175°C, 90 to 150°C, or 100 to 125°C, are used. In particular, when used to produce articles in which the biocomposite will / may come into contact with a boiling substance or liquid during the intended use, it is preferable to select a biodegradable polyester, preferably a polyhydroxyalkanoate having a melting point above 100°C.

[0050] As will be apparent to those skilled in the art, according to this specification, the composite material is typically produced and molded at a temperature above the melting temperature of the polyester, preferably polyhydroxyalkanoate material, thereby yielding a polyester, preferably polyhydroxyalkanoate material that is typically distributed to substantially uniformly cover the surface of the non-wood lignocellulosic material particles, as well as resulting in increased adhesion of the particles and the formation of a composite material having the desired properties.

[0051] In certain embodiments of the present invention, the composite material comprises at least 35 wt.%, preferably at least 40 wt.%, at least 45 wt.%, at least 50 wt.%, at least 55 wt.%, at least 60 wt.%, at least 65 wt.%, or at least 70 wt.% of the total (dry) weight of the composite material, of the non-wood lignocellulosic material. The composite material typically comprises less than 99 wt.%, for example, less than 95 wt.%, less than 90 wt.%, less than 85 wt.%, or less than 80 wt.%, of the total (dry) weight of the composite material, of the non-wood lignocellulosic material.

[0052] In certain embodiments of the present invention, the composite material contains biodegradable polyester in an amount of at least 1 wt.%, preferably at least 2.5 wt.%, at least 5 wt.%, at least 7.5 wt.%, at least 10 wt.%, at least 12.5 wt.%, at least 15 wt.%, at least 17.5 wt.%, or at least 20 wt.%, based on the total (dry) weight of the composite material. The composite material typically contains non-wood lignocellular material in an amount of less than 65 wt.%, for example, less than 50 wt.%, less than 40 wt.%, less than 35 wt.%, or less than 30 wt.%, based on the total (dry) weight of the composite material.

[0053] In certain embodiments of the present invention, the composite material contains a biodegradable polyhydroxyalkanoate in an amount of at least 1 wt.%, preferably at least 2.5 wt.%, at least 5 wt.%, at least 7.5 wt.%, at least 10 wt.%, at least 12.5 wt.%, at least 15 wt.%, at least 17.5 wt.%, or at least 20 wt.% based on the total (dry) weight of the composite material. Typically, the composite material contains a biodegradable polyhydroxyalkanoate in an amount of less than 65 wt.%, for example, less than 60 wt.%, less than 50 wt.%, less than 45 wt.%, less than 40 wt.%, less than 35 wt.%, or less than 30 wt.%, based on the total (dry) weight of the composite material.

[0054] In a particular embodiment of the present invention, the composite material comprises a biodegradable polyester and a non-wood lignocellulosic material such that the ratio (w / w) of the biodegradable polyester to the non-wood lignocellulosic material is at least 0.05, for example, at least 0.1, at least 0.25, at least 0.40, at least 0.50, at least 0.60, or at least 0.75.

[0055] In a particular embodiment of the present invention, the composite material comprises a biodegradable polyhydroxyalkanoate and a non-wood lignocellulosic material in (relative) amounts such that the ratio (w / w) of the biodegradable polyhydroxyalkanoate to the non-wood lignocellulosic material is at least 0.05, for example, at least 0.1, at least 0.25, at least 0.40, at least 0.50, at least 0.60, or at least 0.75.

[0056] In a particular embodiment of the present invention, the composite material comprises a biodegradable polyester and a non-wood lignocellulosic material such that the ratio (w / w) of the biodegradable polyester to the non-wood lignocellulosic material is at most 3, for example, at most 2.5, at most 2, at most 1.75, at most 1.5, at most 1.25, at most 1, or at most 0.75.

[0057] In a particular embodiment of the present invention, the composite material comprises a biodegradable polyhydroxyalkanoate and a non-wood lignocellulosic material in a (relative) amount such that the ratio (w / w) of the biodegradable polyhydroxyalkanoate to the non-wood lignocellulosic material is at most 10, for example, at most 7.5, for example, at most 5, for example, at most 2.5, at most 2, at most 1.75, at most 1.5, at most 1.25, at most 1, or at most 0.75. In a particular embodiment of the present invention, the composite material comprises a biodegradable polyester and a non-wood lignocellulosic material such that the ratio (w / w) of the biodegradable polyester to the non-wood lignocellulosic material is in the range of 0.05 to 3, for example, in the range of 0.1 to 2.5, in the range of 0.25 to 2, or in the range of 0.5 to 1.5.

[0058] In a particular embodiment of the present invention, the composite material comprises a biodegradable polyhydroxyalkanoate and a non-wood lignocellulosic material in (relative) amounts such that the ratio (w / w) of the biodegradable polyhydroxyalkanoate to the non-wood lignocellulosic material is in the range of 0.05 to 3, for example, in the range of 0.1 to 2.5, in the range of 0.25 to 2, or in the range of 0.5 to 1.5.

[0059] In certain embodiments of the present invention, the non-wood lignocellular material and the biodegradable polyhydroxyalkanoate comprise a composite material comprising at least 90 wt.% (based on total dry weight), for example, at least 92.5 wt.%, at least 95 wt.%, at least 96 wt.%, at least 97.5 wt.%, and at least 98 wt. (on-wood) lignocellular material and a biodegradable polyhydroxyalkanoate combination.

