liquid composition comprising biological entities and use thereof

专利摘要:
The present invention relates to a new liquid composition that comprises biological entities that have a polymer degradation activity, a carrier and a solvent that can be advantageously used for the manufacture of a biodegradable plastic product.
公开号:BR112020004083A2
申请号:R112020004083-5
申请日:2018-08-31
公开日:2020-10-13
发明作者:Elodie Guemard；Mediha Dalibey
申请人:Carbios；
IPC主号:

专利说明:

[0001] [0001] The present invention relates to an innovative liquid composition comprising both biological entities with the capacity to degrade a polymer and a carrier with the capacity to protect and stabilize such biological entities during a heating process, such as extrusion. The invention also relates to the use of such a liquid composition for the manufacture of biodegradable plastic articles, in which biological entities are homogeneously dispersed in the plastic articles. BACKGROUND OF THE INVENTION
[0002] [0002] Different biodegradable plastic compositions have been developed to answer environmental questions about plastic and the accumulation of plastic articles in landfills and natural habitats, and to comply with restrictive legislation, in particular, on short-lived products ( such as bags, packaging including trays, containers, bottles, agricultural films, etc.).
[0003] [0003] Plastic compositions generally contain polyester, flour or starches derived from various cereals. Recently, an innovative solution was proposed to further control the degradation of plastic articles, by including biological entities with the ability to degrade polyesters in the plastic composition used to manufacture plastic articles (documents nº WO 2013/093355; WO 2016/198652; WO 2016/198650; WO 2016/146540; WO 2016/062695). The resulting plastic product contains biological entities, particularly enzymes, dispersed in a polymer, and has improved biodegradability as compared to plastic articles deprived of such biological entities.
[0004] [0004] However, the inclusion of biological entities in a partially or fully melted polymer during the manufacture of plastic articles can give rise to technical problems. In fact, the composition of biological entities can hardly be miscible in the polymer, the biological entities can be non-homogeneously dispersed in the polymer and / or at least partially lose its degradation activity. SUMMARY OF THE INVENTION
[0005] [0005] When working on these problems, the inventors developed a liquid composition of biological entities that make it possible to homogeneously disperse such biological entities in a polymer in a totally or partially fused state. the resulting plastic articles show enhanced physical properties as compared to plastic products manufactured with biological entities in solid form. In particular, the inventors have revealed that the presence of a specific carrier in the composition that contains biological entities can preserve the degradation activity of biological entities even during and after a heat treatment. The inventors have thus developed a liquid composition that contains at least biological entities that have a polymer degradation activity, a particular protective and stabilizing carrier and an aqueous solvent and have shown that such stabilized liquid composition leads to plastic articles with enhanced biodegradability as compared to plastic products produced with liquid prior art compositions.
[0006] [0006] Interestingly, the inventors have further revealed that, in certain cases, the use of a two-step process for the manufacture of a plastic article containing biological entities further preserves the degradation activity of biological entities. More particularly, the first stage consists of the introduction of the liquid composition containing biological entities in a first polymer with a low melting point (below 140 ºC), after the introduction of such a mixture in a second polymer with a high melting point ( above 140 ºC).
[0007] [0007] The invention provides a new liquid composition comprising biological entities and a carrier. The composition of the invention is particularly useful for the production of biodegradable plastic articles that comprise biological entities capable of degrading at least one polymer of the plastic article and with enhanced mechanical properties such as Turbidity, surface roughness, elongation at break, tensile strength at break, dynamic friction coefficient or Young's modulus and biodegradability performance as compared to plastic articles manufactured with biological entities in solid form. In particular, the use of such a liquid composition makes it possible to reduce the surface roughness and, eventually, the thickness of the plastic article without going through expensive and heavy operations of a solid composition (for example: in the form of powder). In addition, the powderiness of the constituents of such a liquid composition is reduced as compared to the solid composition (for example: in the form of powder), which leads to less risk of particulate inhalation during the plastic article production process.
[0008] [0008] Thus, an objective of the invention is to provide a liquid composition suitable to be incorporated into a partially or fully melted polymer and comprising biological entities that have a polymer degradation activity, a carrier and an aqueous solvent, wherein i ) the carrier is a polysaccharide selected from starch derivatives, natural gums, marine extracts, microbial polysaccharides and animal polysaccharides and ii) the composition comprises, based on the total weight of the composition: - from 0.01% to 35% in weight of biological entities, - from 15% to 95% by weight of an aqueous solvent, - from 3% to 80% by weight of a carrier.
[0009] [0009] Preferably, the composition of the invention comprises, based on the total weight of the composition: - from 0.3% to 30% by weight of biological entities, preferably selected from protease, esterase or lipase - from 19 % to 608% by weight of an aqueous solvent, preferably water - from 15% to 70% by weight of a carrier
[0010] [0010] Alternatively, the composition of the invention comprises, based on the total weight of the composition: - from 0.01% to 35% of biological entities, preferably selected from PLA-degrading enzymes - from 30% to 75 % of water
[0011] [0011] The liquid composition of the invention is particularly useful for the manufacture of plastic compositions and plastic articles. Advantageously, the biological entities of the composition are able to degrade at least one polymer of the plastic article. The biological entities are homogeneously dispersed in the resulting plastic articles. Interestingly, said plastic articles have satisfactory degradability and mechanical properties.
[0012] [0012] Thus, another objective of the invention is to provide a process for making a plastic article using the composition of the invention, preferably by extrusion and a plastic article made from such a composition.
[0013] [0013] An additional objective of the invention is to provide a process for the manufacture of a plastic article containing biological entities which successively comprise a step of introducing the liquid composition of the invention into a first polymer to obtain a mixture, and a step of introducing said mixture in a second polymer different from the first polymer, in which the first polymer has a melting point below 140 ° C and the second polymer has a melting point above 140 “C.
[0014] [0014] The invention also relates to a method for increasing the dispersion homogeneity of biological polymer degrading entities in a biodegradable plastic article, wherein said method comprises introducing the liquid composition of the invention during the plastic article manufacturing process .
[0015] [0015] The invention also provides a method for increasing the biodegradability of a plastic article comprising at least one polymer, wherein said method comprises introducing during the production process of the plastic article, the liquid composition of the invention. DETAILED DESCRIPTION OF THE INVENTION
[0016] [0016] The present invention relates to innovative liquid compositions that comprise stabilized biological entities that can be used to manufacture plastic articles in which said biological entities are homogeneously dispersed. The liquid compositions of the invention comprise a carrier, selected from starch derivatives, natural gums, marine extracts, microbial polysaccharides and animal polysaccharides, which allows, solubilized in an aqueous solvent, to protect and stabilize biological entities during a process of heating, as an extrusion process. The composition of the present invention allows the manufacture of biodegradable plastic articles, in which the biological entities are homogeneously distributed and have a degradation activity. These results are compatible with the physical / mechanical properties and degradability expected for plastic articles of short life and single use. Definitions
[0017] [0017] The present disclosure will be better understood with reference to the following definitions.
[0018] [0018] In the context of the invention, the term "plastic article" refers to any item made of at least one polymer, such as plastic sheet, film, tube, rod, profile, massive block format, fiber, etc. Preferably, the plastic article is a manufactured product, such as a rigid or flexible packaging, agricultural films, bags and bags, disposable items or the like. Preferably, the plastic article comprises a mixture of semicrystalline and / or amorphous polymers or semicrystalline polymers and additives. Plastic articles may contain additional substances or additives, such as plasticizers, mineral or organic fillers. According to the invention, the plastic article can be selected from a plastic film, a rigid plastic article or a non-woven fabric.
[0019] [0019] According to the invention, the term "plastic film" refers to a flexible plastic sheet (that is, capable of flexing without breaking) with a thickness below 250 µm. Thin film is considered to have a thickness below 100 µm, preferably below 50 µm and is preferably produced by blowing film extrusion, while thick film has a thickness above 100 µm and is, preferably produced by casting film extrusion. Examples of plastic films include agricultural films, plastic bags or bags, flexible packaging films, food films, postage films, coating films, multipack films, industrial films, personal care films, nets, etc.
[0020] [0020] According to the invention, the term "rigid plastic article" refers to a plastic article that is not a film. These articles are preferably produced by calendering, injection molding, thermoforming, cork molding or even rotational molding and 3D printing. Examples of rigid plastic items are thin-walled packaging, such as food and beverage packaging, boxes, trays, containers, food service items, electronic wrappers, cosmetic cases, outdoor gardening items such as vases, rigid packaging , containers, cards, swabs, irrigation tubes, etc. Some rigid plastic articles can be produced by thermoforming plastic sheets with a thickness of 250 µm or more, in which such plastic sheets are produced by calendering or film casting. According to the invention, the rigid plastic article has a thickness below 5 mm, preferably below 3 mm.
[0021] [0021] As used in this document, the term "plastic composition" means a mixture of polymers and biological entities and, possibly, additional compounds (eg additives, filler, etc.) before any forming or conditioning step to produce a plastic article. In a particular embodiment of the invention, the plastic composition is a main batch in solid form, prior to its introduction into a polymer-based matrix.
[0022] [0022] A "polymer-based matrix" refers to a matrix that comprises, as the main ingredient, one or more polymers. The polymer-based matrix comprises at least 51% by weight of polymer (s), based on the total weight of the composition, preferably at least 60% or 70%. The polymer-based matrix can additionally comprise additional compounds, as additives. According to the invention, the polymer-based matrix is deprived of any biological entities. A "polyester-based matrix" refers to a matrix that comprises, as the main ingredient, one or more polyesters (or polyester).
[0023] [0023] As used in this document, the term "main batch" means a concentrated mixture of ingredients (for example, biological entities, additives, etc.) and selected polymer that can be used to introduce said ingredients into plastic articles or compositions in order to give the desired properties to that. The main batch compositions allow the processor to introduce economically selected ingredients during the plastic manufacturing process. Advantageously, the main batch is composed of a polymer in which the selected ingredients are incorporated in high concentration. In general, the main batch is directed to be mixed with polymer (or polymers) or a polymer-based matrix to produce a final plastic that has a desired amount of selected ingredients. The main batch may additionally comprise mineral or organic fillers. According to the invention, the main batch comprises at least 5% of a composition of biological entities of the invention that have polymer degradation activity.
[0024] [0024] A "polymer" refers to a chemical compound or mixture of compounds whose structure is made up of multiple units linked by covalent chemical bonds. Within the context of the invention, the term "polymer" includes natural or synthetic polymers, which comprise a single type of repeating unit (i.e., homopolymers) or different types of repeating units (i.e., block copolymers and random copolymers) . As an example, synthetic polymers include polymers derived from petroleum oil or bio-based polymers, such as polyolefins, aliphatic or aromatic polyesters, polyamides, polyurethanes and polyvinyl chloride. Natural polymers include lignin and polysaccharides, such as cellulose, hemicellulose, starch and derivatives thereof, which may or may not be plasticized.
[0025] [0025] "Synthetic polymers" refer to polymers derived from petroleum oil or bio-based polymers, and can be selected from the group consisting of polyolefins, aliphatic or semi-aromatic polyesters, polyamides, polyurethanes or vinyl polymers and derivatives thereof or mixtures / mixtures of these materials. Preferred polyolefins for use in the present invention include, without limitation, polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-l (PB-l1), polyisobutylene (PIB), ethylene propylene rubber (EPR) ), ethylene propylene diene monomer rubber (EPDM), cyclic olefin copolymer (COC) and derivatives or blends / mixtures thereof. Preferred aliphatic polyesters for use in the invention include, but are not limited to, polylactic acid (PLA) (such as poly (L-lactic acid) (PLLA), poly (D-lactic acid) (PDLA), poly (D, L- lactic) (PDLLA) or PLA stereocomplex (scPLA)), polyglycolic acid (PGA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), polybutylene succinate (PBS); and semi-aromatic polyesters are selected from polybutylene terephthalate (PET), polyethylene isosorbide terephthalate (PTT), polybutylene succinate adipate (PBT), polyethylene adipate terephthalate (PEIT), polyethylene terephthalate (PBSA), polytrimethylene terephthalate (PBAT), polyethylene furonate (PEF), poly (ethylene) adipate (PEA), polyethylene naphthalate (PEN), and derivatives or mixtures thereof. Preferred polyamide polymers (also called nylon) for use in the invention include, without limitation, polyamide-6 or poly (B-caprolactam) or polycaproamide (PAG6), polyamide-6.6 or Ppoli (hexamethylene adipamide) (PA6, 6), poly (11-aminoundecanoamide) (PAl1), polydodecanolactam (PAl2), poly (tetramethylene adipamide) (PA4,6), poly (pentamethylene sebacamide) (PA5,10), poly (hexamethylene azelamide) (PA6,9) , poly (hexamethylene sebacamide) (PA6,10), poly (hexamethylene dodecanoamide) (PA6,12), poly (m-xylylene adipamide) (PAMXD6), polyhexamethylene adipamide / polyhexamethyleneterephthalamide copolymer (PA66 / 6T), copolymer of polyhexamethylene adipamide / polyhexamethyleneisophthalamide (PA66 / 61) and derivatives or blends / mixtures thereof. Preferred Vvinyl polymers include polystyrene (PS), polyvinyl chloride (PVC), polyvinyl chloride (PVdC), ethylene vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), polyvinyl alcohol (PVOH) and derivatives or blends / mixtures of these materials.
[0026] [0026] Within the context of the invention, the term "polyester" refers to a polymer that contains an ester functional group in its main chain. The ester functional group is characterized by a carbon bond to three other atoms: a single bond to a carbon, a double bond to an oxygen, and a single bond to an oxygen. The single oxygen bond is bonded to another carbon. Depending on the composition of your main chain, polyesters can be aliphatic, aromatic or semi-aromatic. The polyester can be homopolymer or copolymer. As an example, polylactic acid is an aliphatic homopolymer composed of a monomer, lactic acid; and polyethylene terephthalate is an aliphatic aromatic copolymer composed of two monomers, terephthalic acid and ethylene glycol. Such polyesters can be native or chemically modified.
[0027] [0027] In the context of the invention, the term "charge" refers to a substance that is incorporated into a plastic composition and / or a plastic article to reduce its costs or, optionally, improve its physical properties (for example, their hardness, stiffness or strength.) The fillers can be inactive (ie, inert) or active material, and can form chemical bonds with the components of the composition or plastic article.The fillers can be natural, synthetic or modified fillers. The filler can be selected from mineral or organic fillers. In a particular embodiment of the invention, the filler is chosen from the group consisting of, without limitation, calcite, carbonate salts or metal carbonate such as calcium carbonate ( or limestone), potassium carbonate, magnesium carbonate, aluminum carbonate, zinc carbonate, copper carbonate, chalk, dolomite, silicate salts such as water magnesium silicate such as talc or soapstone, silicate here calcium (wollastonite), potassium silicate, magnesium silicates (talc), aluminum silicate (kaolin), or mixtures thereof such as mica, smectite such as montmorillonite, vermiculite, and paligorskite-sepiolite, sulphate salts such as barium sulphate, or calcium sulfate
[0028] [0028] As used in this document, the term "biological entities" means active enzymes or microorganisms that produce enzyme, such as sporolated microorganisms, as well as combinations thereof. According to the invention, "biological entities" refer, preferably, to enzymes. Biological entities can be in solid (for example, powder) or liquid form.
[0029] [0029] As used herein, the term "polysaccharides" refers to molecules composed of long chains of monosaccharide units linked together by glycosidic bonds. The polysaccharide structure can be linear to highly branched. Examples include storage polysaccharides, such as starch and glycogen, and structural polysaccharides, such as cellulose and chitin. polysaccharides include native polysaccharides or chemically modified polysaccharides by crosslinking, oxidation, acetylation, partial hydrolysis, etc. Carbohydrate polymers can be classified according to their origin (marina, vegetable, microbial or animal), structure (linear, branched) and / or physical behavior (such as the designation as gum or hydrocolloid that refers to the property that these polysaccharides are found in) hydrate in hot or cold water to form “viscous solutions or dispersions in low concentration gum or hydrocolloid). In the context of the invention, polysaccharides can be classified according to the classification described in “Encapsulation Technologies for Active Food Ingredients and Food Processing - Chapter 3 - Materials for Encapsulation - Christine Wandrey, Artur Bartkowiak, and Stephen E. Harding”: - Starch and derivatives, such as amylose, amylopectin, maltodextrin, glucose syrups, dextrin, cyclodextrin.
[0030] [0030] Polysaccharides can be further classified according to their solubility in water. In particular, cellulose is not soluble in water. According to the invention, the polysaccharides used as a carrier are water soluble.
[0031] [0031] As used in this document, the term "room temperature" or "room temperature" means a temperature between 10 ºC and 30 "ºC, particularly between 20" * C and 25 "C.
