biodegradable polyester article comprising enzymes

专利摘要:
  The present invention relates to new biodegradable plastic articles comprising a polyester and biological entities capable of degrading that polyester, and in which the biological entities are homogeneously dispersed in the plastic articles. The invention also relates to a process for producing these plastic articles, comprising a step of mixing biological entities with a carrier selected in a liquid composition or in a masterbatch with the polyester.
公开号:BR112020004040A2
申请号:R112020004040-1
申请日:2018-08-31
公开日:2020-09-01
发明作者:Mediha Dalibey；Clémentine ARNAULT；Nadia Auclair
申请人:Carbiolice；
IPC主号:

专利说明:

[001] [001] The present invention relates to new biodegradable plastic articles comprising a polyester and biological entities capable of degrading that polyester, and in which the biological entities are homogeneously dispersed in the plastic articles. The invention also relates to a process for producing these plastic articles, comprising a step of mixing biological entities with a carrier selected in a liquid composition or in a masterbatch with the polyester. BACKGROUND OF THE INVENTION
[002] [002] Different biodegradable plastic compositions have been developed in order to answer the environmental questions of 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.).
[003] [003] These plastic compositions generally contain polyester, flour or starches from various cereals (US 5,739,244; US 6,176,915; US 2004/0167247; WO 2004/113433; FR 2 903 042; FR 2 856 405). Several solutions have been proposed to improve the control of the degradation of these plastics by mineral chemical additives (WO 2010/041063) or by the inclusion of biological entities capable of degrading polyesters (WO 2013/093355; WO 2016/198652; WO 2016/198650; WO 2016 / 146540; WO 2016/062695). The resulting plastic article contains biological entities, particularly enzymes dispersed in a polymer, and has improved biodegradability compared to plastic articles deprived of these biological entities.
[004] [004] If the manufacture of articles comprising polyester and enzymes has already been described, its implementation may raise technical problems in relation to homogeneity, surface roughness and the mechanical properties of the obtained article. Known or suggested manufacturing methods lead to non-homogeneous articles that exhibit enzyme aggregates. A lack of homogeneity in the distribution of enzymes in the plastic composition has many disadvantages in terms of physical properties, and from an aesthetic point of view.
[005] [005] The present invention thus provides biodegradable plastic articles exhibiting a homogeneous dispersion of the enzymes in the article, leading to expected physical performances. The present invention also provides plastic articles with improved degradability. SUMMARY OF THE INVENTION
[006] [006] The invention provides new biodegradable plastic articles comprising at least one polyester and biological entities and exhibiting expected physical and degradation performances.
[007] [007] It is, therefore, an objective of the invention to provide a biodegradable plastic article, comprising at least one polyester and biological entities having a polyester degradation activity, in which the biological entities are able to degrade said polyester and are homogeneously dispersed in the plastic article.
[008] [008] The invention provides a biodegradable plastic article comprising at least one polyester and biological entities having a polyester degradation activity, wherein it comprises a carrier selected from polysaccharides and, optionally, a polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C (a carrier polymer) and mixtures thereof, the biological entities being able to degrade said polyester and being homogeneously dispersed in the plastic article.
[009] [009] In particular, the invention provides a plastic article comprising, based on the total weight of the plastic article: - from 10 to 98% polylactic acid (PLA)
[0010] [0010] The invention also provides a process for the preparation of a plastic article comprising at least one polyester and biological entities having a polyester degradation activity dispersed homogeneously in the plastic article, said process, comprising a step (a) of mixing between 0.01% and 10% by weight of biological entities having a polyester degradation activity with at least said polyester and a step (b) of molding said mixture from step (a) into a plastic article, in which the entities biological substances are mixed during step (a) in an appropriate form to allow homogeneous dispersion of said biological entities in the plastic article, selected from - a liquid composition comprising biological entities having a polyester degradation activity, a carrier and water, or - a masterbatch comprising biological entities having a polyester degradation activity and a carrier polymer having a fuel temperature they are below 140 ° C and / or a glass transition temperature below 70 ° C.
[0011] [0011] The invention also provides a method for increasing the homogeneity of the dispersion of biological entities in a plastic article comprising a polyester, said method comprising the introduction during the production process of that plastic article, the biological entities in the form of a composition liquid comprising biological entities having a polyester degrading activity, a carrier and water, or in the form of a masterbatch comprising biological entities having a polyester degrading activity and a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C.
[0012] [0012] The invention also provides a masterbatch comprising biological entities having a polyester degrading activity and a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C and optionally a polysaccharide . DETAILED DESCRIPTION OF THE INVENTION