[0060] In certain embodiments of the present invention, the composite material exhibits at least 60 percent biodegradation over a period of 45 days or less when tested at a temperature of 58°C (±2°C) under aerobic composting conditions in accordance with ISO 14855-1 (2012). In some cases, it is possible to exhibit at least 60 percent biodegradation over a period of 44 days or less, or 43 days or less, or 42 days or less, or 41 days or less, or 40 days or less, or 39 days or less, or 38 days or less, or 37 days or less, or 36 days or less, or 35 days or less, or 34 days or less, or 33 days or less, or 32 days or less, or 31 days or less, or 30 days or less, or 29 days or less, or 28 days or less, or 27 days or less when tested under such conditions, also known as “industrial composting conditions”. These conditions must not be aqueous or anaerobic. In some embodiments, the composite material may exhibit a total biodegradation of at least about 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 87, or at least 88, or at least 89, or at least 90, or at least 91, or at least 92, or at least 93, or at least 94, or at least 95 percent when tested in accordance with ISO 14855-1 (2012) over a period of 45 days under industrial composting conditions. In some cases, composite materials may exhibit biodegradation of at least approximately 91, at least 92, at least 93, at least 94, at least 95, at least 96, at least 97, at least 98, at least 99, or at least 99.5 percent within a range of 180 days or less, when measured in accordance with ISO 14855-1 (2012) under industrial composting conditions, or composite materials may exhibit 100 percent biodegradation within a range of 180 days or less.Additionally or alternatively, composite materials may exhibit a minimum of 90 percent biodegradation within a range of approximately 175 days or less, or 170 days or less, or 165 days or less, or 160 days or less, or 155 days or less, or 150 days or less, or 145 days or less, or 140 days or less, or 135 days or less, or 130 days or less, or 125 days or less, or 120 days or less, or 115 days or less, or 110 days or less, or 105 days or less, or 100 days or less, or 95 days or less, or 90 days or less, or 85 days or less, or 80 days or less, or 75 days or less, or 70 days or less, or 65 days or less, or 60 days or less, or 55 days or less, or 50 days or less, or 45 days or less, when measured in accordance with ISO 14855-1 (2012) under industrial composting conditions. In some cases, composite materials may be biodegradable to at least approximately 97, 98, 99, or 99.5 percent in tests conducted under industrial composting conditions in accordance with ISO 14855-1 (2012) for a range of approximately 65 days or less, or 60 days or less, or 55 days or less, or 50 days or less, or 45 days or less.

[0061] In certain embodiments of the present invention, the composite material exhibits at least 90 percent biodegradation within a range of one year or less, when measured in accordance with ISO 14855-1 (2012) under home composting conditions. In some cases, the composite material may exhibit at least about 91, or at least 92, or at least 93, or at least 94, or at least 95, or at least 96, or at least 97, 99, or at least 8, or at least 99, or at least 99.5 percent biodegradation within a range of one year or less, when measured in accordance with ISO 14855-1 (2012) under home composting conditions, or the composite material may exhibit 100 percent biodegradation within a range of one year or less. In some cases, composite materials may exhibit at least 90 percent biodegradation within a range of approximately 350 days or less, or 325 days or less, or 300 days or less, or 275 days or less, or 250 days or less, or 225 days or less, or 220 days or less, or 210 days or less, or 200 days or less, or 190 days or less, or 180 days or less, or 170 days or less, or 160 days or less, or 150 days or less, or 140 days or less, or 130 days or less, or 120 days or less, or 110 days or less, or 100 days or less, or 90 days or less, or 80 days or less, or 70 days or less, or 60 days or less, or 50 days or less, when measured in accordance with ISO 14855-1 (2012) under home composting conditions. In some cases, composite materials may be biodegradable to at least about 97%, at least 98%, at least 99%, or at least 99.5 percent in tests conducted under home composting conditions in accordance with ISO 14855-1 (2012) for a range of about 70 days or less, or 65 days or less, or 60 days or less, or 50 days or less. In certain embodiments of the tests of the preceding embodiments, the specifications for significant organic components as specifically provided in EN 13432 (2000) (§A.2.1) and the disclaimers for naturally occurring materials as specifically provided in EN 13432 (2000) (§4.3.2) may apply.

[0062] In certain embodiments of the present invention, the composite material exhibits at least 60 percent soil biodegradation within a range of 130 days or less when measured in accordance with ISO 17556 (2012) under aerobic conditions and ambient temperature. In some cases, the composite material may exhibit at least 60 percent biodegradation within a period of 130 days or less, or 120 days or less, or 110 days or less, or 100 days or less, or 90 days or less, or 80 days or less, or 75 days or less when tested under such conditions, also known as “soil composting conditions.” These conditions must not be aqueous or anaerobic conditions. In some cases, the composite material may exhibit total biodegradation of at least about 65%, or at least 70%, or at least 72%, or at least 75%, or at least 77%, or at least 80%, or at least 82%, or at least 85 percent when tested in accordance with ISO 17556 (2012) over a period of 195 days under soil composting conditions. To be considered "biodegradable," under soil composting conditions in accordance with (international) national standards and regulations, the material must typically exhibit at least 90 percent biodegradation in total (e.g., compared to an initial sample), or at least 90 percent of the maximum degradation of a suitable reference material after both the reference and test items have reached a plateau. The maximum test duration for biodegradability under soil composite conditions is two years. Composite materials may exhibit at least 90 percent biodegradation within a range of two years, 1.75 years, one year, nine months, or six months or less, when measured under soil composting conditions in accordance with ISO 17556 (2012). In some cases, the composite material may exhibit biodegradation of at least approximately 91, at least 92, at least 93, at least 94, at least 95, at least 96, at least 97, at least 98, at least 99, or at least 99.5 percent within a range of two years or less, when measured in accordance with ISO 17556 (2012) under soil composting conditions, or the composite material may exhibit 100 percent biodegradation within a range of two years or less.Additionally or alternatively, composite materials may exhibit at least 90 percent biodegradation within a range of approximately 700, 650, 600, 550, 500, 450, 400, 350, 300, 275, 250, 240, 230, 220, 210, 200, or 195 days or less, when measured in accordance with ISO 17556 (2012) under soil composting conditions. In some cases, composite materials may be biodegradable to at least approximately 97, at least 98, at least 99, or at least 99.5 percent in tests conducted in accordance with ISO 17556 (2012) under soil composting conditions within a range of approximately 225 days or less, or 220 days or less, or 215 days or less, or 210 days or less, or 205 days or less, or 200 days or less, or 195 days or less. In certain embodiments of the tests of the preceding embodiments, the specifications for significant organic components as specifically provided in EN13432(2000)(§A.2.1) and the disclaimers for naturally occurring materials as specifically provided in EN13432(2000)(§4.3.2) may apply.