[0032] [0032] As used in this document, the term "soluble" refers to the ability of a solute (ie, carrier, enzymes) to be dissolved in a liquid solvent. The solubility of a substance depends on the physical and chemical properties of both the solute and the solvent, as well as the temperature, pressure and pH of the solution and can be defined according to international standards such as IUPAC. According to the IUPAC definition, solubility is the analytical composition of a saturated solution expressed as a proportion of a designated solute in a designated solvent. Solubility can be indicated in several concentration units, such as molarity, molality, molar fraction, molar ratio, mass (solute) by volume (solvent) and other units. Solubility is defined at a particular temperature and at a particular atmospheric pressure. The extent of solubility varies widely, from infinitely soluble (without limit) or completely miscible, like ethanol in water, to slightly soluble, like silver chloride in water. The term insoluble is often applied to sparingly or sparingly soluble solute. The term "maximum solubility" refers to the saturation concentration of the solute in a solvent, in which an additional amount of the solute does not increase the concentration of the solution and in which the excess amount of solute begins to precipitate. According to the invention, maximum solubility refers to the carrier saturation concentration in the liquid composition, in which other components, such as biological entities, can confer solubility to the solute.
[0033] [0033] As used in this document, the term "by weight" refers to the ratio based on the total weight of the composition or product considered.
[0034] [0034] In the context of the invention, the term "about" refers to a margin of +/- 5%, preferably +/- -1% or within the tolerance of a suitable measuring device or instrument. Net composition
[0035] [0035] Therefore, an objective of the invention is to provide a liquid composition suitable to be incorporated into a partially or fully melted polymer and comprising biological entities that have a polymer degradation activity, a carrier and an aqueous solvent, in which: i) the carrier is a polysaccharide selected from starch derivatives, natural gums, marine extracts,
[0036] [0036] According to the invention, the expression "suitable to be incorporated into a partially or fully molten polymer" means that the biological entities of the composition retain an activity after the heat treatment. In particular, biological entities retain polymer degradation activity in the plastic composition and / or in the final plastic article.
[0037] [0037] In a particular embodiment, the composition is suitable for extrusion with a polymer. Preferably, the composition is suitable for extrusion with a synthetic polymer, such as polyolefins, aliphatic or aromatic polyesters, polyamides, polyurethanes and polyvinyl chloride or a natural polymer, such as lignin and polysaccharides, such as cellulose, hemicellulose, starch and derivatives thereof. . In a preferred embodiment, the composition is suitable to be extruded with a polymer with a low melting temperature or melting point (Tm), that is, with a Tm below 140 “C.
[0038] [0038] In a preferred embodiment, the aqueous solvent is water. In such modality, the composition comprises, based on the total weight of the composition, from 15% to 95% of water, and from% to 85% of other components, such as at least 0.01% to 358% of entities biological and 38% to 80% of a carrier.
[0039] [0039] In a particular embodiment, the composition comprises, based on the total weight of the composition: - from 0.3% to 30% of biological entities - from 19% to 85% of an aqueous solvent - from 4% to 80% of a carrier
[0040] [0040] In a preferred embodiment, the composition comprises 19% to 85% water and 15% to 81% other components, such as at least 0.01% to 35% biological entities and 3% to 80% % of a carrier, based on the total weight of the composition.
[0041] [0041] In a particular embodiment, the composition comprises less than 35% by weight of biological entities. In another particular embodiment, the composition comprises less than 30% by weight of biological entities. In another particular embodiment, the composition comprises less than% by weight of biological entities.
[0042] [0042] In a particular preferred embodiment, the composition comprises less than 80% by weight of aqueous solvent, preferably less than 75%, less than 70%, even more preferably, less than 60%, based on the total weight composition. In another preferred embodiment, the composition comprises more than 20% by weight of aqueous solvent, preferably more than 30%, and less than 80%, based on the total weight of the composition. In another particular embodiment, the composition comprises from 20% to 80% by weight of aqueous solvent, preferably from 30% to 75%, more preferably from 40% to 60%. In another particular embodiment, the composition comprises about 50% aqueous solvent. In another particular embodiment, the composition comprises about 40% aqueous solvent.
[0043] [0043] In a preferred embodiment, the aqueous solvent is water. In a preferred embodiment, the composition comprises less than 75% by weight of water, preferably less than 70%, more preferably less than 60%, based on the total weight of the composition. In another preferred embodiment, the composition comprises more than 20% by weight of water, preferably more than 30% and less than 80%, based on the total weight of the composition. In particular, the composition comprises from 20% to 80% by weight of water. In another particular embodiment, the composition comprises from 30% to 75% by weight of water, preferably from 40% to 60%. In another particular embodiment, the composition comprises about 50% water. In another particular embodiment, the composition comprises about 40% water.
[0044] [0044] In a particular preferred embodiment, the composition comprises more than 5% by weight of carrier, preferably more than 10%, even more preferably, more than 15%.
[0045] [0045] Thus, in a preferred embodiment, the composition comprises, based on the total weight of the composition: - from 0.3% to 30% by weight of biological entities - from 19% to 60% by weight of an aqueous solvent - from 15% to 70% by weight of a carrier
[0046] [0046] In another preferred embodiment, the composition comprises less than 70% by weight of carrier, preferably less than 60%. In a particular embodiment, the composition comprises 5 8% and 70% carrier, preferably 10% to 60%. In another particular embodiment, the composition comprises from 10 8% to 508% carrier.
[0047] [0047] In another particular modality, the composition comprises, based on the total weight of the composition: - from 0.01% to 35% of biological entities - from 30% to 75% of water - from 10% to 69.99 % of a carrier
[0048] [0048] In another particular modality, the composition comprises, based on the total weight of the composition: - from 0.01% to 35% of biological entities - from 30% to 60% of water - from 20% to 45% of a carrier
[0049] [0049] In another particular modality, the composition comprises, based on the total weight of the composition: - from 0.01% to 35% of biological entities - from 40% to 60% of water - from 20% to 45% of a carrier
[0050] [0050] In another particular modality, the composition comprises about 50% of water, and from 0.01% to 35% of biological entities, and from 20% to 49.99% of carrier.
[0051] [0051] In another particular modality, the composition comprises about 40% water, and 0.01% to 35% biological entities, and 20% to 59.99% carrier.
[0052] [0052] In a particular embodiment, the carrier / aqueous solvent ratio by weight is below 4.
[0053] [0053] In a particular embodiment, the amount of carrier in the composition is 4% to 100% of the maximum carrier solubility in the aqueous solvent, that is, from 4% to 100% of the carrier's saturation concentration in the aqueous solvent.
[0054] [0054] Alternatively or additionally, the amount of carrier in the composition is 4% to 100% of the maximum solubility of the carrier in the composition, that is, from 4% to 100% of the carrier saturation concentration in the composition.
[0055] [0055] According to the invention, the presence of particular carriers in the composition allows the protection and stabilization of biological entities not only in the composition, but also during a heat treatment, such as an extrusion process in which the composition is introduced in a partially or fully melted polymer.
[0056] [0056] In a particular mode, the carrier is in a solid form at room temperature. Advantageously, the carrier is also soluble in aqueous solvent, such as water, at room temperature. Preferably, the carrier is soluble in the liquid composition, at least at room temperature. Alternatively or additionally, the carrier is soluble in the liquid at the temperature at which said composition is introduced into a polymer that is in a partially or fully molten state
[0057] [0057] In a particular embodiment, the carrier is a derivative of starch. Preferably, the carrier is maltodextrin. In such a particular embodiment, the weight ratio of maltodextrin / aqueous solvent is preferably between 3 and 4. In a particular embodiment, the amount of maltodextrin in the composition is preferably 5 to 100% of its maximum solubility in the composition, preferably , from 26 to 100%, more preferably from 39 to 100%. Consequently, the composition comprises more than 48% by weight of maltodextrin, based on the total weight of the composition, preferably more than 20%, preferably more than 30%.
[0058] [0058] In a particular mode, the carrier is a natural gum. Preferably, the carrier is selected from gum arabic, guar gum, tragacanth gum, gum
[0059] [0059] In another particular modality, the carrier is a marine extract. Preferably, the carrier is selected from carrageenan or alginate.
[0060] [0060] In another particular modality, the carrier is a microbial polysaccharide. Preferably, the carrier is xanthan.
[0061] [0061] In another particular modality, the carrier is an animal polysaccharide. Preferably, the carrier is chitosan.
[0062] [0062] In a particular embodiment, the composition comprises at least two carriers selected from starch derivatives, natural gums, marine extracts, animal and microbial polysaccharides.
[0063] [0063] In another particular embodiment, the weight ratio of carrier / biological entities is between 0.8 and 1.2, preferably about 1. In another particular embodiment, the weight ratio of carrier / biological entities is above 1, preferably above 2.
[0064] [0064] According to the invention, the composition can additionally comprise sugars, proteins, lipids, organic acids, salts and vitamins that originate from the culture supernatant of a polymer degrading microorganism used as biological entities in the composition. Such a supernatant can be preliminarily treated (for example, mechanically, physically or chemically) to increase the concentration of enzymes and / or to remove other components such as DNA or cellular debris.
[0065] [0065] In a particular embodiment, the composition may additionally comprise polyols, such as glycerol, sorbitol or propylene glycol. This is particularly the case when producing the composition of the invention with commercial biological entities, preferably commercial enzymes, conditioned in a stabilization solution comprising polyols. According to a particular embodiment, the composition comprises a maximum of 10% by weight of polyols based on the total weight of the composition, preferably a maximum of 5%. According to another particular embodiment, the composition comprises between 10% and 20% by weight of polyols based on the total weight of the composition.
[0066] [0066] According to a particular embodiment, the composition may comprise non-soluble components with a particle size below 20 µm.
[0067] [0067] Alternatively or additionally, the composition additionally comprises mineral components, such as calcium components that are known to increase the thermostability of some biological entities, such as calcium carbonate, calcium chloride or other calcium minerals.
[0068] [0068] Advantageously, the composition of the invention is stable, that is, chemically and biologically stable. In the context of the invention, "chemically stable" refers to a composition in which the biological entities do not show any significant loss of activity during a defined period at room temperature, in the dark. More particularly, "chemically stable" refers to a composition in which the loss of degradation activity of biological entities is less than 50%, preferably less than 25%, more preferably less than 10% as compared to the activity of degradation of said biological entities prior to introduction into the composition, over a period of time of at least 30 days, preferably at least 90 days, more preferably, at least 1 year. In a particular embodiment, the composition of the invention is advantageous and chemically stable for at least 90 days at 4 "ºC. In particular, the loss of degradation activity of biological entities in the composition of the invention is less than% as compared to the degradation activity of said biological entities before introduction into the composition, over a period of time of at least 90 days.
[0069] [0069] In the context of the invention, the term "biologically stable" refers to a composition that does not show any subsequent bacterial, yeast and fungal proliferation for a defined period of at least 30 days, preferably at least 90 days, with more preferably, at least 1 year, at room temperature, in the dark. In particular, the composition additionally comprises antifungal and / or antibacterial components, such as sorbic acid and / or salts thereof, benzoic acid and salts thereof, sulfite or sulfurous anhydride, nitrate or nitrite, propionic acid, butyric acid, natamycin, paraben, acid acetic, citric acid, boric acid, plant extracts.
[0070] [0070] In another particular embodiment, the composition comprises, based on the total weight of the composition: - from 0.01% to 35% of PLA degradation enzymes - from 30% to 75% of water - from 10% to 69.99% gum arabic
[0071] [0071] In another particular embodiment, the composition comprises, based on the total weight of the composition: - from 0.01% to 35% of PLA degradation enzymes - from 30% to 60% of water - from 20% to 45% gum arabic
[0072] [0072] In another particular embodiment, the composition comprises, based on the total weight of the composition: - from 0.01% to 35% of PLA degradation enzymes - from 40% to 60% of water - from 20% to 45% gum arabic
[0073] [0073] In another particular embodiment, the composition comprises about 50% water, and 0.01% to 35% PLA degrading enzymes, and 20% to 49.99% arabic gum.
[0074] [0074] In another particular embodiment, the composition comprises about 40% water, and 0.01% to 35% PLA degrading enzymes, and 20% to 59.99% arabic gum.
[0075] [0075] All the compositions defined above may optionally comprise from 0% to 20%, preferably from 0% to 5%, by weight based on the total weight of the composition, of other components, preferably selected from proteins, salts, polyols.
[0076] [0076] In a particular embodiment, the PLA-degrading enzymes of such compositions are preferably proteases.
[0077] [0077] In a particular embodiment, the composition of the invention comprises, based on the total weight of the composition: - from 20% to 80% by weight of water, preferably from 40% to 60% of water - from 0.01 % to 30% by weight of PLA degradation enzymes, preferably from 58% to 30% of PLA degradation enzymes as protease - from 10% to 50% by weight of gum arabic, preferably from 15% to 35 8%
[0078] [0078] In a particular embodiment, the composition of the invention comprises, based on the total weight of the composition: - from 20% to 80% by weight of water, preferably from 40% to 60% of water from 0.01% to 30% by weight of PLA degradation enzymes, preferably from 5% to 30% of PLA degradation enzymes as protease - from 10% to 50% by weight of gum arabic, preferably from 15% to 35 8%
[0079] [0079] In a particular embodiment, the composition of the invention comprises, based on the total weight of the composition: - from 20% to 80% by weight of water, preferably from 40% to 60% of water - from 0.01 % to 30% by weight of PLA degradation enzymes, preferably from 58% to 30% of PLA degradation enzymes as protease - from 10% to 50% by weight of maltodextrin, preferably from 15% to 40 8%
[0080] [0080] In a particular embodiment, the composition of the invention comprises, based on the total weight of the composition: - from 20% to 80% by weight of water, preferably from 40% to 60% of water - from 0.01 % to 30% by weight of PLA degradation enzymes, preferably from 58% to 20% of PLA degradation enzymes as protease - from 10% to 50% by weight of maltodextrin, preferably from 15% to 40 % - from 0% to 20% of other components, preferably selected from proteins, salts, polyols.
[0081] [0081] Advantageously, the liquid composition is in a liquid form at least at room temperature. Preferably, the liquid composition is in a liquid form at the temperature at which said composition is introduced into a polymer that is in a partially or fully molten state.
[0082] [0082] Advantageously, in all the compositions indicated above, the amount of carrier and biological entities are expressed on a dry matter basis, that is, in the amount of such carrier and biological entities after complete dehydration, water evaporation or water removal . Consequently, the amount of aqueous solvent in the composition includes all the liquid parts of the constituents of the composition, such as the liquid part of the biological entities when introduced in a liquid form and / or in the residual water that may be contained in the carrier (even when supplied in a powder).
[0083] [0083] According to the invention, the composition comprises biological entities suitable for degrading at least one polymer. In another particular embodiment, the composition comprises biological entities suitable for degrading at least two polymers.
[0084] [0084] In a preferred embodiment, biological entities comprise at least one enzyme with polymer degradation activity and / or at least one microorganism that expresses, and optionally that excretes, an enzyme that has polymer degradation activity. In a particular embodiment, biological entities comprise or consist of at least one enzyme with synthetic polymer degradation activity and / or at least one microorganism that expresses, and optionally excretes, an enzyme that has synthetic polymer degradation activity. In a preferred embodiment, biological entities consist of at least one enzyme with synthetic polymer degradation activity. In another particular embodiment, biological entities comprise or consist of at least two enzymes with polymer degradation activity. Examples of suitable enzymes that have a polymer degradation activity for use in the invention include, without limitation, depolymerase, esterase, lipase, cutinase, hydrolase, protease, polyesterase, carboxylesterase, oxygenase and / or oxidase such as laccase, peroxidase or oxygenase.
[0085] [0085] In a particular embodiment, biological entities comprise or consist of at least one enzyme with polyester degradation activity and / or at least one microorganism that expresses and, optionally excretes, an enzyme that has polyester degradation activity. Examples of suitable enzymes that have a polyester degrading activity for use in the invention include, without limitation, depolymerase, esterase, lipase, cutinase, carboxylesterase, protease or polyesterase. In another particular embodiment, biological entities comprise or consist of at least two enzymes with polyester degradation activity.
[0086] [0086] In a preferred embodiment, biological entities comprise or consist of an enzyme with a PLA degradation activity. Most preferably, biological entities consist of an enzyme with a PLA-degrading activity. The biological entities consist of a protease, preferably selected from Amycolatopsis sp., Amycolatopsis orientalis, proteinase K from Tritirachium album, Actinomadura keratinilytica, Laceyella sacchari LP175, Thermus sp., Bacillus licheniformis, Bacillus thermoproteolyticus or any commercial enzymes that is, filtered to remove the commercial carrier) known to degrade
[0087] [0087] Enzymes can be in pure or enriched form, or in admixture with other excipients or diluents. A combination of enzymes can be used as well.
[0088] [0088] In an alternative embodiment, biological entities comprise microorganisms that produce such enzymes, either naturally or as a result of specific manipulation (for example, recombinant microorganisms). Preferred examples of suitable microorganisms include, without limitation, bacteria, fungi and yeasts. In one embodiment, biological entities comprise sporulated microorganisms and / or spores thereof.