[0063] In certain embodiments of the present invention, the composite material exhibits at least 90 percent biodegradation within a range of 56 days or less, when measured under aqueous aerobic conditions in accordance with ISO 14851 (2019) or ISO 14852 (2021). In some cases, the composite material may exhibit at least about 91, at least 92, at least 93, at least 94, at least 95, at least 96, at least 97, 99, at least 8, at least 99, or at least 99.5 percent biodegradation within a range of 56 days or less, when measured under aqueous aerobic conditions in accordance with ISO 14851 (2019) or ISO 14852 (2021), or the composite material may exhibit 100 percent biodegradation within a range of 56 days or less. In some cases, composite materials may exhibit at least 90 percent biodegradation within a range of approximately 55 days or less, or 52.5 days or less, or 50 days or less, or 47.5 days or less, or 45 days or less, or 42.5 days or less, or 40 days or less, or 37.5 days or less, or 35 days or less, or 32.5 days or less, or 30 days or less, or 27.5 days or less, or 25 days or less, or less, or 22.5 days or less, or 20 days or less, or 19 days or less, or 18 days or less, or 17 days or less, or 16 days or less, or 15 days or less, or 14 days or less, or 13 days or less, or 12 days or less, or 10 days or less, when measured in accordance with ISO 14851 (2019) or ISO 14852 (2021) under aqueous aerobic conditions. In some cases, composite materials may be biodegradable to at least about 97%, at least 98%, at least 99%, or at least 99.5 percent in tests conducted under aqueous aerobic conditions in accordance with ISO 14851 (2019) or ISO 14852 (2021) for a range of about 45 days or less, or 40 days or less, or 35 days or less, or 25 days or less. In certain embodiments of the tests of the preceding embodiments, the specifications for significant organic components as specifically provided in EN 13432 (2000) (§A.2.1) and the disclaimers for naturally occurring materials as specifically provided in EN 13432 (2000) (§4.3.2) may apply.

[0064] In certain embodiments of the present invention, the composite material exhibits at least 90 percent biodegradation within a range of 6 months or less, when measured in accordance with ASTM D6691 (2017) under aerobic conditions in seawater. In some cases, the composite material may exhibit at least about 91, at least 92, at least 93, at least 94, at least 95, at least 96, at least 97, 99, at least 8, at least 99, or at least 99.5 percent biodegradation within a range of 6 months or less, when measured in accordance with ASTM D6691 (2017) under aerobic conditions in seawater, or the composite material may exhibit 100 percent biodegradation within a range of 6 months or less. In some cases, composite materials may exhibit at least 90 percent biodegradation within a range of approximately 175 days or less, or 162.5 days or less, or 150 days or less, or 137.5 days or less, or 125 days or less, or 112.5 days or less, or 110 days or less, or 105 days or less, or 100 days or less, or 95 days or less, or 90 days or less, or 85 days or less, or 80 days or less, or 75 days or less, or 70 days or less, or 65 days or less, or 60 days or less, or 55 days or less, or 50 days or less, or 45 days or less, or 40 days or less, or 35 days or less, or 30 days or less, or 25 days or less, when measured in accordance with ASTM D6691 (2017). In some cases, composite materials may be biodegradable by at least approximately 97, at least 98, at least 99, or at least 99.5 percent in tests conducted in accordance with ASTM D6691 (2017) under aerobic conditions in seawater for a range of approximately 70 days or less, or 65 days or less, or 60 days or less, or 50 days or less.

[0065] In certain embodiments of the present invention, the composite material contains virtually no polylactic acid (PLA), and for example, preferably, the composite material contains PLA in an amount of less than 5 wt.% based on the total (dry) weight of the composite, for example, less than 2.5 wt.%, less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.%. In certain preferred embodiments of the present invention, the composite material is essentially or completely PLA-free.

[0066] In certain embodiments of the present invention, the composite material contains virtually no starch or starch-based polymers, for example, preferably, the composite material contains less than 5 wt.% of starch and / or starch-based polymers based on the total (dry) weight of the composite, for example, less than 2.5 wt.%, less than 1 wt.%, less than 0.5 wt.%, or less than 0.1 wt.% (combined). In certain preferred embodiments of the present invention, the composite material is essentially or completely starch and / or starch-based polymer-free.

[0067] As described above in this specification, the composite materials of the present invention typically impart the strength and stiffness typically required for (single-use) items such as plates, cups, and cutlery. Stiffness, along with strength, hardness, and toughness, is one of the key mechanical properties of plastics. The stiffness of a plastic is its ability to distribute load and resist deformation or deflection (failure to function). The stiffness of a plastic can be expressed as the flexural modulus. The strength of a plastic, typically expressed as tensile strength, reflects how much stress the plastic can withstand when stretched or pulled without fracturing (physical failure). Stiffness and strength are often required to work together in demanding applications.

[0068] In preferred embodiments, the composite material of the present invention has a flexural modulus in the range of 1500 to 5000 MPa, preferably in the range of 2000 to 4000 MPa, more preferably in the range of 2500 to 3500 MPa, and most preferably in the range of 2700 to 3100 MPa, as determined in accordance with DIN 53457. In preferred embodiments, the composite material of the present invention has a flexural strength in the range of 40 to 100 MPa, preferably in the range of 50 to 90 MPa, more preferably in the range of 55 to 80 MPa, and most preferably in the range of 60 to 70 MPa.

[0069] In preferred embodiments, the composite material of the present invention has a tensile modulus in the range of 1500 to 4000 MPa, preferably in the range of 1800 to 3500 MPa, more preferably in the range of 2000 to 3000 MPa, and most preferably in the range of 2200 to 2600 MPa, as determined in accordance with DIN 53457.

[0070] In preferred embodiments, the composite material of the present invention has a breaking strength in the range of 5 to 25 MPa, preferably 7.5 to 22.5 MPa, more preferably 10 to 20 MPa, and most preferably 12.5 to 17.5 MPa, as determined in accordance with DIN 53455.

[0071] In preferred embodiments, the composite material of the present invention has an elongation at break in the range of 0.5 to 5%, preferably in the range of 1 to 4%, more preferably in the range of 1.25 to 3%, and most preferably in the range of 1.5 to 2.5%, as determined in accordance with DIN 53455.

[0072] Furthermore, the composite material of the present invention can typically be used to produce articles that come into direct contact with hot (liquid or (semi)solid) compositions, including liquids that are specifically boiling during use. Therefore, in preferred embodiments of the present invention, the composite material can resist significant deformation and / or damage at temperatures in the range of 80–100°C. In preferred embodiments, the composite material of the present invention has a Vicat softening temperature (Rate B, 10N) greater than 85°C, more preferably greater than 87.7°C, even more preferably greater than 90°C, and most preferably greater than 92.5°C, as determined in accordance with ASTM D1525. Furthermore, in preferred embodiments, the composite material of the present invention has a thermal strain temperature (Metot B, 0.45MPa) at least 70°C, more preferably at least 75°C, even more preferably at least 77.5°C, and most preferably at least 80°C, as determined in accordance with ASTM D648.

[0073] A second aspect of the present invention provides a method for producing a molded article as defined herein, the method being as follows: a) A step of providing a certain amount of crushed / finely ground non-wood lignocellulosic plant material as defined herein, b) Providing a certain amount of a biodegradable or compostable polyester, preferably a polyhydroxyalkanoate, as defined herein; c) A step of mixing the pulverized / fine-grained lignocellular plant material with the particulate biodegradable and / or compostable polyester, preferably polyhydroxyalkanoate, to convert it into a pumpable mass, d) A step of processing the mass into a molded article, Includes.

[0074] As will be understood by those skilled in the art, based on this teaching, step a) may include any conventional operation suitable for converting a non-wood lignocellulosic tissue, preferably containing plant material in the form of agricultural waste, into a specific composition having the morphological, chemical, and physical properties defined herein. Such operation would typically include one or more cutting and / or grinding steps to achieve a desired particle size distribution. Additional steps, such as washing, sieving, and debris removal, may also be applied as optional. As will be obvious to those skilled in the art, based on this teaching, it is preferable that the process does not include any steps that result in a modification of the chemical composition of the material. More specifically, the process does not include any steps in which the lignocellulosic material is treated with chemicals such as acids, bases, and / or peroxide treatment agents to extract a particular component. Also, as will be obvious to those skilled in the art, based on this teaching, it is preferable that the process does not include any steps that result in a modification of the primary, secondary, and / or tertiary structure of the lignocellulosic (cell wall) material. More specifically, the process does not include any step in which the lignocellular material is subjected to (high) mechanical shearing operations that alter the length and / or structure of the fiber components, such as a high-shear fibrillation treatment.

[0075] According to the present invention, step c) of the process includes the conversion of particulate lignocellulosic material and polyester, preferably polyhydroxyalkanoate, into a pumpable mass. As used within the scope of the present invention, the term “pumpable” means the ability of the composition or mass to flow under appropriate driving force. For example, the driving force required to flow the material through a tubular system can be provided by any type of positive displacement pump known in the art, such as a progressive cavity pump, piston pump, gear pump, lobe pump, diaphragm pump, peristaltic pump, screw pump, etc. The conversion of peeled raw potatoes into a pumpable mass can be achieved by mechanical processing such as slicing, pulverizing, crushing, grinding, or cutting. In a preferred embodiment of the present invention, a process as defined herein is provided, wherein step c) includes the step of combining the lignocellulosic material, biodegradable and / or compostable polyester, preferably polyhydroxyalkanoate, while heating the mixture to a temperature above the melting temperature of the polyester, preferably polyhydroxyalkanoate, and maintaining that temperature. Typically, according to the present invention, a pumpable mass is produced by combining and mixing particulate lignocellulosic material and polyester, preferably polyhydroxyalkanoate, in a molten state, and typically, the addition of further (liquid) components such as water is not required. Embodiments in which some water is added to increase followability are envisioned. In a preferred embodiment of the present invention, a process defined herein is provided in which step c) produces a mass having a dry matter content of more than 50 wt.% based on the total weight of the mass, for example, more than 75 wt.%, more than 80 wt.%, more than 85 wt.%, more than 90 wt.%, more than 92.5 wt.%, more than 95 wt.%, more than 97.5 wt.%, more than 98 wt.% or more than 99 wt.%.

[0076] Typically, step c) of the process involves heating a mixture of particulate lignocellulosic material and polyester, preferably polyhydroxyalkanoate, to a temperature above 60°C, above 70°C, above 75°C, above 80°C, above 85°C, above 90°C, above 100°C, above 110°C, above 120°C, or above 125°C and maintaining that temperature. The temperature represents the core temperature, i.e., the temperature achieved throughout the entire mass. In preferred embodiments of the present invention, the pumpable mass is not exposed to temperatures above 250°C, above 200°C, above 175°C, above 150°C, or above 140°C. Exposure of the mixture to very high temperatures over a long period of time can, in particular, cause undesirable changes to the lignocellulosic material.