[0089] [0089] In a specific embodiment, biological entities comprise enzymes encapsulated in nanocapsules, enzymes encapsulated in molecules in cages, and enzymes aggregated together. The term "cage molecule" means a molecule that can be inserted into the structure of said enzymes to stabilize them and to make them resistant to high temperatures. Encapsulation techniques are well known to those skilled in the art and include, for example, nanoemulsions.
[0090] [0090] Biological entities can be supplied in a liquid or solid form. For example, biological entities can be in a powder form. Alternatively, biological entities can be supplied in suspension or dissolved in a liquid. In such a case, the quantities of “biological entities revealed in the present specification correspond, preferably, to the quantities of biological entities on a dry matter basis (ie, deprived of the liquid). Production of the composition of the invention
[0091] [0091] Another objective of the invention is also to provide a method for producing the liquid composition.
[0092] [0092] As indicated above, biological entities can be supplied in a solid or liquid form.
[0093] [0093] Liquid biological entities, including commercial enzymes and / or culture supernatant from a polymer degrading microorganism, can be subjected to a pretreatment in order to increase the concentration of enzymes and / or remove unwanted components. In particular, biological entities in a liquid form can be subjected to filtration, ultrafiltration or diafiltration. This step is particularly useful for liquid commercial compositions that are generally marketed in polyols containing water solutions. The resulting liquid solution is then mixed with the carrier in a powder form and the volume is adjusted with aqueous solvent to obtain the composition of the invention. The mixture is then subjected to stirring in order to homogenize the composition of the invention.
[0094] [0094] The biological entities in a solid form, preferably in a powder form, are mixed with the carrier in a powder form and the aqueous solvent in order to obtain the composition of the invention. The mixture is then subjected to stirring in order to homogenize the composition of the invention.
[0095] [0095] The composition of the invention obtained is a solution that can contain insoluble components with a particle size below 20 µm suspended in the aqueous solvent. Use of the composition of the invention
[0096] [0096] Another objective of the invention is also to provide methods using the composition of the invention. In particular, the composition of the invention is used for the production of a plastic composition, wherein such a plastic composition is additionally used for the production of a plastic article. According to the invention, the composition of the invention is particularly useful for the production of thin plastic articles, such as plastic films. In fact, the absence of particles with a particle size above 20 pum reduces the surface roughness of the film.
[0097] [0097] In a preferred embodiment, the composition of the invention is used for the production of a plastic article in which the biological entities of the composition are able to degrade at least one polymer of the plastic article.
[0098] [0098] In general, the liquid composition of the invention is introduced into a polymer in a partial or fully melted step before or during the shaping of said polymer to produce a biodegradable plastic article. According to the invention, the biological entities of the composition retain an activity after its introduction into a polymer in a partially or fully molten state.
[0099] [0099] In a particular embodiment, the liquid composition is introduced into a first polymer that has a melting temperature (Tm) above 140 ºC. In another particular embodiment, the liquid composition is introduced into a first polymer that has a low Tm (below 140 ºC, preferably below 120 ºC), such as PCL, PBSA, PBAT, PHA or PLA. Regarding the amorphous polymer, in the context of the invention,
[0100] [0100] Advantageously, the residence time of the liquid composition and, therefore, of the biological entities in the first polymer at a temperature above 100 ºC is as short as possible and, preferably, between 5 seconds and 10 minutes, with more preferably less than 5 minutes, 3 minutes, 2 minutes.
[0101] [0101] An object of the invention is to provide a process for preparing a plastic article using a main batch.
[0102] [0102] For example, the process comprises the steps of: a) preparing a main batch comprising biological polymer degradation entities and at least one first polymer by (i) heating the first polymer; and (ii) introducing 5% to 50% by weight of the composition as described above, based on the total weight of the main batch during the heating of the first polymer; and (b) introducing the main batch into a polymer-based matrix during the production of the plastic article in which step a) is carried out at a temperature where the first polymer is in a partially or fully molten state and step b) is carried out at a temperature where both the first polymer and the polymer-based matrix polymer are in a partially or fully molten state and where the biological entities of the composition are able to degrade a polymer-based matrix polymer.
[0103] [0103] Step (a) of mixing can then be carried out at a temperature of 40 ºC or above, particularly at or above 45 ºC, 55 ºC, 60 ºC, 70 ºC, 80 ºC, 90 ºC, 100 " C, or above 150 ºC, depending on the nature of the first polymer. Typically, this temperature does not exceed 300 “ºC. More particularly, the temperature does not exceed 250 “* C. In a particular embodiment, step (a) is carried out using a polymer with a Tm above 140 ºC. In a preferred embodiment, step (a) is performed using a polymer with a low melting point, that is, with a melting point below 140 ºC. For example, step (a) is performed using PCL, PBAT, PLA, PHA or PBSA. The temperature of the mixing step can be adapted by a person skilled in the art depending on the type of polymer and / or biological entities used for the production of the main batch. In particular, the temperature is chosen according to the melting point or melting temperature of the first polymer. In a particular embodiment, step (a) is carried out at the melting point of the first polymer. The polymer is then in a partially or fully molten state. In another embodiment, step (a) is carried out at a temperature above the glass transition temperature of said polymer, particularly between the glass transition temperature (Tg) and the melting temperature of said polymer. In a specific embodiment, step (a) of mixing is carried out at a temperature above the melting temperature of said polymer.
[0104] [0104] In a particular embodiment, the first polymer has a melting temperature below 140 ºC. According to the invention, the first polymer is heated to a temperature below 140 ° C, and the composition is introduced into the first polymer during said heating step. In another particular embodiment, the first polymer has a melting temperature above 140 ºC. According to the invention, the first polymer is heated to a temperature above 140 ° C, and the composition is introduced into the first polymer during said heating step. More generally, the main batch preparation step (step a) is carried out at a temperature at which the first polymer is in a partially or fully molten state, so that the biological entities of the composition are integrated into the first polymer during extrusion. Preferably, step a) is carried out by extrusion.
[0105] [0105] In the preferred embodiment, the main batch is prepared by (1) extruding a first polymer, wherein said first polymer has a melting temperature below 140 ° C and (ii) introducing the composition during the extrusion of the first polymer , before introducing said main batch in a polymer based matrix in order to prepare the plastic article. In another embodiment, the main batch is prepared by (i) extruding a first polymer, in which said first polymer has a melting temperature above 140 ° C and (ii) introducing the composition during the extrusion of the first polymer, before introducing said main batch into a polymer based matrix in order to prepare the plastic article.
[0106] [0106] In a particular embodiment, the first polymer is a polyester, preferably selected from polycaprolactone (PCL), poly (butylene succinate) (PBS) polybutylene succinate adipate (PBSA), poly (butylene adipate co-terephthalate ) (PBAT), polyhydroxyalkanoate (PHA), polylactic acid (PLA) or copolymers. In another particular embodiment, the first polymer is a natural polymer, preferably selected from starch. In another particular embodiment, the main batch comprises a "universal" polymer, that is, a polymer that is compatible with a wide range of polymers, such as a copolymer (for example, ethylene vinyl acetate EVA copolymer).
[0107] [0107] In a particular embodiment, the main batch comprises a first polymer that has a melting temperature below 140 ºC and / or a glass transition temperature below 70 "* C. preferably, the first polymer of the main batch has a melting temperature below 120 ° C and / or a glass transition temperature below ° C. For example, such a first polymer is selected from the group consisting of PCL, PBS, PBSA, PBAT, PLA and EVA. Preferably, such a first polymer is selected from the group consisting of PCL, PBAT, EVA and PLA and mixtures thereof. In a particular embodiment, the first polymer is PCL. In another particular embodiment, the first polymer is PLA. The advantage of such a modality is that it reduces the heating of biological entities in the composition during the main batch production process.
[0108] [0108] The main batch comprises between 5% and 50 8% by weight of the liquid composition, based on the total weight of the main batch. Preferably, the composition of the invention represents between 10% and 40%, more preferably between% and 30%. In a particular embodiment, the main batch comprises about 20% by weight of the composition of the invention, based on the total weight of the main batch. In another particular embodiment, the main batch comprises about 10% by weight of the composition of the invention, based on the total weight of the main batch. In a particular embodiment, the biological polymer degradation entities of the composition are able to degrade the first polymer. Alternatively or in addition, biological polymer degradation entities are able to degrade at least one polymer from the final plastic article that incorporates the main batch.
[0109] [0109] The main batch may additionally comprise one or more additional compounds. In particular, the main batch may additionally comprise one or more additives. In general, additives are used to improve specific properties in the final product. For example, additives can be selected from the group consisting of, but not limited to, plasticizers, coloring agents, processing aids, rheological agents, antistatic agents, anti-UV agents, tempering agents, impact modifiers, compatibilizers, slip additives, flame retardant agents, antioxidants, pro-oxidants, light stabilizers, oxygen scavengers, adhesives, products, excipients, slip additives. Advantageously, the main batch comprises less than 20% by weight of such additives, preferably less than 10%, typically between 0.1 and 10% by weight of such additives. Preferably, the main batch comprises at least one additive selected from plasticizers, glide additives and light stabilizers. In particular, the main batch may additionally comprise at least one charge. The load can be selected from any conventional load used in the plastic industry. The exact type and quantity of fillers can be adapted by an expert in the art depending on the type of main batch composition. Advantageously, the main batch comprises at least one filler selected from antacid fillers, such as calcium carbonate, talc or silica.
[0110] [0110] In a particular embodiment, the main batch composition comprises, based on the total weight of the main batch: - from 50% to 95% by weight of a first polymer; - from 5% to 50% by weight of the liquid composition which comprises biological polymer degradation entities; and optionally - at least one additive.
[0111] [0111] In another particular embodiment, the main batch comprises, based on the total weight of the main batch: - from 70% to 90% by weight of a first polymer; - from 10% to 30% by weight of the liquid composition which comprises biological polymer degradation entities; and optionally - at least one additive.
[0112] [0112] In another particular modality, the main batch comprises, based on the total weight of the main batch: - from 70% to 80% by weight of a first polymer; - from 10% to 20% by weight of the liquid composition comprising biological polymer degradation entities; and optionally - at least one additive.
[0113] [0113] In a particular embodiment, the main batch comprises, based on the total weight of the main batch: - from 70% to 80% by weight of PCL - from 10% to 20% by weight of the liquid composition, which comprises biological entities of degradation of PLA; and optionally - at least one additive.
[0114] [0114] In another particular modality, the main lot comprises, based on the total weight of the main lot: - from 70% to 80% by weight of PLA - from 10% to 20% by weight of the liquid composition that comprises biological entities of degradation of PLA; and optionally - at least one additive.
[0115] [0115] In a particular embodiment, the main batch is produced by a process called "compounding", often an extrusion granulation process, in which the first polymer is melted and mixed with the composition of the invention. Compound formation combines mixing and mixing techniques during a thermal process, in order to guarantee uniformity, homogeneity and dispersion in the main batch. Compound formation is a technique known to a person skilled in the art. Such compounding process can be carried out with an extruder, such as single-screw extruders, multiple-screw extruders of co-rotating or counter-rotating design, dispersive kneaders, reciprocating single-screw extruders (co-kneaders).
[0116] [0116] More generally, step (a) of preparing the main batch can be performed with an extruder, in which the The first polymer is heated, melted and mixed with the composition. The first polymer can be introduced into the extruder in a granulated or powdered form, preferably in a granulated form.
[0117] [0117] In a preferred embodiment, the extruder used for the production of the main batch of step (a) is a multi-screw extruder, preferably a double-screw extruder, more preferably, a cogiratory double-screw extruder. In a specific embodiment, the extruder additionally comprises, after the threads, a static mixer. In another embodiment, the extruder is used with a perforated die with holes, preferably at least a two-hole die. In another preferred embodiment, the extruder is used with an orifice die. An element skilled in the art will easily adapt the characteristics of the die (for example, the number and size of the orifices, etc.), for the pressure, the outlet or the desired main batch.
[0118] [0118] In a preferred embodiment, the residence time of the first polymer mixture and the composition in the extruder is between 5 seconds and 3 minutes, preferably less than 2 minutes. When the main batch comprises a polymer with a melting temperature below 120 ° C, the residence time of the mixture is between 5 seconds and 10 minutes in the extruder, preferably less than 5 minutes.
[0119] [0119] An element skilled in the art will easily adapt the characteristics of the extruder (for example, the length and diameter of the thread (or threads), the profile of threads, degassing zones etc.), and the residence time for the first polymer , the composition and type of main batch desired.
[0120] [0120] In particular, such an extruder may contain a main feeder and several successive heating zones, where the temperature can be independently controlled and regulated and where additional components can be added at different times during the process. Natural and vacuum degassing zones are required during extrusion to remove volatile products such as water.
[0121] [0121] The liquid composition is introduced with a pump. In a particular embodiment, the liquid composition is introduced at a later stage of the mixing step (i.e., in the last heating zones) and, more particularly, when the first polymer is in a partially or fully molten state. In this way, the exposure of biological entities to high temperature is reduced. Preferably, the residence time of the liquid composition in the extruder is half the length of the residence time of the first polymer or less. In another particular embodiment, the liquid composition of the invention is introduced before the polymer in the extruder. In this way, the contact between the liquid composition and the polymer is increased.
[0122] [0122] According to the invention, after step (a) of preparing the main batch, said main batch can be conditioned in any suitable solid form. In this regard, in a preferred embodiment, the main batch is formed into a rod through a matrix. The stem is then cooled, before being cut in the form of granules and / or pellets from the main batch and optionally dried. An underwater pelletizer can also be used. In a further embodiment, said granules of the main batch can be pulverized or micronized to produce a powder from said main batch. It is then possible to subject the powder to an extrusion-granulation process, preferably in an extruder so that the mixture is in a partially or fully melted state, before step (b).
[0123] [0123] According to the process of the invention, the main batch is introduced during step (b) in a polymer based matrix in order to produce a plastic article. The step of introducing the main batch into the polymer-based matrix is carried out at a temperature where both the first polymer and at least one polymer of the polymer-based matrix are in a partially or fully molten state. When the main batch emitted from step (a) and the polymer-based matrix are in a granulated form, it is possible to submit the granules to a dry mixing step before step (b) of introducing the main batch into the matrix based on polymer.
[0124] [0124] The polymer-based matrix comprises at least one polymer selected from natural or synthetic polymers and / or derivatives and / or mixtures thereof. An element skilled in the art has the ability to choose the polymer (or polymers) of the polymer-based matrix depending on the nature of the final plastic article.
[0125] [0125] In a particular embodiment, step (b) is carried out using a polymer with a high melting point, that is, with a melting point above 140 ºC. For example, step (b) is performed using PLA.
[0126] [0126] In a particular embodiment, the polymer-based matrix comprised at least one polymer selected from synthetic polymers.
[0127] [0127] In a particular embodiment, the polymer-based matrix comprises at least one polyester chosen from copolymers of lactic acid and / or succinic acid and / or terephthalic acid or a mixture thereof. Advantageously, the polyester-based matrix comprises at least one polyester chosen from polylactic acid (PLA), polyglycolic acid (PGA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), poly (butylene succinate) (PBS), polybutylene adipate succinate (PBSA), poly ((butylene adipate co-terephthalate) (PBAT) and derivatives or blends / mixtures thereof. In a preferred embodiment, the polyester-based matrix comprises at least one polyester chosen from PLA and / or PCL and / or PBAT, more preferably, PLA.
[0128] [0128] According to another particular embodiment, the polymer-based matrix comprises at least one polymer selected from natural polymers. Natural polymers can be selected from the group of lignin, polysaccharides, such as cellulose or hemicellulose, starch, chitin, chitosan and derivatives thereof or mixtures / mixtures thereof. In a particular embodiment, natural polymers are plasticized (for example, by a plasticizer such as water or glycerol) before being used to produce the main batch composition. Such plasticization stage modifies the chemical structure of natural polymers allowing its use through a plastic production process.
[0129] [0129] In particular, the polymer-based matrix may additionally comprise at least one filler and / or at least one additive. The load can be selected from any conventional load used in the plastic industry. The exact type and quantity of fillers can be adapted by an expert in the art depending on the type of main batch composition. Advantageously, the plastic article comprises at least one filler selected from calcium carbonate, talc or silica.
[0130] [0130] Advantageously, the plastic article comprises less than 20% by weight of such additives, preferably less than%, more preferably less than 5%, typically between 0.1 and 4% by weight of such additives, with based on the total weight of the plastic article. Alternatively, the plastic article comprises between 5% to 10% by weight of such additives.