[0077] Step d) of the process may include any preferred operation known to those skilled in the art. Embodiments are envisioned in which the pump-operable mass is subjected to operations such as die casting, injection molding, blow molding, and extrusion molding. As will be understood by those skilled in the art, which operation is preferable and economically feasible will depend on the type and shape of the article to be produced. In a particular preferred embodiment of the present invention, the pump-operable mass obtained in step c) is subjected to an extrusion process. The extruder typically acts as a complete processing apparatus in which the supply of lignocellulosic material and polyester, preferably polyhydroxyalkanoate, to the extruder, kneading / heating, and shaping of the mass are performed in one continuous process. In a typical setup, the extruder includes barrels with meshing co-rotating screws (or opposite-rotating screws, subject to selection) that cooperate to generate and / or maintain a homogenized mixture, which is then continuously extruded through a die to produce the shaped article. In an extruder, various regions may be distinguishable, namely: i) one or more supply zones for lignocellulosic material and polyester, preferably polyhydroxyalkanoate; ii) heating (and evaporation) zone; and iii) forming zone. In the supply zone, lignocellulosic material and polyester, preferably polyhydroxyalkanoate, are supplied to the extruder head (away from the die). In the heating zone, the mass is heated. In the forming zone, the mass is pressed through the die. In preferred embodiments, a twin-screw extruder (TSE) is utilized due to its improved mixing capacity, milder processing capacity, and improved kneading capacity. The TSE also benefits from the fact that it provides greater process control compared to a single-screw extruder and ensures reliable material transport between flights and elements on the screw. Generally, temperature control (including temperature maintenance) can be achieved through the use of external heaters strategically positioned along the zones of the extruder.The extrusion pressure typically depends on the selection of materials used, e.g., polyester, preferably polyhydroxyalkanoate; the particle size of the lignocellulosic material; the ratio of the lignocellulosic material to the polyester, preferably polyhydroxyalkanoate; the use of additional liquids; the temperature of the extrusion mass; the rate at which the lignocellulosic material and polyester, preferably polyhydroxyalkanoate, are supplied to the extruder; and the extrusion speed. According to a preferred embodiment of the present invention, the process is carried out so that the mass is subjected to a pressure drop of at least 0.5 MPa, for example, at least 1 MPa, at least 2 MPa, at least 3 MPa, at least 4 MPa, or at least 5 MPa. Typically, the process is carried out so that the mass is subjected to a pressure drop of less than 8 MPa, less than 7 MPa, less than 6 MPa, or less than 5 MPa.

[0078] The material exiting the extruder is preferably cut into pieces as it leaves the extruder, resulting in the formation of individual / discrete pieces during expansion. For this purpose, a rotating blade may be positioned adjacent to the extruder die to cut the emerging extruded flow into pieces of the desired size and shape.

[0079] According to certain embodiments, a process defined in this disclosure is provided, wherein one or more further processing steps, such as a drying and / or cooling step, are followed by step d). As will be understood by those skilled in the art, based on this teaching, it is possible to use the processes described herein to obtain molded articles that can constitute a molded article by itself (i.e., a ready-to-use article) or that can be combined with other components or materials to produce a desired article. The extrusion processes disclosed herein are particularly suitable for the production of rod-shaped or tubular products, such as drinking straws, lollipop sticks, cotton swap sticks, and chopsticks.

[0080] Further aspects of the present invention relate to products that can be obtained by any of the processes defined herein. Whenever a “formed article” and / or “monolithic body” (consisting of composite material) is referenced herein, it means the products described herein, and moreover, products that can be obtained by the processes described herein, based on their structural / chemical properties, which may be identical or different, as will be understood by those skilled in the art, based on this teaching. Specifically, properties may be unique to products obtained using the processes described herein, even if such properties are not expressly described herein.

[0081] Further aspects of the present invention are as follows: - A non-wood lignocellulosic material, the material which can be obtained by crushing, milling, or macerating a non-wood lignocellulosic plant material as defined herein above, - A biodegradable and / or compostable polyester as defined above in this specification, preferably a polyhydroxyalkanoate, The present invention relates to a product in the form of granules, pelletized compositions, or free-flowing powders containing a combination of the above.

[0082] Such products constitute a “premix” for the production of molded articles according to the present invention. As will be apparent to those skilled in the art, such premixes can be processed into molded articles by heating, mixing / kneading, and molding operations based on this teaching. The preferred properties of the particulate non-wood lignocellulosic material and particulate biodegradable and / or compostable polyester, preferably polyhydroxyalkanoate, constituting the granules will be apparent to those skilled in the art, as are disclosed herein for molded articles and the processes for making them. According to specific embodiments of the present invention, the individual particles, granules, or pellets contained in the premix comprise a combination of the non-wood lignocellulosic material and the biodegradable and / or compostable polyester, preferably polyhydroxyalkanoate; that is, in the form of a composite. Such composite particles, granules, or pellets can be produced by mixing a specific form of non-wood lignocellulosic material with a biodegradable and / or compostable polyester, preferably a polyhydroxyalkanoate, at a temperature above the melting temperature of the polyester, preferably the polyhydroxyalkanoate, and converting the mass into composite particles, granules, or pellets by any preferred means, for example, by extruding the mass, cooling it, and typically subjecting the extruded material to a grinding or cutting operation after cooling. According to a specific embodiment of the present invention, the premix is ​​characterized by having a melting temperature range of 100 to 250°C, more preferably 125 to 225°C, and most preferably 140 to 200°C. According to specific embodiments of the present invention, the premix is ​​characterized by having a melt flow index (230°C / 10kg) in the range of 0.05 to 1 g / 10min, preferably 0.075 to 0.75 g / 10min, more preferably 0.1 to 0.5 g / 10min, and most preferably 0.15 to 0.25 g / 10min, when determined in accordance with ISO 1133. These values, in particular, ensure good processability in the extrusion process.

[0083] According to specific embodiments of the present invention, the premix is ​​characterized by exhibiting a limited molding shrinkage percentage, for example, 0.5 to 2%, preferably 0.7 to 1.5%, and most preferably 0.8 to 1.25%.

[0084] Unless otherwise defined, all terms used in the disclosure of this invention, including scientific and technical terms, have the meanings that are ordinarily understood by those skilled in the art to which this invention pertains.

[0085] As used herein, "a," "an," and "the" refer to both singular and plural forms unless otherwise explicitly stated in the context. For example, "a compartment" refers to one or more compartments.

[0086] As used herein with reference to measurable values ​​such as parameters, quantities, and durations, “about” means to include variations of ±10%, more preferably ±5%, and even more preferably ±1% from the specifically indicated values, provided that such variations function adequately in the inventions of this disclosure. However, it should be understood that the values ​​themselves that the modifier “about” refers to are also specifically disclosed.

[0087] As used herein, “comprise,” “comprising,” “comprises,” and “comprised of” are synonymous with “include,” “including,” “includes,” or “contain,” “containing,” and “contains,” and are inclusive or open-ended terms that specifically indicate the existence of subsequent elements, such as components, and do not exclude or preclude the existence of other unlisted components, features, elements, members, or steps known or disclosed in the Art.

[0088] The enumeration of numerical ranges by endpoints includes all numbers and fractions contained within that range, as well as the enumerated endpoints. Those skilled in the art will see that any number of the specific features described above can be incorporated into the present invention.

[0089] Throughout this document, the use of terms in parentheses generally indicates that the terms in parentheses specifically represent possible options or possible meanings and should therefore not be considered limiting.

[0090] The advantages of the present invention will become apparent from the non-limiting examples given below, which are merely illustrative.

[0091] Particularly preferred embodiments of the present invention include the following: Embodiment 1: A molded article comprising a three-dimensional monolithic body made of a composite material comprising a non-wood lignocellulosic material and a biodegradable and / or compostable polyhydroxyalkanoate, wherein the composite material contains the biodegradable and / or compostable polyhydroxyalkanoate in an amount of less than 90 wt.% based on the total (dry) weight of the composite material, and the non-wood lignocellulosic material and the biodegradable and / or compostable polyhydroxyalkanoate together constitute at least 92.5 wt.%, preferably at least 95 wt.%, and more preferably at least 97.5 wt.% of the composite material.

[0092] Embodiment 2: The fabricated article according to Embodiment 1, wherein the non-wood lignocellulose material comprises a network structure of cellulose, hemicellulose, and lignin fibers.

[0093] Embodiment 3: The molded article according to Embodiment 1 or 2, wherein the non-wood lignocellulosic material includes particles that can be obtained by crushing, milling, or pulverizing a non-wood lignocellulosic plant material.

[0094] Embodiment 4: The molded article according to Embodiment 3, wherein the non-wood lignocellulosic plant material is selected from the group consisting of flax, hemp, bagasse, wheat straw, barley straw, oat straw, rye straw, rice straw, sugarcane, maize stalk, cotton, tobacco, bamboo, and the outer husk or shell of grains, rice, etc., preferably wheat straw.

[0095] Embodiment 5: A molded article according to any one of Embodiments 1 to 4, wherein the composite material comprises 40 to 99 wt.%, preferably 55 to 95 wt.%, and more preferably 60 to 90 wt.%, of non-wood lignocellulosic material based on the total weight of the composite material.

[0096] Embodiment 6: The molded article according to Embodiment 1, wherein the composite material does not contain polylactic acid (PLA).

[0097] Embodiment 7: The molded article according to Embodiment 1, wherein the composite material does not contain starch.

[0098] Embodiment 8: The molded article according to Embodiment 1, wherein the biodegradable and / or compostable polyhydroxyalkanoate is a homopolymer of 3-hydroxybutyrate or 4-hydroxybutyrate or a copolymer containing 3-hydroxybutyrate and / or 4-hydroxybutyrate, preferably a homopolymer of 3-hydroxybutyrate or 4-hydroxybutyrate or a copolymer containing 3-hydroxybutyrate and 4-hydroxybutyrate, more preferably a homopolymer of 3-hydroxybutyrate or 4-hydroxybutyrate or a copolymer containing 3-hydroxybutyrate and 4-hydroxybutyrate, even more preferably a copolymer containing 3-hydroxybutyrate and 4-hydroxybutyrate, most preferably a copolymer of 3-hydroxybutyrate and 4-hydroxybutyrate having a 4-hydroxybutyrate content of at least 30 mol%.

[0099] Embodiment 9: A molded article according to any one of Embodiments 1 to 8, wherein the composite material contains a biodegradable and / or compostable polyhydroxyalkanoate in an amount of 1 to 60 wt.%, preferably 5 to 45 wt.%, and more preferably 10 to 40 wt.%, based on the total (dry) weight of the composite material.

[0100] Embodiment 10: The following biodegradability characteristics: - When measured in accordance with ISO 14855-1 (2012) under industrial composting conditions, at least 90% biodegradation within a period of 180 days or less. - When measured in accordance with ISO 17556 (2012) under soil composite conditions, at least 90% biodegradation occurred within a period of 2 years or less, and - When measured in accordance with ISO 14855-1 (2012) under home composting conditions, at least 90% biodegradation within a period of one year or less. A molded article according to any one of embodiments 1 to 9, having one or more of the above.