[0131] [0131] The purpose of the invention is also to provide a process in which a polymer-based matrix is mixed with a main batch comprising a high quantity of biological entities to make a plastic article in which the biological entities are precisely added and homogeneously distributed.
[0132] [0132] According to the invention, after step (a) of mixing, and the optional conditioning of the mixture in a suitable solid form, the plastic composition produced is (b) shaped into a plastic article.
[0133] [0133] Advantageously, step (b) is implemented at a temperature where the polymer matrix polymer and the first polymer are in a partially or fully molten state. For example, step (b) can be performed at a temperature at or above 40 ”“ C, particularly at or above 45 ºC, 55 ºC, 60 ºC, 70 “ºC, 80 ºC, 90 ºC, 100 ºC or still above 150 ºC, depending on the nature of the polymer. Typically, this temperature does not exceed 300 ºC. More particularly, the temperature does not exceed 250 ºC. The temperature of step (b) can be adapted by a person skilled in the art depending on the type of main batch and the polymer-based matrix and / or the type of plastic articles desired. In particular, the temperature is chosen according to the melting point or the melting temperature of the polymer of the polymer matrix and the first polymer.
[0134] [0134] In a particular embodiment, step (b) is carried out at the melting point of the polymer of the polymer-based matrix. The polymer is then in a partially or fully molten state. In another embodiment, step (b) is carried out at a temperature between the glass transition temperature (Tg) and the melting point of said polymer. In another particular embodiment, step (b) is carried out at a temperature above the melting point of said polymer.
[0135] [0135] Typically, said step (b) can be performed by extrusion, extrusion composition, extrusion cork molding, blown film extrusion, casting film extrusion, calendering and thermoforming, injection molding, compression molding, extrusion expansion, rotary molding, ironing, coating, stratification, expansion, pultrusion, compression granulation or 3D printing. Such operations are well known to the person skilled in the art, who will easily adapt the process conditions according to the type of plastic articles desired (eg temperature, residence time, etc.). As an example, casting and blown film extrusions are particularly suitable for the production of plastic films. As another example, the calendering process is particularly suitable for the production of plastic sheets and injection molding, thermoforming, cork molding, rotational molding or 3D printing are particularly suitable for the production of rigid plastic articles.
[0136] [0136] In a particular embodiment, step (b) is implemented with a solid main batch in a granulated or powder form, preferably in a granulated form.
[0137] [0137] In a particular embodiment, 0.5 to 30% by weight of the main batch is added to the polymer-based matrix, based on the total weight of the plastic article, preferably less than 20%, more preferably, less than% and even more preferably less than 10%. In a particular embodiment, about 5% by weight of the main batch is introduced into the polymer-based matrix. In a particular embodiment, about 10% by weight of the main batch is introduced into the polymer-based matrix.
[0138] [0138] In another particular embodiment, 1% to 5% by weight of the main batch are incorporated and / or mixed with 95% to 99% by weight of a polymer based matrix in a partially or fully molten state.
[0139] [0139] In another particular embodiment, the present invention relates to a process for preparing a plastic article comprising at least PLA, which comprises the steps of a) preparing a main batch comprising biological PLA and PCL degradation entities by (1) heating of PCL; and (ii) introducing from 5% to 50% by weight of a liquid composition of the invention containing biological PLA degradation entities based on the total weight of the main batch during PCL heating; and (b) introducing the main batch into a PLA-based matrix during the manufacture of the plastic article; where step a) is carried out at a temperature where PCL is in a partially or fully molten state, preferably above 65 ° C, more preferably about 70 ° C and step b) is carried out at a temperature where both PCL and PLA are in a partially or fully molten state, preferably above 120 ° C, more preferably about 155 “C.
[0140] [0140] In another particular embodiment, the present invention relates to a process for preparing a plastic article comprising at least PLA, which comprises the steps of a) preparing a main batch comprising biological PLA and PLA degradation entities by (1) heating PLA; and (ii) introducing from 5% to 50% by weight of a liquid composition of the invention containing biological PLA degradation entities based on the total weight of the main batch in PLA during the heating of PLA; and (b) introducing the main batch into a matrix based on
[0141] [0141] In another embodiment, the liquid composition of the invention is directly introduced into the polymer (or polymers) that make up the plastic article.
[0142] [0142] An object of the invention is also to provide a process for preparing a plastic article, comprising: - a step (a) of mixing less than 11%, particularly between 0.1% to 10% by weight of the composition as described above based on the total weight of the mixture, with at least one polymer, in which the biological entities of the composition have the capacity to degrade said polymer and,
[0143] [0143] - a step (b) of forming said mixture of step (a) in a plastic article.
[0144] [0144] In a particular embodiment, the process further comprises a step of mixing at least one additive and / or at least a second synthetic polymer and / or a natural polymer with the polymer and biological entities, prior to step (b). Alternatively, such an additive and / or polymer (or polymers) can be mixed in step (a) with the polymer and biological entities.
[0145] [0145] In a particular embodiment, the polymer used in step (a) is in a granulated form. In another embodiment, the polymer is in powder form. For this purpose, the polymer can be mechanically pretreated before mixing step (a), to lead to such a powder form. In particular, the polymer can be crushed.
[0146] [0146] Mixing step (a) is carried out at a temperature where the polymer is in a partially or fully molten state. Mixing step (a) can then be carried out at a temperature of 40 ° C or above, particularly at or above 45 ° C, 55 ° C, 60 ° C, 70 “° C, 80 ° C, 90 ° C, 100 ° C, or still above 150 ºC, depending on the nature of the polymer. Typically, this temperature does not exceed 300 ºC. More particularly, the temperature does not exceed 250 * C. The temperature of the mixing step can be adapted by a person skilled in the art depending on the type of polymer and / or the composition used for the production of the plastic article. In particular, the temperature is chosen according to the melting point or melting temperature of the polymer. In a particular embodiment, step (a) of mixing is carried out at the melting point of the polymer of the plastic article. The polymer is then in a partially or fully molten state. In another embodiment, the mixing step (a) is carried out at a temperature above the glass transition temperature of said polymer, particularly between the glass transition temperature (Tg) and the melting temperature of said polymer. In a specific embodiment, step (a) of mixing is carried out at a temperature above the melting temperature of said polymer.
[0147] [0147] In a particular embodiment, the plastic composition of step a) can be produced by a process called "compounding", often "an extrusion granulation process, in which the polymer is melted and mixed with the composition of the invention. Compound formation combines mixing and mixing techniques during a thermal process, in order to guarantee uniformity, homogeneity and dispersion in the final compound. Compound formation is a technique known to a person skilled in the art. Such compounding process can be carried out with an extruder, such as single-screw extruders, multiple-screw extruders of co-rotating or counter-rotating design, dispersive kneaders, reciprocating single-screw extruders (co-kneaders).
[0148] [0148] Preferably, step (a) of mixing the polymer (or polymers) and the liquid composition can be carried out with an extruder, in which the polymer is heated and melted and mixed with the composition of the invention. The polymer can be introduced into the extruder in a granulated or powdered form, preferably in a granulated form.
[0149] [0149] According to a particular embodiment, the mixing step (a) comprises a first step of introducing the liquid composition into a first polymer that has a low melting point (below 140 "ºC, preferably below 120 ºC), such as PCL, PBS, PBSA, PLA, PHA, PBAT; and a second step in which a polymer-based matrix comprising a second polymer that has a high melting point, such as PLA, is then added to the mixture that results from the first step. For example, the liquid composition is added to the PCL which has been heated to about 70 ° C to be in a partially molten state. Then, PLA that has been heated to about 150 ° C to be in a partially molten state is added directly to the mixture.
[0150] [0150] In a preferred embodiment, the extruder used for the production of the plastic composition of step a) is a multi-screw extruder, preferably a double-screw extruder, more preferably, a cogiratory double-screw extruder. In a specific embodiment, the extruder additionally comprises, after the threads, a static mixer. In another embodiment, the extruder is used with a hole-punched mold (or holes).
[0151] [0151] In a preferred embodiment, the residence time of the mixture in the extruder is between 5 seconds and 3 minutes, preferably less than 2 minutes. When the plastic composition comprises a polymer with a melting temperature below 120 ° C, the residence time of the mixture in the extruder is preferably less than 5 minutes.
[0152] [0152] An element skilled in the art will easily adapt the characteristics of the extruder (for example, the length and diameter of the thread (or threads), the thread profile (or threads), degassing zones etc.), and the dwell time for the polymer, the liquid composition of biological entities and the type of plastic composition desired.
[0153] [0153] In particular, such an extruder may contain a main feeder and several successive heating zones, where the temperature can be independently controlled and regulated and where additional components can be added at different times during the process. Natural and vacuum degassing zones are required during extrusion to remove volatile products such as water.
[0154] [0154] The liquid composition is introduced with a pump. In a particular embodiment, the liquid composition comprising biological entities is introduced at a later stage of the mixing step (that is, in the last heating zones) and, more particularly, when the polymer is in a partially or fully molten state. In this way, exposure to elevated temperature is reduced. Preferably, the residence time of the liquid composition in the extruder is half the length of the residence time of the polymer or less. In another particular embodiment, the liquid composition of the invention is introduced before the polymer in the extruder. In this way, the contact between the liquid composition and the polymer is increased.
[0155] [0155] According to the invention, after step (a) of mixing, the mixture can be conditioned in any suitable solid form. In this sense, in a preferred embodiment, the mixture emitted from step (a) is formed on a stem through a mold. The rod is then cooled and, optionally, dried before being cut in the form of granules of plastic composition. In an additional embodiment, said granules of the plastic composition can be pulverized or micronized to produce a powder of said plastic composition.
[0156] [0156] The polymer can be selected from synthetic polymers. In a particular embodiment, the polymer is selected from aliphatic polyesters, preferably from PLA.
[0157] [0157] In another particular embodiment, the process further comprises a step of mixing at least one additive and / or at least a second polymer and / or at least one filler with the polymer and the composition, before step (b). Alternatively, such an additive and / or polymer and / or filler can be mixed in step (a) with the polymer and the composition of the invention.
[0158] [0158] The second polymer can be selected from synthetic or natural polymers. The load can be selected from any conventional load used in the plastic industry. Advantageously, the plastic article comprises at least one filler selected from calcium carbonate, talc or silica. Advantageously, the plastic article comprises less than 20% by weight of such additives, preferably less than 10%, more preferably less than 5%, typically between 0.1 and 4% by weight of such additives.
[0159] [0159] According to the invention, after step (a) mixing, and the optional conditioning of the mixture in a suitable solid form, the plastic composition produced is (b) shaped into a plastic article.
[0160] [0160] Advantageously, step (b) is implemented at a temperature at which the polymer of the plastic composition is in a partially or fully molten state. For example, step (b) can be carried out at a temperature at or above 40 "C, particularly at or above 45 ºC, 55 ºC, 60 ºC, 70 ºC, 80 ºC, 90 ºC, 100 ºC, or even above 150 * C, depending on the nature of the polymer in the plastic composition. Typically, this temperature does not exceed 300 ºC. More particularly, the temperature does not exceed 250 ºC. The temperature of the step (Db) can be adapted by a person skilled in the art depending on the type of plastic composition and the polymer it comprises and / or the type of plastic articles desired. In particular, the temperature is chosen according to the melting point or the melting temperature of the polymer of the plastic composition produced from step (a).
[0161] [0161] In a particular embodiment, step (b) is carried out at the melting point of the polymer of the plastic composition. The polymer is then in a partially or fully molten state. In another embodiment, step (b) is carried out at a temperature between the glass transition temperature (Tg) and the melting point of said polymer. In another particular embodiment, step (b) is carried out at a temperature above the melting point of said polymer.
[0162] [0162] Typically, said step (b) can be performed by extrusion, extrusion composition, extrusion cork molding, blown film extrusion, casting film extrusion, calendering and thermoforming, injection molding, compression molding, extrusion expansion, rotary molding, ironing, coating, stratification, expansion, pultrusion, compression granulation or 3D printing. Such operations are well known to the person skilled in the art, who will easily adapt the process conditions according to the type of plastic articles desired (eg temperature, residence time, etc.). As an example, cast or blown film extrusions are particularly suitable for the production of plastic films. As another example, the calendering process is particularly suitable for the production of plastic sheets and injection molding, thermoforming, cork molding, rotational molding or 3D printing are particularly suitable for the production of rigid plastic articles.
[0163] [0163] In a preferred embodiment, step (b) is implemented with a solid plastic composition in a granulated or powder form, preferably in a granulated form.
[0164] [0164] The plastic article comprises between 0.1% and 10% by weight of the plastic composition, based on the total weight of the plastic article. Preferably, the composition represents between 0.1% and 58%, more preferably between 0.1% and 3% of the plastic article. Alternatively, the plastic composition represents about 5% of the plastic article.
[0165] [0165] In another embodiment, the liquid composition of the invention is directly introduced in step (b) of forming the plastic article.
[0166] [0166] In a particular embodiment, the present invention relates to a process for preparing a plastic article, which comprises: - a step (a) of mixing between 0.1% to 10% by weight of the composition as described above with at least less PLA, in which the biological entities of the composition are selected from proteases that have a PLA degradation activity and, - a step (b) of forming said mixture of step (a) in a plastic article, in which the mixing step (a) is preferably carried out at a temperature between 150 and 180 ° C and / or in an extruder, preferably a twin screw extruder and, more preferably, a cogiratory twin screw extruder.
[0167] [0167] More generally, plastic articles can be produced by any techniques known to a person skilled in the art using the liquid composition of the invention.
[0168] [0168] Advantageously, the plastic article of the invention comprises, based on the total weight of the plastic article: - from 10 to 98% of a polyester as defined above, particularly polylactic acid (PLA), - from 0.01 to 10% of a polysaccharide carrier, selected from starch derivatives, natural gums, marine extracts, animal and microbial polysaccharides as defined above, - from 0 to 30% of a first polymer that has a melting temperature below 140 ºC and / or a glass transition temperature below 70 ºC, as defined above and - from 0.01 to 108% of biological entities that have PLA degradation activity.
[0169] [0169] Preferably, the plastic article comprises at least 3% of a first polymer, more preferably, at least 4% of a first polymer. In another preferred embodiment, the plastic article comprises from 0.1% to 1% of polysaccharide carrier. In another preferred embodiment, the plastic article comprises PLA as the main component and less than 1% of biological entities that have a PLA degradation activity, preferably less than 0.5 8%, preferably about 0.25 %. In another particular embodiment, the plastic article comprises from 0.1 to 0.5% of enzymes that have a PLA-degrading activity, preferably about 0.25%. Plastic article with homogeneous dispersion of biological entities
[0170] [0170] Another objective of the invention is also to provide a method to homogenize the dispersion of biological polymer degradation entities in a plastic article comprising at least one polymer and said biological entities, wherein said method comprises introducing, during the production process of such plastic article, the liquid composition as described above.
[0171] [0171] Thus, another objective of the invention is to provide a plastic article comprising at least one polymer and the composition as described above, in which the biological entities of the composition are able to degrade said polymer and are homogeneously dispersed in the article plastic.
[0172] [0172] The inventors revealed that the production of plastic article with the composition of the invention led to the plastic article with an increased homogeneity of the dispersion of biological entities in the plastic article compared to the plastic article produced with biological entities in a solid form, thereby way, to a plastic article with improved physical properties. The inventors also revealed that the choice of carrier is of importance in order to protect biological entities during the production process and led to plastic articles with expected technical performance and degradation.
[0173] [0173] The inventors showed that it is possible to improve the degradability and the physical and / or mechanical characteristics of plastic articles that comprise polymer and biological entities that have a polymer degradation activity by using the liquid composition of the invention during the production process of the plastic article, in comparison to the use of a liquid or solid composition of biological entities of the technique.
[0174] [0174] Thus, another objective of the invention is to provide a method to homogenize the dispersion of biological entities in a plastic article, wherein said method comprises introducing, during the plastic article production process, the liquid composition of the invention .
[0175] [0175] The homogeneity of the dispersion of biological entities in the plastic article can be evaluated by an element skilled in the art, according to the methods known per se in the art. For example, and within the context of the invention, the homogeneity of the dispersion of biological entities in the plastic article can be assessed by measuring at least one of the following properties: Turbidity, surface roughness, dynamic friction coefficient, Young's modulus, elongation at break , tensile strength at break, maximum stress, stress at maximum stress, impact resistance and biodegradability.