[0101] Embodiment 11: A molded article according to any one of Embodiments 1 to 10, wherein the article is a disposable article or item, preferably a disposable article or item selected from the group consisting of (drinking) straws, cutlery such as spoons, forks, knives, chopsticks, plates, drinking cups, lollipop sticks, plant pots, cotton swaps, etc.

[0102] Embodiment 12: A product in the form of granules, free-flowing powder, or pelletized composition, wherein the product is as follows: - A particulate non-wood lignocellulosic material, wherein the material can be obtained by crushing, milling, or macerating a non-wood lignocellulosic plant material. - Particulate biodegradable and / or compostable polyhydroxyalkanoates, This includes combinations of, The composite material comprises a biodegradable and / or compostable polyhydroxyalkanoate in an amount of less than 90 wt.% based on the total (dry) weight of the composite material, and the non-wood lignocellulosic material and the biodegradable and / or compostable polyhydroxyalkanoate together constitute at least 92.5 wt.%, preferably at least 95 wt.%, and more preferably at least 97.5 wt.%, of the granules or powder in the product.

[0103] Embodiment 13: A method for producing a molded article as defined in any one of Embodiments 1 to 11, wherein the method is as follows: a) A step of providing a certain amount of crushed / finely ground non-wood lignocellulosic plant material, b) Providing a certain amount of biodegradable and / or compostable polyhydroxyalkanoate, c) A step of mixing the pulverized / fine-grained lignocellulosic plant material with the particulate biodegradable and / or compostable polyhydroxyalkanoate and processing it into a pumpable mass, d) A step of processing the mass into a molded article, Methods that include...

[0104] Embodiment 14: The method according to Embodiment 13, wherein step a) is to provide a certain amount of non-wood lignocellulosic plant material and process it with a grinder, mill, sieve, compounder, etc., to obtain a pulverized / fine material characterized by a fiber length in the range of 0.05 to 3.5 mm.

[0105] Embodiment 15: The method according to any one of Embodiments 13 to 14, wherein step d) includes die casting, injection molding, blow molding, or extrusion molding of a pump-operable mass.

[0106] Embodiment 16: The method according to any one of Embodiments 13 to 15, wherein in step c) and / or d), the pump-operable mass is preferably heated to a temperature above the melting point of a biodegradable and / or compostable polyhydroxyalkanoate, and / or to a temperature in the range of 60 to 160°C, more preferably to a temperature in the range of 70 to 150°C, and most preferably to a temperature in the range of 80 to 140°C.

[0107] Embodiment 17: A molded article that can be obtained by a process defined in any one of Embodiments 13 to 16. [Examples]

[0108] Example 1: Manufacturing of a compostable single-use article according to the present invention 1.1 Compounding of lignocellulosic materials and P(3HB) The premix according to the present invention is produced by combining 50 wt% shredded wheat straw material (processed into particles characterized by fiber lengths in the range of 0.5 to 3.5 mm) and 50 wt% P(3HB) (ENMAT Y3000P). Compounding is carried out using a co-rotating twin-screw extruder equipped with an LWF feeder, by feeding the required amount of material into the extruder side feeder, adding wheat to the process, and removing volatile substances with a vacuum vent. The screw design includes a light melting zone to avoid polymer degradation and a light mixing zone to disperse wheat and avoid compound degradation, in order to carefully melt the polymer and disperse the wheat. During compounding, the temperature in the mixing zone is set to 160°C. Subsequently, the compound is pelletized by passing it through an air-cooling unit and then processing it with a rotating knife.

[0109] 1.2 Manufacturing of single-use articles by injection molding This premix material is then processed into compostable single-use articles (cutlery) by an injection molding process, in which case the premix is ​​heated to a temperature of 190°C (to generate a mass with sufficient fluidity for the injection molding operation). Therefore, the resulting molded articles have good optical properties. The molded articles were subjected to various tests and yielded the following results.

[0110] [Table 1]

[0111] Example 2: Manufacturing of a compostable single-use article according to the present invention 2.1 Compounding of lignocellulosic materials and P(3HB3HV) The premix according to the present invention is produced by combining 50 wt% shredded wheat straw material (processed into particles characterized by fiber lengths in the range of 0.05 to 3.5 mm) with 50 wt% (3HB3HV)(M-Vera GP1045). Compounding is performed using a co-rotating twin-screw extruder equipped with an LWF feeder, by feeding the required amount of material into the extruder side feeder, adding wheat to the process, and removing volatile substances with a vacuum vent. The screw design includes a light melting zone to avoid polymer degradation and a light mixing zone to disperse wheat and avoid compound degradation, in order to carefully melt the polymer and disperse the wheat. During compounding, the temperature in the mixing zone is set to 160°C. Subsequently, the compound is pelletized by passing it through an air-cooling unit and then processing it with a rotating knife.

[0112] 2.2 Manufacturing of single-use articles by injection molding This premix material is then processed into compostable single-use articles (cutlery) by an injection molding process, in which case the premix is ​​heated to a temperature of 190°C (to generate a mass with sufficient fluidity for the injection molding operation). Therefore, the resulting molded articles have good optical properties. The molded articles were subjected to various tests and yielded the following results.

[0113] [Table 2]

[0114] Example 3: Compounding of lignocellular material and PBAT The premix according to the present invention is produced by combining 45 wt% shredded wheat straw material (processed into particles characterized by fiber lengths in the range of 0.05 to 3.5 mm) with 55 wt% PBAT (Ecoflex® F Blend A1200 ex BASF). Compounding is performed using a co-rotating twin-screw extruder equipped with an LWF feeder, by feeding the required amount of material into the extruder side feeder, adding wheat to the process, and removing volatile substances with a vacuum vent. The screw design includes a light melting zone to avoid polymer degradation and a light mixing zone to disperse wheat and avoid compound degradation, in order to carefully melt the polymer and disperse the wheat. During compounding, the temperature in the mixing zone is set to 160°C. Subsequently, the compound is pelletized by passing it through an air-cooling unit and then processing it with a rotating knife.

[0115] [Table 3]

[0116] Example 4: Manufacturing of a compostable single-use article according to the present invention (by injection molding) The premix material according to Example 3 is processed into compostable single-use articles (cutlery) by an injection molding process, in which case the premix is ​​heated to a temperature of 190°C (to generate a mass with sufficient fluidity for the injection molding operation). Therefore, the resulting molded articles have good optical properties. The molded articles were subjected to various tests and yielded the following results.

[0117] [Table 4]

Claims

1. A molded article comprising a three-dimensional monolithic body made of a composite material comprising a non-wood lignocellular material and a biodegradable and / or compostable polyester, wherein the non-wood lignocellular material and the biodegradable and / or compostable polyester are present in a ratio of at least 1:2 and constitute at least 90 wt.%, preferably at least 95 wt.%, and more preferably at least 97.5 wt.% of the composite material.

2. The molded article according to claim 1, wherein the non-wood lignocellulose material comprises a network structure of cellulose, hemicellulose, and lignin fibers.

3. The molded article according to claim 1 or 2, wherein the non-wood lignocellulosic material includes particles that can be obtained by crushing, milling, or pulverizing a non-wood lignocellulosic plant material.

4. The molded article according to claim 3, wherein the non-wood lignocellulosic plant material is selected from the group consisting of flax, hemp, bagasse, wheat straw, barley straw, oat straw, rye straw, rice straw, sugarcane, maize stalk, cotton, tobacco, bamboo, and the outer husk or shell of grains, rice, etc., preferably wheat straw.

5. The molded article according to any one of claims 1 to 4, wherein the composite material comprises 40 to 99 wt.%, preferably 65 to 95 wt.%, and more preferably 70 to 90 wt.%, of the non-wood lignocellulosic material based on the total weight of the composite material.

6. The molded article according to claim 1, wherein the composite material does not contain polylactic acid.

7. The molded article according to claim 1, wherein the composite material does not contain starch.

8. The molded article according to claim 1, wherein the biodegradable and / or compostable polyester is polybutylene adipate terephthalate (PBAT).

9. The molded article according to any one of claims 5 to 8, wherein the composite material comprises up to 65%, preferably 1 to 60 wt.%, more preferably 5 to 35 wt.%, and even more preferably 10 to 30 wt.%, of the total weight of the composite material, the biodegradable and / or compostable polyester.

10. The following are biodegradability potential characteristics: - When measured in accordance with ISO 14855-1 (2012) under industrial composting conditions, at least 90% biodegradation within a period of 180 days or less. - When measured in accordance with ISO 17556 (2012) under soil composite conditions, at least 90% biodegradation occurred within a period of two years or less, and - When measured in accordance with ISO 14855-1 (2012) under home composting conditions, at least 90% biodegradation within a period of one year or less. A molded article according to any one of claims 1 to 9, having one or more of the above.

11. The molded article according to any one of claims 1 to 10, wherein the article is a disposable article or item, preferably a disposable article or item selected from the group consisting of (drinking) straws, cutlery such as spoons, forks, knives, chopsticks, plates, drinking cups, lollipop sticks, plant pots, cotton swaps, etc.

12. Products in the form of granules, free-flowing powders, or pelletized compositions, wherein the products are as follows: - A particulate non-wood lignocellulosic material, wherein the material can be obtained by crushing, milling, or macerating a non-wood lignocellulosic plant material. - Particulate biodegradable and / or compostable polyester, This includes combinations of, A product wherein the non-wood lignocellular material and the biodegradable and / or compostable polyester are present in a ratio of at least 1:2 and constitute at least 90 wt.%, preferably at least 95 wt.%, and more preferably at least 97.5 wt.% of the granules or powder.

13. A method for producing a molded article as defined in any one of claims 1 to 10, wherein the method is as follows: a) A step of providing a certain amount of crushed / finely ground non-wood lignocellulosic plant material, b) Providing a certain amount of biodegradable and / or compostable polyester, c) A step of mixing the crushed / fine-grained lignocellular plant material with the particulate biodegradable and / or compostable polyester and processing it into a pumpable mass, d) A step of processing the mass into a molded article, Methods that include...

14. The method according to claim 13, wherein step a) provides a certain amount of non-wood lignocellulosic plant material and processes it with a grinder, mill, sieve, compounder, etc., to obtain a pulverized / fine material characterized by a fiber length in the range of 0.05 to 3.5 mm.

15. The method according to claim 13 or 14, wherein step d) includes die casting, injection molding, blow molding, or extrusion molding of the pump-operable mass.

16. The method according to any one of claims 1 to 15, wherein the kneadable mass is heated in step c) and / or d) preferably to a temperature above the melting point of the biodegradable and / or compostable polyester, and / or to a temperature in the range of 60 to 160°C, more preferably to a temperature in the range of 70 to 150°C, and most preferably to a temperature in the range of 80 to 140°C.

17. A molded article that can be obtained by a process defined in any one of claims 13 to 20.

18. A molded article comprising a three-dimensional monolithic body made of a composite material comprising a non-wood lignocellulosic material and a biodegradable and / or compostable polyhydroxyalkanoate, wherein the composite material contains the biodegradable and / or compostable polyhydroxyalkanoate in an amount of less than 90 wt.% based on the total (dry) weight of the composite material, and the non-wood lignocellulosic material and the biodegradable and / or compostable polyhydroxyalkanoate together constitute at least 92.5 wt.%, preferably at least 95 wt.%, and more preferably at least 97.5 wt.% of the composite material.

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