[0176] [0176] Turbidity is defined as the percentage of incident light dispersed by more than 2.5º through the plastic article. Turbidity is caused by impurities contained in the plastic article (such as accumulation of tiny particles in the article or very small defects on the surface) or its level of crystallinity. The lower the turbidity value, the greater the sharpness of the article. Turbidity has no specific unit, expressed in%. If the turbidity value is greater than 30 &%, the article is dispersed. Turbidity meters and spectrophotometers can be used to measure the level of Turbidity. Turbidity of plastic articles can be measured according to ASTM D1003 or NF EN 2155-9. According to the invention, the Turbidity of the article is measured according to NF EN
[0177] [0177] Elongation at break or stress at break of the plastic article is related to the ability of a plastic article to resist changes in shape without cracking. Elongation at break is also known as fracture stress or tensile elongation at break. This is measured in% and can be calculated by dividing the extension to rupture of the plastic article by the initial useful length of the plastic article and multiplying by 100.
[0178] [0178] The tensile strength at break also known as tensile strength at break or as the tensile strength of the plastic article is defined as the tensile stress at which the test specimen breaks. The tensile stress also known as ultimate tensile stress or maximum stress corresponds to the maximum tensile stress supported by the test specimen during the tensile test. It is calculated by dividing the maximum load by the area in the original minimum cross section of the specimen. The result must be expressed in force per unit area, often megapascals (MPa).
[0179] [0179] The stress at maximum tension or tensile strength at the tensile strength is the tensile strength at the point corresponding to the tensile strength. It is measured in% and can be calculated by dividing the maximum tension extension of the plastic article by the initial useful length of the plastic article and multiplying by 100.
[0180] [0180] Young's modulus of the plastic article, also known as the elastic modulus or tensile modulus, is a measure of the stiffness of a solid material. The same is a “mechanical property of linear elastic solid materials. This defines the relationship between stress (force per unit area) and effort (proportional deformation) in a material. The result must be expressed in pascal or megapascals (MPa).
[0181] [0181] Young's modulus, elongation at break, tensile strength at break, maximum stress, stress at maximum tension, of plastic articles can be measured according to ASTM D882-12 or NF EN ISO 527-3 for plastic article with a thickness below 1 mm. They can be particularly measured in two different directions: machine direction or cross direction. The determination of these criteria for plastic articles with a thickness of 1 mm to 14 mm is made with ASTM D638-14 or NF EN ISO 527-2.
[0182] [0182] Elongation at break, tensile strength at break (or ultimate tensile strength), maximum stress, stress at maximum tension, and Young's module of plastic articles can be measured according to ASTM D882-12 or NF EN ISO 527 -3 for plastic items less than 1 mm thick. They can be measured in two different directions: machine direction or transversal direction with the following parameters (adhesion separation rate for Young's modulus: 10 mm / min, adhesion separation rate for other properties: 50 mm / min, separation by initial adhesion 100 mm, dimension of plastic article: length 150 mm; width 15 mm; average thickness 17 µm) or other conditions as indicated in the standards. The determination of these criteria for plastic articles with a thickness of l1 mm to l4 mm is made with ASTM D638-14 or NF EN ISO 527-2.
[0183] [0183] In particular, the plastic article, obtained by using a liquid composition as explained above, may exhibit a greater elongation at break than the same plastic article produced from a solid composition of biological entities. Typically, the plastic article shows an elongation at break, in at least one direction selected from the machine direction or transverse direction, 10% greater, preferably 20%, 50%, 100% greater, or more, than the elongation the rupture of a plastic article produced with a solid composition of biological entities.
[0184] [0184] In particular, the plastic article produced with a liquid composition of the invention may exhibit a greater tensile strength at break than the same plastic article produced from a solid composition of biological entities. Typically, the plastic article shows a tensile strength at break 20% higher, preferably 30%, 40%, 50% higher, or more, than the tensile strength at break of a plastic article produced with a solid composition of entities biological. Typically, the plastic article shows a tensile strength at break 5 MPa greater, preferably 7 MPa, 10 MPa, 15 MPa greater, or more, than the tensile strength at break of a plastic article produced from a solid composition of biological entities, in at least one direction selected from the machine direction or transversal direction.
[0185] [0185] In particular, the plastic article produced from a liquid composition of the invention may exhibit a larger Young module than the same plastic article produced from a solid composition of biological entities. Typically, the plastic article shows a Young module of about 20% larger, preferably 30%, 40%, 50% larger, or more, than the Young module of a plastic article produced from a solid composition of biological entities, in at least one direction selected from the machine direction or transverse direction. Typically, the plastic article shows a Young module of about 20 MPa larger, preferably 30 MPa, 50 MPa, 100 MPa larger, or more, than the Young module of a plastic article produced from a solid composition of biological entities, in at least one direction selected from the machine direction or transverse direction.
[0186] [0186] The dynamic friction coefficient or sliding friction coefficient or kinetic friction coefficient (also abbreviated as naked ”) occurs when two objects are moving relative to each other and rubbing (like a mass on the ground). According to the invention, up is measured when a plastic article is sliding over another plastic article. The sliding friction coefficient is defined as the ratio between the dynamic friction force faced by the plastic article (force necessary to overcome the friction) and the normal N force that acts perpendicular to both plastic articles. The coefficient has no unity. The surfaces to be tested are placed in flat contact and under uniform contact pressure (normal N force). The force required to move the surfaces in relation to each other is recorded (dynamic frictional force). According to the invention, pp is measured according to the standard NF EN ISO-8295 (December 2004) which is suitable for plastic film or plastic sheet with a thickness below 0.5 mm. The apparatus comprises a horizontal test table on which the plastic article is placed, where a mass generates the press force (1.96 N) and to which the plastic article is attached, and a traction mechanism to produce a relative movement between the dough and the test table. According to the invention, the mass is pulled and moved on the test table (test speed = 500 mm - min). The measure is accurate at about 0.01%. In particular, the plastic article produced from a liquid composition of biological entities may exhibit a lower coefficient of dynamic friction than the same plastic article produced from a solid composition of biological entities. Typically, the plastic article shows a dynamic friction coefficient 5% less, preferably%, 15%, 20% less, or more, than the dynamic friction coefficient of a plastic article produced from a solid composition of biological entities .
[0187] [0187] The surface roughness of the plastic article can be assessed by a visual test by a user panel. The plastic article shows no visible defects on its surface, it is soft. The plastic article produced from a solid composition shows irregularities on the surface due to the aggregates of particles that can be felt by touch and are visible to the naked eye. This is also assessed by measuring the thickness using a Mitutoyo thickness gauge to demonstrate the presence of aggregates in the plastic article.
[0188] [0188] Impact resistance is defined as the resistance of a material to fracture under stress applied at high speed, defined by the amount of energy absorbed before fracture. For the rigid plastic article, the impact resistance can be measured according to the NF EN ISO 179 standard using plastic specimens produced with the same material as that plastic article and which has a thickness of 4 mm and a total length of 80 mm . The determination of impact resistance for rigid plastic articles with a thickness below 4 mm can also be measured directly on such plastic articles according to the standard NF EN ISO 6603-1. In particular, the plastic article obtained by using a liquid composition of biological entities of the invention may exhibit greater impact resistance than the same plastic article produced from a solid composition of biological entities. Typically, the plastic article of the invention shows an impact resistance of about 20% greater, preferably 25%, 30%, 40% greater than the impact resistance of a plastic article produced from a solid composition of biological entities .
[0189] [0189] The inventors also showed that the introduction of biological entities through the liquid composition of the invention during the production process of a plastic article does not affect the technical performances of such plastic articles compared to plastic articles that do not contain biological entities.
[0190] [0190] The invention also provides a method for increasing the biodegradability of a plastic article comprising at least one polymer, wherein said method comprises introducing during the production process of the plastic article, the liquid composition of the invention.
[0191] [0191] The biodegradability of the plastic article is defined as the release of monomers, dimers or water and carbon dioxide for a defined period of time under aqueous conditions. In particular, according to the invention, the biodegradability of a plastic article containing PLA is measured according to the release of lactic acid and lactic acid dimer. In particular, the plastic article obtained by using a liquid composition of the invention may exhibit greater biodegradability than the same plastic article produced from a liquid or solid composition of biological entities in the art. Typically, the plastic article of the invention shows a biodegradability of about 25%, 30%, 40%, or 100% greater than the biodegradability of a plastic article produced from a liquid or solid composition of biological entities in the art after 2 days .
[0192] [0192] In a particular embodiment, the plastic article is a plastic film, which comprises at least one polyester and biological entities capable of degrading said polyester.
[0193] [0193] Alternatively or additionally, the plastic film of the invention is a film with a thickness below 100 µm, preferably below 50 µm, more preferably below 30 µm, even more preferably below 20 µm.
[0194] [0194] In particular, the plastic film produced from the composition of the invention shows a lower turbidity value of about 3%, 4%, 5% or more, as compared to the turbidity value of a plastic film produced from a solid composition of biological entities. Consequently, the turbidity value of plastic film is comprised between 80% and 95%, preferably between 85% and 93%. Alternatively, the turbidity value of plastic film is above 30%, preferably above 50%, more preferably above 70%, even more preferably above 85%. Otherwise, the plastic film turbidity value is below 98%, preferably below 96%, more preferably below 95%, even more preferably below 94%. In another embodiment, the turbidity value of plastic film is below 60%.
[0195] [0195] In another particular embodiment, the Young's modulus of the film is preferably above 200 MPa in both directions (machine or transversal), and / or the tensile strength at break of the film is preferably above 15 MPa in both directions (machine or transverse), and / or the elongation at break of the film is preferably above 130% in the machine direction and above 300% in the transverse direction. In another particular embodiment, the film according to the invention has an elongation at break greater than 130 &, in the longitudinal direction and greater than 240 &% transversely, measured according to EN ISO 527-3, e ”or a resistance to tear greater than 30 N - mm in the transversal direction of the film, measured according to EN ISO 6383-1 and having a high PLA content. It also has an elastic modulus greater than 200 MPa in the longitudinal direction and greater than 150 MPa transverse, measured according to EN ISO 527-3 and 7 “or a maximum stress greater than 15 MPa in the longitudinal direction and greater than 13 MPa in transverse direction,
[0196] [0196] In another particular embodiment, the plastic article is a rigid plastic article, which comprises at least one polyester and biological entities that have a polyester degradation activity.
[0197] [0197] In a particular embodiment, the rigid plastic article of the invention shows an impact resistance above 17 kJI / m2, preferably above 20 kJI / m2 according to NF EN ISO 179.
[0198] [0198] In another particular embodiment, the rigid plastic article of the invention shows, according to NF EN ISO 527-2, a tensile module below 4 GPa, preferably below 3 GPa, and the tensile strength to rupture is above 40 MPa, preferably above 55 MPa.
[0199] [0199] According to a particular embodiment, the rigid plastic article of the invention is a sheet with a thickness below 800 µm, preferably below 450 pum. The sheet of the invention shows an impact resistance above 1 JJ, preferably above 1.5 J, more preferably above 2 J, according to NF EN ISO 7765-1. The elastic modulus of the sheet is below 2 GPa in both directions (machine and transverse) while maintaining sufficient stiffness for the intended application, and the stress at maximum sheet tension is above 3%, preferably above 4% in both directions.
[0200] [0200] In another particular embodiment, the plastic article is a non-woven fabric, comprising at least one polyester and biological entities that have a polyester degradation activity.
[0201] [0201] Advantageously, the resulting plastic article is a biodegradable plastic article that conforms to at least relevant standards and / or labels known to an element skilled in the art such as standard EN 13432, standard NFT51800, standard ASTM D6400, OK Biodegradation Soil ( Label TUV Austria), OK Biodegradation Water (Label TUV Austria), OK Compost (Label TUV Austria), OK Compost Home (Label TUV Austria).
[0202] [0202] A biodegradable plastic article refers to a plastic article that is at least partially transformed under environmental conditions into oligomers and / or monomers of at least one polyester of the plastic article, water, carbon dioxide or methane or biomass. For example, the plastic article is biodegradable in water. Preferably, about 90% by weight of the plastic article is biodegraded in water within less than 90 days, more preferably within less than 60 days, even more preferably within less than 30 days. More preferably, the plastic article can be biodegraded when exposed to the humid and temperature conditions that occur in the environment. Preferably, about 90% by weight of the plastic article is biodegraded in less than 3 years in the environment, more preferably in less than 2 years, even more preferably in less than 1 year. Alternatively, the plastic article can be biodegraded under industrial composting conditions, where the temperature is maintained above 50 “C.
[0203] [0203] Different liquid compositions were prepared using a commercial protease, Savinase6 16L (Novozymes) sold in a liquid form (which contains more than 50% by weight of polyols based on the total weight of the liquid composition and water). Such an enzyme is known for its ability to degrade polylactic acid (Degradation of Polylactide by commercial proteases; Y.Oda, A. Yonetsu, T. Urakami and K. Tonomura; 2000).
[0204] [0204] Liquid composition A (LC-A) was obtained by ultrafiltration and diafiltration of commercial Savinase6O 16L on the 3.5 Kd membrane (diafiltration factor of about 50) using 5 mM CaCl2. Such a process allows the polyols contained in commercial SavinaseO to be removed. Since no carrier was added to liquid composition A, this composition corresponds to the negative control.
[0205] [0205] Liquid compositions B and C (LC-B and LC-C) were also obtained from the commercial liquid form of Savinase6O by ultrafiltration and diafiltration on a 3.5 Kd membrane using 5 mM CaCl2 ( diafiltration of about 50). Respectively, maltodextrin (Maldex-TEREOS) and gum arabic (INSTANT GUM AA - NEXIRA), were added in powder form to the filtrate in the same percentage, in about 23% by weight based on the total weight of the liquid composition, in order to compare the protective effect of these two carriers. The description of the different liquid compositions is summarized in Table 1. Table 1: Description of liquid compositions of the invention (LC-B and LC-C) and a negative control (LC-A).
[0206] [0206] The main batch compositions were prepared from polycaprolactone polymer (PCL) pellets (Cover "" 6500 from Perstorp) and compositions of the invention described in Example 1.1. The enzyme activity of said main batch has been further described.
[0207] [0207] A compound forming machine, or cogiratory double screw extruder, was used (Leistritz ZSE 18MAXX). This compound forming machine comprised nine successive heating zones Z1 to 29, where the temperature can be independently controlled and regulated. An additional zone Z10 was present after zone 29, which corresponds to the double thread head (7210) which is also a heated part. A suitable thread profile was used in order to effectively mix the liquid composition of the invention with the molten polymer. The parameters used for each main extrudate batch are summarized in Table 2.
[0208] [0208] The molten polymer reached the Z10 thread which comprises a matrix plate with a 3.5 mm hole and was immediately immersed in a 2 m long cold water bath filled with a mixture of water and crushed ice. The resulting extrudate was granulated into solid pellets <3 mm.
[0209] [0209] According to this experiment, 80% by weight of the PCL was extruded with 20% by weight of the liquid composition. Table 2: Temperature profile and process parameters of the main compound formation process. speed (The 21st zone of | TIL, | zone of | ". | of thread z10 introduction | (xg / m) | introduction | (43 / h) (rpm) MB1 PCL / 710-70-70-70- (control | LC-A 70-65-65-65- z2 2.6 zo 0.66 negative 150) | (80/20) | 65-65 MB2 PCL / 10-70-70-70- LC-B 710-65 -65-65- z2 2.8 zo 0.7 175 (80/20) | 65-65 MB3 PCL / 10-70-70-70- Lc-C T70-65-65-65- z2 2.4 zo 0.6 150 (80/20) | 65-65
[0210] [0210] The enzyme activity in the main batches was determined according to the protocol described below. 50 mg of pellets were mixed with 10 ml of dichloromethane (Sigma Aldrich, CAS 75-09-2) in a 50 ml Falcon tube. The solution was mixed using a vortex (Genie2-Scientific Industrie) until the compound was completely dissolved. Then, 0.1 M ml of Tris Buffer pH 9.5 was added. Each tube was manually shaken to create an emulsion. The aqueous and organic phases were then separated by centrifugation at 10000G for 5 min (Heraeus Multifuge X302- Thermoscientific). The aqueous phase was removed and maintained separately. An additional 5 ml of 0.1 M Tris buffer pH 9.5 was added to the organic phase and the protocol was repeated until the aqueous phase was removed. Both 5 ml of aqueous phase are mixed. To remove the trace of dichloromethane in 10 ml of aqueous phase, oxygen was bubbled into the sample for 20 minutes. The protease activity of each sample was determined using a colorimetric test: 20 pl of sample in the correct dilution were mixed with 180 pl of a 5 mM PNA solution (N-succinyl-Ala-Ala-Ala-p- Nitroanilide, Sigma Aldrich-CAS 52299-14-6). The optical density was measured at 30 ºC-420 nm using an absorption spectrophotometer (Clariostar-BMG Labtech). The mass of active enzyme was thus determined using a calibration curve.
[0211] [0211] The comparison of the active enzyme mass and theoretical enzyme mass in the compound allowed the percentage of residual activity in the main batches to be determined.
[0212] [0212] The residual activities of the main batches are summarized in Table 3. Table 3: Residual activities of the main batches containing the liquid composition of the negative invention (arabic maltodextrin)) the EEA and
[0213] [0213] The main batches produced with the liquid compositions of the invention (LC-B and LC-C) demonstrate a greater residual activity compared to the main batch produced with a liquid composition that does not contain carrier (LC-A - negative control), which indicates greater protection of the enzyme during the extrusion process. The main batch produced with the composition of the invention which comprises gum arabic shows an even greater residual activity than the main batch produced with the composition of the invention which comprises maltodextrin.
[0214] [0214] The granulated main batch compositions of Example 1.2 were used to produce biodegradable polylactic acid-based plastic articles through an extrusion process. The biodegradability of said plastic articles was further tested. Preparation of the PLA-based matrix
[0215] [0215] The PLA-based die was extruded using the twin screw extruder described in Example 1.2. The composition of this matrix is 42.3% by weight of PLA 4043D by NatureWorks, 51.7% by weight of PBAT PBEO006 by NaturePlast and 6% by weight of CaCO3z by OMYA.
[0216] [0216] All materials were dried before extrusion. PLA and PBAT were dried for about 16 hours in a desiccator at 60 and 40 ºC respectively. The vacuum oven at 40 “* C-40 mb for 16 h was used for calcium carbonate. The temperature was set at 185 ºC in the ten zones of the extruder. The screw speed rate was 175 rpm, and the total inlet mass rate was about 7 kg / h. CaCCE was introduced in zone 7 for melted polymers using a gravimetric feeder to obtain the matrix. The resulting extrudate was cooled in a cold water bath before pelletizing. Main batches: The main batches MB1-MB2-MB3 described in Example 1.2 were used to produce the plastic films. Film blowing step
[0217] [0217] Before the film blowing extrusion, the main batches and the PLA-based matrix were dried in the desiccator for 40 h at 50 ºC. The blends were prepared in order to introduce the same amount of enzyme in all films, based on theoretical enzyme mass in the main batch according to Table 4: Table 4: composition of films manufactured from negative PLA film) PCL / 1C - | PCL / 1C- Matrix PCL / 1C-AB Cc Film 97% 3% - - pr e E FE EEE
[0218] [0218] A LabTech compact film blowing line of type LF-250 with a 20 mm 30 L / D extruder of type LBE20-30 / C was used to produce films. The screw speed rate was 50 rpm. The defined temperatures are detailed in Table 5. Table 5: Die and extruder temperature settings
[0219] [0219] depolymerization tests were performed, using plastic films produced in Example
[0220] [0220] 100 mg of each film was weighed and placed in a plastic bottle containing 50 ml of 0.1 M Tris buffer pH 8. Depolymerization was started by incubating each sample at 28 ºC, 150 rpm in a shaker incubation Infors HT Multitron Pro. The 1 ml aliquots of buffer were sampled regularly and filtered through a 0.22 pm syringe filter, the samples were analyzed by High Performance Liquid Chromatography (HPLC) with an Aminex HPX-87H column for monitor the release of lactic acid (LA) and lactic acid dimer. The chromatography system used was an UHPLC Ultimate 3000 system (Thermo Lisher Scientific, Inc. Waltham, MA, USA) including a pump module, a self-sampler, a column oven with a thermostat at 50 “ºC, and a UV detector at 220 nm. The eluent was 5 mM H2S04. The injection was 20 ul of sample. LA was measured according to standard curves prepared from commercial LA.
[0221] [0221] The hydrolysis of plastic films was calculated based on the LA and released LA dimer. The percentage of degradation is calculated in relation to the percentage of PLA in the films.
[0222] [0222] The results of depolymerization of the films, after 2 days, are shown in Table 6. Table 6: Comparison of the depolymerization of the film produced with the composition of the invention (B and C) and a negative control
[0223] [0223] Films produced with the compositions of the invention (MB2 / 1C-B and MB3 / 1C-C) show a higher depolymerization rate, due to a higher residual activity as compared to the control film produced with a private liquid carrier composition (MBl / 1C-A - negative control). These results confirm that the use of the liquid composition of the invention leads to greater protection of the enzyme during the extrusion process. The film produced with the composition comprising arabic gum shows even greater degradability than the film produced with the composition comprising maltodextrin. Example 2 - Preparation of a liquid composition of the invention, use of such a composition for the production of films and evaluation of the mechanical and degradation properties of the films.
[0224] [0224] A liquid composition (“LC”) was prepared from the commercial protease, Savinase6O 16L (Novozymes).
[0225] [0225] LC was obtained by ultrafiltration and diafiltration of commercial Savinase6 16L (diafiltration factor about 100 in the 3.5Kd membrane using 5 mM CaCl ;, to obtain a concentrated liquid composition and to remove polyols present in the commercial solution. About 23% gum arabic (INSTANT GUM AA -NEXIRA), based on the total weight of the liquid composition, was then added as a carrier in the liquid composition.
[0226] [0226] A solid composition was also prepared according to the same protocol using a commercial protease, SavinaseO 16L and the protocol defined above. The obtained liquid composition was concentrated and was then dried by freeze drying to obtain a solid composition called "SC".
[0227] [0227] Comparisons of the different compositions are summarized in Table 7. Table 7: Liquid and solid compositions Composition of liquid composition | Composition enzyme (LC) solid (SC) Aqueous solvent 51.3% 0.58% (water) Carrier (Gum 23.3% 15.7 & Arabica) Entities 23.0 &% 33% Biological Other components | 2.4 &% 50.8 &% including polyols (glycerol, propylene glycol) and other additives% are given by weight, with based on the total weight of the final composition
[0228] [0228] The main batches were prepared with polycaprolactone polymer pellets (PCL - Cover ”6500 from Perstorp) and the liquid or solid compositions of 2.1, using the same compound forming machine as in Example
[0229] [0229] More particularly, a main batch comprising PCL and the LC liquid enzyme composition of the Example
[0230] [0230] In parallel, a main batch comprising PCL and the SC solid enzyme composition of Example 2.1 were produced. SC was introduced in Zone 7 with the use of a gravimetric feeder suitable for dosing the solid in powder form. The main batch obtained was designated “MB-S”.
[0231] [0231] The parameters used for extrusion of the main batch are detailed in table 8 and table 9. A suitable thread profile was used in order to effectively mix the corresponding compositions with the polymer. Table 8: Je EEE extruder temperature settings. | Table 9: Extrusion parameters used for main batches Composition thread inlet speed (rpm) total (kg / h)% mm% mm
[0232] [0232] The molten polymer reached the Z10 thread which comprises a matrix plate with a 3.5 mm hole and was immediately immersed in a 2 m long cold water bath filled with a mixture of water and crushed ice. The resulting extrudate was granulated into solid pellets <3 mm.
[0233] [0233] Three different PLA-based matrices were used for the production of the films: two commercial compounds ecovioO
[0234] [0234] Matrix 1 was manufactured using a CLEXTRAL EV25HT twin screw extruder comprising twelve zones Z1 to Z12, in which the temperature is independently controlled and regulated. Matrix 1 is composed of 33% pre-plasticized PLA containing 10% by weight of tributyl acetyl citrate (CITROFOLO BII of Jungbunzlauer), 32% of PBAT Ecoflex C1200 supplied by BASF, 30% of thermoplastic starch in which the starch is standard corn starch 171111 supplied by Roquette and 5% calcium carbonate from OMYA.
[0235] [0235] For film blowing, a LabTech compact film blowing line type LF-250 with a 20 mm 30 L / D extruder type LBE20-30 / C was used. The thread speed rate used was 60 rpm. The film blowing ratio was about 5 for an object of 17 µm.
[0236] [0236] Before blowing the film, the MB-L (example 2.2) and the different PLA-based matrix were dried in a desiccator for 40 h at 50 ºC. Then, MB-L was mixed with the PLA-based matrix with a weight ratio between PLA and main batch of 93/7.
[0237] [0237] The films obtained with PLA matrix based on ecovioO F2332 and ecovioO F2223 were designated as film 1 and film
[0238] [0238] The film produced with Matrix 1 was designated as film 3 and Table 12 shows the parameters used for the extrusion. Table 12: Matrix and extruder temperature definitions; and ; o C- Production of control films with solid composition (MB-S)
[0239] [0239] The PLA-based matrix ecovioo F2332 and ecovioo F2223 and Matrix 1 were used as a PLA-based matrix to produce films with the main batch comprising the solid composition of biological entities and were respectively designated as film 4, film 5 and film 6.
[0240] [0240] Before blowing the film, the MB-S and the PLA-based matrix were dried in a desiccator for 40 h at 50 ºC. An additional main batch comprising only PCL and 70/30 w / w gum arabic was added to the MB-S / PLA-based matrix mixture in order to obtain the same concentration of biological entities in all films of the invention.
[0241] [0241] Finally, the films were made using 93%
[0242] [0242] MB-S was then mixed dry with the PLA-based matrix and introduced into the film blowing extruder.
[0243] [0243] The same process for films 1, 2 and 3 was used to produce the films, except for the temperature profile as shown in table 13: Table 13: Die and extruder temperature settings
[0244] [0244] Movies 1 and 4, Movies 2 and 5, and Movies 3 and 6 respectively have the same compositions, except for the nature of the main batch (solid vs. liquid).
[0245] [0245] Turbidity is determined using a Perkin Elmer 650S UV-Visible spectrometer equipped with a 150 mm integration sphere in accordance with NF EN 2155-9 (August 1989). The values are determined on a 50x30 mmº sample. In each film, measurements are repeated 3 times in 3 different parts of the film.
[0246] [0246] The dynamic friction coefficient (pp) is measured according to the standard NF EN ISO-8295 (December 2004) that fits the plastic film or plastic sheet with a thickness below 0.5 mm. The same is determined using a Floyd Instruments LS5 testing machine equipped with a sensor capacity of 20 N. The device comprises a horizontal test table on which the first sample is placed, a mass that generates with the press force (1 , 96 N) and to which the second sample is attached, and a traction mechanism to produce a relative movement between the mass and the test table. The dough is pulled and moved on the test table (test speed = 500 mm / min). The measure is accurate at about 0.01%. The sample dimensions are as follows: 80 mm x 200 mm.
[0247] [0247] The dynamic frictional force Fa is the average force in the first 6 centimeters of relative motion. C. Mechanical tensile and thickness properties
[0248] [0248] The mechanical tensile properties (elongation at break, tensile strength at break, Young's modulus) were determined using a Zwick testing machine equipped with a 50 N sensor capacity according to the ASTM D882-12 standard (at 23 ºC and 55% RH). Two film directions: machine direction and transverse direction were analyzed with the following parameters: - Adhesion separation rate for Young's modulus = mm / min - Adhesion separation rate for other properties = 50 mm / min - Adhesion separation initial: 100 mm, - Sample dimensions: 150 mm x 15 mm. - Average thickness: 17 um
[0249] [0249] The thickness used for tensile analysis was determined based on the weights, dimensions and film densities. This choice was made to overcome overestimation of thickness due to the presence of particulate aggregates on the film surface, especially when solid compositions are used.
[0250] [0250] However, thickness measurement can be done using a Mitutoyo thickness gauge to demonstrate the surface roughness observed for films containing aggregates. D. Depolymerization test
[0251] [0251] The protocol was the same as that used in the Example
[0252] [0252] The results obtained for the film produced with the liquid composition of the invention were compared to the results obtained for the film produced with the solid composition: Film 1 versus Film 4; Film 2 versus Film 5 and Film 3 versus Film 6. - Mechanical properties
[0253] [0253] Table 14 shows the turbidity results measured in Films 1, 2, 4 and 5. The turbidity values of Films 1 and 2 are respectively lower than those of Films 4 and 5. Turbidity is caused by impurities contained in the article plastic (such as accumulation of tiny particles in the article or very small surface defects). The lower the turbidity value, the greater the sharpness of the article. The use of a liquid composition of the invention during the production process of a plastic article allowed the reduction of the turbidity of the film compared to the use of a solid composition of biological entities, which indicates that the liquid composition of the invention allows the increase of the dispersion of biological entities in the film.
[0254] [0254] Tables 15 and 16 show the dynamic friction coefficient, tensile and thickness properties measured by the Mitutoyo thickness gauge of the films produced in 2.3. “S” corresponds to the standard deviation in the same unit as the measured characteristic. Table 15: Dynamic friction coefficient, tensile properties and film thickness Direction Film | Unit Feature Film | Movie 1 | Movie 4 | Movie 2 | Movie 5 | “MO the ecovicê test | ecovios | ecovios | ecovics | Matrix | Composition Matrix F2332 + | F2332 + | F2223 + | 2223 + | 1+ 1+ MB-L MB-S MB-L MB-S MB-L MB-S Thickness> ss 21 to> [loves | | and | 2 | poa a | 2 | and | Young module - -:
[0255] [0255] In Table 16, films produced from MB-S are used as a reference and considered as 100% of the defined parameter. Table 16: Coefficient of dynamic friction and tensile properties of films on the base 100 s Direction Ti é le: 2 7 Locale characteristic | Movie 1 | Movie 4 | Movie 2 | Film 5 | Film 3 | Test film 6 ecovicThe ecovioo ecovioo ecovio & 8 | Matrix | Matrix Composition F2332 + | F2332 + | rF2223 + | rF2223 + | 1 + MB- | 1 + MB- MB-L MB-S MB-L MB-S L Ss Coefficient of - 2 00 5) 100 dynamic friction MD N 293,6 100 14, 5 100 100 Young module He ee Ts e = e] Effort to TD% 154 100 307 100 383 100 sue E De o De q Ts | Resistance of
[0256] [0256] The friction coefficient is the ratio between the sliding force and the holding force of the two surfaces in contact. This coefficient characterizes the difficulty for two materials to slide into each other. This difficulty can be increased in the case of superficial roughness. The values of dynamic friction coefficient of films 1, 2 and 3 are lower than those of films 4, 5 and 6, respectively, indicating less surface roughness. The use of a liquid composition of the invention during the production process allows the reduction of the dynamic friction coefficient and, thus, the reduction of surface roughness compared to the use of a solid composition of biological entities.
[0257] [0257] This feature was also visible to the naked eye: films 4, 5, 6 show irregularities on the surface due to particle aggregates.
[0258] [0258] The thickness measurement using a Mitutoyo thickness gauge also demonstrates this surface roughness observed for films produced from solid composition of biological entities that lead to the aggregates in the film.
[0259] [0259] Young's module, breaking stress and final tensile strength measured for the films are significantly higher with the liquid composition of the invention compared to the solid composition. The liquid composition of the invention has a smaller particle size which leads to a fine and homogeneous dispersion of particles in the film and, as a consequence, an improvement in the mechanical properties. - Depolymerization test
[0260] [0260] The depolymerization test showed that the films obtained from the liquid composition of the invention have a significantly higher percentage of depolymerization rate compared to that obtained with the solid enzyme composition, as shown in Table 17 (ecovioo films F2332) , Table 18 (ecovio films F2223) and Table 19 (Matrix 1 films). Films produced from MB-S are used as a reference and their depolymerization level is considered to be 100. Table 17: Case of ecovio6 F2332 - Depolymerization level after 16 days Depolymerization enzyme level composition Film | ecovio6 F2332 2 Movie | ecovio6o F2332 z; Table 18: Case of ecovio6 F2223 - Depolymerization level after 16 days Composition Level of enzyme | depolymerization; ecovio6 F2223 27; ecovio6 F2223; ; - Table 19: Matrixl case - Depolymerization level after 2 days Composition Depolymerization enzyme level
[0261] [0261] An injection molding machine was used for the production of rigid plastic items: KM 50t / 380 CX type ClassiX with MC6 computer controller system.
[0262] [0262] The rigid plastic articles were produced by incorporating the main batch MB-L of Example 2.2 in two types of matrix based on polyester. The matrices are chosen from the two grades of polylactic acid polymer whose characteristics are shown in the Table
[0263] [0263] Before the dry mix, the polyester-based matrix and the main batch were dried in the desiccator at 50 ºC for 40 h. 10% of MB-L was then added to the polyester-based matrix. The articles with 100% polyester-based matrix were also produced for comparison.
[0264] [0264] Parts of 60 mm x 60 mm with 1 mm of thickness were manufactured by the injection molding process. The parameters were defined depending on the degree of the polyester-based matrix acid used.
[0265] [0265] The parameters defined for injection molding are summarized in Table 21. Table 21: Extrusion parameters used for the production of rigid articles by injection Composition Temperatures Pressure Pressure [Temperature cycle defined in zones - | de de (or barrel mold) , from | injection | retention | cycles) | (ºc of the (MPa (MPa of feed to à (bar)) (bar)) molding front zone (ºC) PAI PLI 003 35/160/160/165/170 - [104 100 30 (control | NaturePlast (1040) (1000) versus PA2) PA2 PLI 003 35/160/160/165/170 [103.5 [909 (900) [43 30 NaturePlast (1035) + 10% of MB-L
[0266] [0266] Total composition residence time in the barrel has been measured and is about 12 min for PAl and PA2 and 13 min for PA3 and PA4.
[0267] [0267] The rigid articles produced were subjected to a depolymerization test, according to a protocol described in Example 1.4. The results are shown in Table 22, PAl and PA3 are used as a reference and their level of depolymerization is considered to be 100. They demonstrate that the use of the composition of the invention allows the production of biodegradable rigid plastic articles.
[0268] [0268] Table 22: Depolymerization test for plastic injection molding articles | sample - [Depolymerization level in 10 days PAl (control) 1500 Table 23: Depolymerization test for plastic injection molding articles | sample - [level of depolymerization in 10 days PA3 (control) 1267 Example 3 - Preparation of a main batch using a liquid composition of the invention, use of such main batch for the production of a rigid PLA-based article and evaluation of traction, impact and degradation properties of such article.
[0269] [0269] The main batches were prepared using polycaprolactone polymer (PCL) pellets (CapaTM 6500 from Perstorp) and liquid or solid enzymatic composition described in Table 24. The liquid composition LC-l and the solid composition SC-l were prepared in the same manner as detailed in Example 2.1. Table 24: Enzymatic compositions used to produce the main batches Composition of liquid composition Solid composition of enzyme LC-1 Ssc-1 Aqueous solvent 53.8 &% 3.2% (water) Dry matter 46.2% including 96.8% including including - Carrier - 22.4 &% - 1.4% (gum arabic) - Entities - 19.8% - 19.4% biological - Others - 4% including polyols and% salts are given by weight, based on weight total final composition
[0270] [0270] The main batch MB-LCl comprising PCL and the liquid composition of the invention LC-l1 were prepared using a Clextral Evolum 25 HT twin screw extruder comprising twelve zones Z1l to zZ12, in which the temperature is independently controlled and regulated. The parameters used for the process are as follows: temperature profile 65 ºC-65 ºC-65 ºC-65 ºC-65 ºC-65 ºC-65 ºC- 65 ºC-65 ºC-65 ºC- 65 ºC-50 ºC, speed of 450 rpm extruder threads and a total flow rate of 40 kg / h. PCL is introduced in Zone 1 at 32 kg / h and the liquid composition LC-1 in Zone 5 at 8 kg / h using a volumetric pump. 20% of the liquid enzymatic composition was introduced into PCL based on the total weight of the extruded main batch.
[0271] [0271] In parallel, a main batch MB-SCl comprising PCL and the solid composition SC-l were prepared in a cogiratory double screw extruder (Leistritz ZSE 18MAXX) with the following parameters: temperature profile of 70 ºC-70 ºC -70 ºC-70 ºC-70 ºC-65 ºC-65 ºC-65 ºC-65 ºC- 65 ºC, thread speed of 150 rpm, and a total flow rate of 2 kg / h. 22% of the solid enzyme composition was introduced into PCL based on the total weight of the main batch using a gravimetric feeder in Zone 7. The cooling and granulation system of both main batches were the same as detailed in Example 1.2.
[0272] [0272] Thus, both the main batch MB-LCl1l and the main batch MB-SCl comprise the same concentration of biological entities.
[0273] [0273] Plastic dumbbells that have a thickness of 4 mm and a total length of 170 mm were produced using an injection molding machine (KM 50t / 380 CX ClassiX).
[0274] [0274] The dumbbells were produced from a NatureWorksO Ingeo "3251D PLA grade injection and the MB-LC1l main lot described in 3.1. The control dumbbells were produced from the same PLA grade and MB-SCl1l main lot. in 3.1, 100% of the PLA dumbbells were also produced for standardized mechanical characterization.
[0275] [0275] Before the manufacture of rigid articles, PLA and MB-LCl were dried using a desiccator for 40 h at 50 ºC and MB-SCl was dried in a vacuum oven at 50 ºC for 48 h. The rigid plastic articles were made using 95% by weight of the PLA-based matrix and 58% by weight of a main batch.
[0276] [0276] The injection molding parameters for each article are detailed in Table 25:
[0277] [0277] Table 25: Injection molding parameters for dumbbell production Composition | Temperatures Pressure | Pressure | Temperatu cycle defined in zones of (or ra de barrel, from | injection | retention | cycles) | mold of the zone of (MPa o (MPa | of (ºC) feed to (bar)) (bar)) | molding front area (ºC) m RA- | 95% 40/145/150/150/160/1 [100 85 70 30 LC1l | PLA + 5% | 60 (1000) (850) MB -LC1 RA- | 95% 40/145/150/150/160/1 [100.5 90 70 30 SCl | PLA + 58% 60 (1005) (900) MB-SC1
[0278] [0278] The tensile and impact properties of the rigid plastic article produced from the liquid composition of the invention and the control plastic article made from a solid composition were characterized. * Traction test
[0279] [0279] Tensile tests were performed using a Zwick Roell testing machine equipped with a 20 kN force sensor. The tests were performed according to the ISO 527-1 standard and the test results are shown in Table 26. Table 26: Tensile properties of the rigid plastic article produced from the liquid composition of the invention (RA-LC1) and the control (RA-SC1) elastic | maximum breaking stress (GPa) om (MPa) maximum in | ob (MPa) and b (%) $
[0280] [0280] The rigid article produced from a main batch of a liquid composition shows no significant difference in measured mechanical characteristics that show that the use of a liquid composition of the invention has no serious impact on the elastic modulus, the maximum stress, the stress at maximum stress, stress at break and stress at break of the rigid article produced from such a composition of the invention. . Charpy Impact Test
[0281] [0281] The tests were carried out according to the NF EN ISO 179-1 standard using a Zwick pendulum impact tester. The test bars were cut from the injected specimens using heated pliers. The bar dimensions are 4 mm * 10 mm * 80 mm. The test results are shown in Table 27. Table 27: Impact properties of the rigid plastic article produced from the liquid composition of the invention (RA-LC1) and the control (RA-SC1)
[0282] [0282] The rigid article of the invention produced from a liquid composition of the invention shows better impact resistance than that produced from a solid composition of biological entities. This is certainly due to the fine distribution of biological entities in the plastic article.
[0283] [0283] Depolymerization tests were performed on a rigid injected article RA-LCl produced from the liquid composition of the invention. First, the rigid article was coarsely ground, immersed in liquid nitrogen and then ground using Ultra-Centrifugal Mill ZM 200 RETSCH equipped with a 500 µm grid. 100 mg of this powder was weighed, introduced and confined to the dialysis tube. The tube was placed in 50 ml of 0.1M Tris buffer pH 9.5. Depolymerization was started by incubating each sample at 45 ºC, 150 rpm in an Infors HT Multitron Pro incubation shaker. The 1 ml aliquots of buffer were sampled regularly and filtered through 0.22 µm of syringe filter, the samples were analyzed by High Performance Liquid Chromatography (HPLC) with an Aminex HPX-87H column to monitor the release of lactic acid (LA) and lactic acid dimer. The chromatography system used was a UHPLC Ultimate 3000 system (Thermo Lisher Scientific, Inc. Waltham, MA, USA) including a pump module, a self-sampler, a column oven with a thermostat at 50 ° C, and a UV detector at 220 nm.
[0284] [0284] The eluent was 5 mM H2S04. The injection was 20 pl of sample. LA was measured according to the 20 standard curves prepared from commercial LA.
[0285] [0285] The depolymerization level of the rigid article reached about 10% after 48 h which shows biological entities retaining a polyester degradation activity in the final plastic article produced from the liquid composition of the invention. Example 4 - Preparation of a main batch using a liquid composition of the invention, use of such a main batch for the production of rigid sheets and evaluation of the traction, impact and degradation properties of such sheets
[0286] [0286] The main batch composition was prepared from polycaprolactone polymer (PCL) pellets (Perstorp Cover "" 6500) and the liquid enzymatic composition of the invention LC-l1 described in example 3.1. The main batch was manufactured using a CLEXTRAL EV25HT twin-screw extruder comprising twelve zones Zl to Z212, in which the temperature is independently controlled and regulated. PCL is introduced in zone 1 at 16 kg / h and the liquid composition in zone 5 at 4 kg / h with the use of a peristaltic pump, in which the zones are heated according to Table 27. 20% of the liquid composition LC has been added PCL based on the total weight of the main batch. This main batch is designated as MB-LC2. Table 27: Extruder temperature settings for the production of the main batch
[0287] [0287] The enzyme activity in the main batch was determined according to the protocol described in Example
[0288] [0288] A degree of Total Thermoforming PLA Corbion Luminy & 6 LX175 was used to manufacture 450 µm thick plastic sheets to be subjected to standardized impact and traction characterization and biodegradability testing.
[0289] [0289] For the manufacture of plastic sheets, a FAIREX extruder comprising four zones Zl to 7274, in which the temperature is independently controlled and regulated with a diameter of 45, a 220 mm flat die equipped with a 1.5mm adjustable rim nominal opening and a three-cylinder calender was used. Before extrusion and calendering, MB-LC2 and PLA were dried and mixed together. The MB-LC2 was dried for 20 hours at 40 ºC in a vacuum oven and the PLA was dried for 4 hours at 40 ºC in dryers. The sheets of 0% (negative control), 5% or 10% of MB-LC2 added in PLA were respectively designated SO, S5 and S10. The extrusion and calendering parameters are detailed in Table 28. Table 28: Extruder and calender definitions for sheet production
[0290] [0290] In order to assess the rate of depolymerization of plastic sheets, a depolymerization test was performed following the protocol already described in Example 3.4.
[0291] [0291] After 8 days, the powder from SO, S5 and S10 leaves shows a PLA depolymerization rate of 0.08%, 0.77% and 13.0%, respectively, which shows that biological entities retain a degradation activity of polyester in the final plastic article produced from the liquid composition of the invention (S5 and S10). 4.4 - Characterization of Dart test of plastic sheets
[0292] [0292] The impact tests were performed according to NF EN ISO 7765-1, using the step method. According to this standard, the samples were cut directly into the plastic sheet. The tests were performed using a BMC-Bl Dart testing machine by Labthink and the results are shown in Table 29.
[0293] [0293] The results of the impact test show that the sheets produced from the liquid composition of the invention (S5 and S10) show an improvement of the impact resistance in comparison to the SO control made of 100% PLA.
[0294] [0294] Tensile tests were performed using a Zwick Roell testing machine equipped with a 20 kN force sensor. The tests were performed according to the standard NF EN ISO 527-l1. The measured tensile properties are shown in Table 30.
[0295] [0295] The comparison of a pure PLA (S0) sheet, of the leaves produced from a main batch itself produced from a liquid composition of the invention and PCL shows an improved flexibility with the increase of the incorporation of such main batch in PLA-based sheets, while maintaining sufficient stiffness required for the intended application. Example 5 - Preparation of liquid compositions of the invention, and use of such compositions for the manufacture of films comprising PCL and PLA
[0296] [0296] Different liquid compositions of the invention were prepared using a commercial protease, Savinase6 16L (Novozymes) marketed in a liquid form.
[0297] [0297] The liquid compositions D, E, F and G were obtained according to the method described in Example 1.1: ultrafiltration and diafiltration of commercial Savinase6 16L in 3.5Kd membrane and in which the gum arabic is added as a carrier.
[0298] [0298] The commercial Savinase6O 16L corresponds to the liquid composition H and is used as a negative control. Such a composition comprises more than 50% by weight of polyols based on the total weight of the liquid composition and water.
[0299] [0299] The description of the different liquid compositions is summarized in Table 31. Table 31: Description of liquid compositions of the invention (LC-D, LC-E, LC-F and LC-G) and a negative control (LC-H) .
[0300] [0300] The main batch compositions were prepared from the polycaprolactone polymer (PCL) pellets (Cover "" 6500 from Perstorp) and the compositions of the invention described in Example 3.1, using the same compound forming machine as in Example 1.2.
[0301] [0301] According to this experiment, 80% by weight of PCL was extruded with 20% by weight of the liquid composition. The parameters used for each main extruded batch are summarized in Table 32. Table 32: Temperature profile and process parameters of the composting process
[0302] [0302] The enzyme activity of said main batch was further described using the protocol described in Example 1.2. The comparison of the active enzyme mass and theoretical enzyme mass in the main batch allowed the percentage of residual activity in the main batch to be determined. The residual activities of the main batches produced are summarized in Table 33. Table 33: Residual activities of main batches that contain the liquid composition of the invention
[0303] [0303] All main batches produced with liquid compositions of the invention (LC-D to LC-G) demonstrate a high residual activity. On the contrary, MB8, which contains Savinase 16L and which corresponds to the negative control, does not show any residual activity. This result confirms the interest in the extrusion process of liquid compositions of the invention that comprise a specific carrier compared to the commercial formulation already described.
[0304] [0304] MB5 and MB7, which have similar water content (or similar dry matter), but different content of biological entities, show equivalent residual activity. This result tends to indicate that the protection of biological entities is equivalent, regardless of the percentage of biological entities involved.
[0305] [0305] Additionally, MB4, produced from the composition that contains the largest amount of water compared to the compositions used to produce MB5, MB6 or MB7, shows the least residual activity. This result tends to indicate that the protection of biological entities is increased when the amount of the aqueous solvent is below 70%, preferably below 60% and / or when the amount of dry matter is above 30%, preferably, above 40 &, regardless of the amount of biological entities introduced into the liquid composition of the invention.
[0306] [0306] The MBA4, MB5 and MB6 granulated main batch compositions of Example 5.2 were used to produce biodegradable polylactic acid-based plastic articles through an extrusion process. The biodegradability of said plastic articles was further tested. Preparation of the PLA-based matrix
[0307] [0307] The PLA-based die was extruded using the twin screw extruder described in Example 1.2. The composition of this matrix is 42.3% by weight of PLA 4043D by NatureWorks, 51.7% by weight of PBAT PBE006 by NaturePlast and 6% by weight of CaCO; by OMYA. All materials were dried before extrusion. PLA and PBAT were dried for about 5 hours in a desiccator at 60 and 40 ºC respectively. The vacuum oven at 40 ºC-40 mb for 16 h was used for calcium carbonate.
[0308] [0308] The temperature was set at 185 ºC in the ten zones of the extruder. The screw speed rate was 175 rpm, and the total inlet mass rate was about 5 kg / h. CaCO; was introduced in zone 7 for melted polymers using a gravimetric feeder to obtain the PLA-based matrix. The resulting extrudate was cooled in a cold water bath before pelletizing. Main lots
[0309] [0309] The main batches MB4-MBS-MB6 described in Example 5.2 are used to produce the plastic films. Film blowing step
[0310] [0310] Before extrusion by film blowing, the main batches and PLA-based matrix were dried in a vacuum oven at 50 ºC - 40 mb for 15 h. The blends were prepared in order to introduce the same amount of enzyme in all films, based on theoretical enzyme mass in the main batch and according to Table 34. For films E and F, it was necessary to add PCL 6500 (also dry under the same conditions) in order to obtain identical composition in all films. Table 34: composition of manufactured films Matrix Reference to | MB4 MB5 MB6 PCL of PCL / 1C-D base film | PCL / 1C-E | PCL / 1C-F | 6500
[0311] [0311] The blowing was performed using the same machine and parameters described in example 1.3.
[0312] [0312] Depolymerization tests were performed on the plastic films produced in Example 5.3, according to the protocol described in example 1.4.
[0313] [0313] The hydrolysis of plastic films was calculated based on FA and released AF dimer. The percentage of degradation is calculated in relation to the percentage of PEA in the films.
[0314] [0314] The results of depolymerization of films, after 4 days, are shown in Table 35. Table 35: Comparison of depolymerization of films produced from the compositions of the invention (LC-D, LC-E and LC-F)
[0315] [0315] All films produced with the compositions of the invention show a high rate of depolymerization, indicating the presence of active enzyme. The more the liquid formulation of the invention contains dry matter, the greater the degradation yield achieved. This result confirms that a greater dry matter in the composition of the invention results in a greater protection of biological entities during both extrusion processes (production of main batch and production of plastic article). Example 6 - Use of a composition of the invention for the manufacture of films comprising PLA
[0316] [0316] The liquid composition of the LC-1 invention of the Example
[0317] [0317] The main batches based on polylactic acid designated as MB-PLAl, MB-PLA2 and MB-PLA3 were prepared in a cogiratory double screw extruder (Leistritz ZSE 18MAXX) with screw speed of 150 rpm and a flow rate total of 2 kg / h. The extrusion temperatures are detailed in Table 36 below. PLA was introduced in the unheated feed zone (20), and LC-1 was introduced in Z6 using a Brabender pump. The cooling and granulation system of both main batches were the same as detailed in Example 1.2. The composition of the main batches is also shown in Table 36. Table 36: Temperature profile and process parameters of the composting process Composition z10 zone | z1 | z22 | z23 | z24 | 25 | 26 | 27 | z8 | z29 | (matrix) MB 80% PLA PLAl LX930U + T ºcl135 / 135] / 135/135/135/120/120/120 | 120 [120 20% LC-1 MB- 90% PLA PLA 2 LX930U + T ºc / l135 / 135/135/135/135/120/120/120/120 | 120% LC-1 mB | 90 % PLA 4043D + 10% | T ºC / 145/145/145 145/145/130/130/130/130/130 PLA3 De LC-1
[0318] [0318] Depolymerization tests were carried out, using main batches produced above according to the protocol defined in Example 3.4 and level of depolymerization after 24 h are shown in table 37.
[0319] [0319] The main batches based on PLA LX930U with lower melting point (MB-PLAl and MB-PLA2), showed lower levels of depolymerization than MB-PLA3 based on PLA4043D so that higher extrusion temperatures were used (even equivalent number of biological entities). The activity of the enzyme in the liquid composition LC-1l is thus significantly better maintained at a lower process temperature using a PLA with a melting temperature below 140 ºC. However, the results show that the liquid composition of the invention is also suitable to be introduced into a partially or fully melted polymer that has a melting point above 140 ° C and that biological entities still preserve polymer degradation activity in the batch. main.
[0320] [0320] MB-PLAl or MB-PLA 2 and PLA-based matrix of Example 1.3 (42.3% by weight of PLA 4043D by NatureWorks, 51.7% by weight of PBAT PBE006 by NaturePlast and 6% by weight CaCO3z by OMYA) were used for film production. Before the film blowing extrusion, the main batches and PLA-based matrix were dried in a vacuum oven at 60 “C for 5 h. The prepared mix compositions are shown in Table 38. Table 38: Composition of manufactured films [Fime Too 8 [= E [Fime 890 8 E E Fime fes E e
[0321] [0321] The film blowing line used and the set temperatures are the same in Example 1.3. The set screw speed rate was 60 rpm. The cooling air range and extraction speed were adjusted to obtain a bubble width of 200 mm and a film thickness between 15 and 20 µm.
[0322] [0322] Depolymerization tests were performed on the films produced above according to the protocol defined in Example 1.4 and the level of depolymerization after 26 days is shown in table 39.
[0323] [0323] All films produced from a main batch comprising PLA with a melting temperature below 140 ° C and the composition of the invention showed degradation in aqueous medium. It is assumed that film 7 and film 9 contain the same amount of biological entities, but film 7 based on the most concentrated main batch (MB-PLAl produced from 20% LC-1) shows a level of degradation greater than film 9 based on MB-PLA2 produced from 10% LC-1. Example 7 - Use of a composition of the invention for the manufacture of rigid plastic article comprising PLA and PCL by 3D printing
[0324] [0324] A liquid composition of the LC-1 invention of the Example
[0325] [0325] The enzyme activity in the main batch was determined according to the protocol described in Example
[0326] [0326] A PLA-based filament was manufactured using Ingeo "" Biopolimer 4043D from NatureWorks. Before the filament extrusion, MB9 and PLA main batch were dried for 15 h at 50 ºC in a vacuum oven. The main batch was dry mixed with PLA in a ratio of 30% / 70% by weight and then extruded in a single screw extruder (Scamex - Rheoscam, 20-11 L / D) at 100 ºC-170 ºC -190 ºC defined in the three zones of the extruder and 180 ºC matrix. A screw speed rate of 47 rpm was used. The extrudate was cooled with pressurized air, the final filament diameter was about 1.75 mm.
[0327] [0327] A Cartesian type printer was used. This printer, model Neocore, has a basalt plateau of 30 x 30 cm that can heat up to 200 ºC and a single nozzle E3D equipped with a BondTech filament system that can heat up to 400 ºC. The 3D printing tests were conducted using 5A tensile specimen geometry according to ISO 537-2. The 3D printing parameters are detailed in Table 40. Table 40: Nozzle 3D printing parameters! specimen 1.203 cm3)
[0328] [0328] Depolymerization tests were performed on 100 mg of micronized 5A (1 mm grade) traction species using the same protocol as Example 3.4. Depolymerization of the specimen reached 11% buffer with pH 9.5 at 45 ºC after 8 days (dialysis system).
[0329] [0329] The depolymerization results confirmed that biological entities retain polymer degradation activity in a 3D printed plastic article produced from the composition of the invention, even after a second heating at high temperature during 3D printing.

权利要求:
Claims (28)
[1]
1. Liquid composition suitable for incorporation into a partially or fully molten polymer characterized by comprising biological entities that have a polymer degradation activity, a carrier and an aqueous solvent, in which i) the carrier is a polysaccharide selected from derivatives starch, natural gums, marine extracts, microbial polysaccharides and animal polysaccharides and ii) the composition comprises, based on the total weight of the composition: - from 0.01% to 35% by weight of biological entities, - from 15% to 95 % by weight of the aqueous solvent, - from 3% to 80% by weight of carrier.
[2]
Composition according to claim 1, characterized in that, based on the total weight of the composition: - from 0.3% to 30% by weight of biological entities, - from 19% to 85% by weight of the aqueous solvent , - from 4% to 80% by weight of carrier.
[3]
Composition according to claim 1 or 2, characterized in that, based on the total weight of the composition: - from 0.3% to 30% by weight of biological entities, - from 19% to 60% by weight of the aqueous solvent, - from 15% to 70% by weight of carrier.
[4]
Composition according to any one of the preceding claims, characterized in that the aqueous solvent is water and the composition comprises more than 20% by weight of aqueous solvent, preferably more than 30%, and less than 80% by weight of water, based on the total weight of the composition.
[5]
5. Composition according to any one of the preceding claims, characterized by the fact that the composition comprises from 30% to 75% by weight of water, preferably from 40% to 60% of water based on the total weight of the composition.
[6]
6. Composition according to any one of the preceding claims, characterized by the fact that the composition comprises about 50% water.
[7]
Composition according to any one of claims 1 to 5, the composition being characterized by comprising about 40% water.
[8]
8. Composition according to any one of the preceding claims, characterized by the fact that biological entities are selected from enzymes that have a polymer degradation activity, more preferably, selected from an enzyme that has an activity of polyester degradation, most preferably selected from protease, esterase or lipase.
[9]
9. Composition according to any one of the preceding claims, characterized by the fact that biological entities are selected from enzymes that have a PLA-degrading activity, preferably selected from protease.
[10]
10. Composition according to any one of the preceding claims, characterized by the fact that the composition comprises less than 70% by weight of carrier,
preferably less than 60%.
[11]
11. Composition according to any one of the preceding claims, characterized by the fact that the carrier is a natural gum, preferably selected from gum arabic, guar gum, tragacanth gum, Karaya gum.
[12]
12. Composition, according to claim 11, characterized by the fact that the carrier is gum arabic.
[13]
13. Composition according to any one of the preceding claims, characterized in that it comprises, based on the total weight of the composition: - from 0.01% to 35% of biological entities, preferably PLA degradation enzymes - from 30% to 75% water - from 10% to 69.99% of a carrier, preferably gum arabic.
[14]
Composition according to any one of the preceding claims, characterized in that, based on the total weight of the composition: - from 0.01 &% to 35% of biological entities, preferably PLA degradation enzymes - from 30 % to 60% water - from 20% to 45% of a carrier, preferably gum arabic.
[15]
15. Composition according to any one of the preceding claims, characterized in that it comprises, based on the total weight of the composition: - from 0.01% to 35% of biological entities, preferably PLA degradation enzymes - from 40% to 60% water
- 20% to 45% of a carrier, preferably gum arabic.
[16]
16. Composition according to any one of the preceding claims, characterized in that, based on the total weight of the composition, it comprises about 50% water and 0.01% to 35% PLA degradation enzymes and 20% to 49.99% gum arabic.
[17]
17. Composition according to any one of claims 1 to 9, characterized in that the carrier is a starch derivative, preferably a maltodextrin.
[18]
18. Use of the liquid composition as defined in claims 1 to 17 characterized by being for the manufacture of a plastic composition.
[19]
19. Use, according to claim 18, characterized by the fact that the biological entities of the liquid composition have the capacity to degrade at least one polymer of the plastic article.
[20]
20. Plastic article characterized by comprising at least one polymer and the composition as defined in any one of claims 1 to 17, wherein the biological entities of the composition are able to degrade said polymer.
[21]
21. Process for preparing a plastic article characterized by comprising the steps of: a) preparing a main batch comprising biological polymer degradation entities and a first polymer by (i) heating said first polymer; and (ii) introducing 5% to 50% by weight of the composition as defined in any one of claims 1 to 17, based on the total weight of the main batch, during the heating of the first polymer; and b) introduction of the main batch in a polymer-based matrix during the production of the plastic article, in which step a) is carried out at a temperature in which the first polymer is in a partially or fully molten state, preferably by extrusion and step b) is carried out at a temperature in which both the first polymer and the polymer matrix polymer are in a partially or fully molten state and where the biological entities of the composition are able to degrade a polymer of the matrix to the polymer base.
[22]
22. Process according to claim 21, characterized by the fact that the first polymer is a polymer that has a melting temperature below 140 "C and / or a glass transition temperature below 70" C selected from among polyester, starch, EVA and mixtures thereof.
[23]
23. Process according to claim 21 or 22, characterized by the fact that the first polymer is selected from PCL, EVA, PBAT, PLA and mixtures thereof.
[24]
24. Process for the manufacture of a plastic article characterized by comprising a step (a) of mixing between 0.01% and 10% by weight of the composition as defined in any one of claims 1 to 17, with at least one polymer, in that the biological entities of the composition have the capacity to degrade said polymer and a step (b) of forming said mixture of step (a) in a plastic article.
[25]
25. Process according to claim 24, characterized by the fact that step (a) of mixing is carried out at a temperature at which the polymer is in a partially or fully molten state.
[26]
26. Method for increasing the dispersion homogeneity of biological entities of polymer degradation in a biodegradable plastic article, said “method characterized by understanding to introduce during the process of production of the plastic article, the liquid composition as defined in any one of the claims 1 to 17.
[27]
27. Method for increasing the biodegradability of a plastic article comprising at least one polymer and biological polymer degradation entities, said method being characterized by including, during the production process of the plastic article, the liquid composition as defined in any one of claims 1 to 17.
[28]
28. Process for the manufacture of a plastic article containing biological entities characterized by successively comprising a step of introducing the liquid composition as defined in any one of claims 1-17, into a first polymer to obtain a mixture, and a step of introducing said mixture into a second polymer different from the first polymer, in which the first polymer has a melting point below 140 "ºC and the second polymer has a melting point above 140" C.

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同族专利:

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公开号 | 公开日

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DK3676316T3|2022-01-10|

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EP3676316B1|2021-10-06|

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CA3072865A1|2019-03-07|

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EP3904431A1|2021-11-03|

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US20200190279A1|2020-06-18|

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EP3904431A4|2021-11-03|

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WO2019043145A1|2019-03-07|

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CN111051394A|2020-04-21|

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JP2020531672A|2020-11-05|

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EP3676316A1|2020-07-08|

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法律状态:
2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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EP17306117|2017-08-31|

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EP17306117.7|2017-08-31|

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PCT/EP2018/073447|WO2019043145A1|2017-08-31|2018-08-31|Liquid composition comprising biological entities and uses thereof|

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