[0013] [0013] The present invention relates to new plastic articles, with improved homogeneous dispersion of biological entities, particularly enzymes and methods for producing them. The invention shows that these articles, with an adequate distribution rate of active biological entities, are of particular interest in meeting the expected physical and degradation characteristics for single-use, short-lived plastic articles.
[0014] [0014] The present disclosure will be better understood by reference to the following definitions.
[0015] [0015] Within 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, shape, solid block, 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 or a rigid plastic article.
[0016] [0016] 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 extrusion of blown film, while thick film has a thickness above 100 µm, and is preferably produced by melt film extrusion.
[0017] [0017] 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, blow 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 utensils, electronic coatings, 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 equal to or greater than 250 µm, these plastic sheets being produced by casting or calendering films. According to the invention, the rigid plastic article has a thickness below 5 mm, preferably below 3 mm.
[0018] [0018] As used in the present invention, the terms "plastic composition" refer to a mixture of polymers and biological entities and, possibly, additional compounds (for example, additives, filler etc.) before any modeling step or conditioning step for produce a plastic article. In a particular embodiment of the invention, the plastic composition is a masterbatch in solid form, prior to its introduction into a polyester-based matrix.
[0019] [0019] A "polyester-based matrix" refers to a matrix that comprises, as the main ingredient, one or more polyester (s). The polyester-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 polyester-based matrix can additionally comprise additional compounds, such as additives. According to the invention, the polyester-based matrix is deprived of any biological entities.
[0020] [0020] As used in the present invention, the term "masterbatch" designates a concentrated mixture of selected ingredients (for example, biological entities, additives etc.) and polymer that can be used to introduce said ingredients into plastic articles or compositions, to in order to give them the desired properties. Masterbatch compositions allow the processor to introduce economically selected ingredients during the plastic manufacturing process.
[0021] [0021] A "polymer" refers to a chemical compound or mixture of compounds whose structure consists of several repeating units linked by covalent chemical bonds. Within the context of the invention, the term
[0022] [0022] 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 attached 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-bonded oxygen is bound 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. These polyesters can be native or chemically modified.
[0023] [0023] Alternatively or in addition, the organic load is chosen from the group consisting of wood flour, plant or vegetable flour, such as cereal flour (corn flour, wheat flour, rice flour, soy flour) , nutshell flour, clam shell flour, corn cob flour, cork flour, rice husk flour); saw dust; vegetable fibers, such as linen fibers, wood fibers, hemp fibers, bamboo fibers, chicken feathers and derivatives thereof or combinations / mixtures of these materials. Natural polymers can also be used as organic fillers, such as, lignin, or polysaccharides, such as, cellulose or hemicellulose, starch, chitin, chitosan and derivatives or combinations / mixtures of these materials.
[0024] [0024] As used in the present invention, the term "biological entities" means active enzymes or enzyme-producing microorganisms, such as sporulated microorganisms, as well as combinations thereof.
[0025] [0025] Within the context of the invention, the term "liquid composition" corresponds to a composition in fluid form, that is, that takes the form of the container in which it is included. In the context of the invention, the composition is in liquid form at room temperature and / or at the temperature of its incorporation into a partially or fully melted polymer. As used in the present invention, 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 source (marine, vegetable, microbial or animal), structure (linear, branched) and / or physical behavior (such as the designation of gum or hydrocolloid, which refers to the property that these polysaccharides 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.
[0026] [0026] - Cellulose and derivatives, such as methylcellulose, hydroxypropylmethylcellulose, ethylcellulose etc.
[0027] [0027] - Exudates and plant extracts, also called vegetable gums or natural gums, including, but not limited to, gum arabic (acacia gum), tragacanth gum, guar gum, locust bean gum, caraia gum, mesquite gum, galactomannans, pectin, soluble soy polysaccharide).
[0028] [0028] - Marine extracts, such as carrageenan and alginate.
[0029] [0029] - Microbial and animal polysaccharides, such as gelan, dextran, xanthan and chitosan.
[0030] [0030] Polysaccharides can additionally be classified according to their solubility in water.
[0031] [0031] As used in the present invention, the term "room temperature" or "room temperature" means a temperature between 10 ° C and 30 ° C, particularly between 20 ° C and 25 ° C.
[0032] [0032] As used in the present invention, the term "soluble" refers to the ability of a solute (i.e., carrier, enzymes) to be dissolved in a liquid solvent.
[0033] [0033] 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 declared in various concentration units, such as molarity, molality, molar fraction, molar ratio, mass (solute) by volume (solvent) and other units. Solubility is defined at a specific atmospheric pressure and temperature.
[0034] [0034] as used in the present invention, the term "by weight" refers to an amount based on the total weight of the composition or product considered (o).
[0035] [0035] 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.
[0036] [0036] It has been shown that it is possible to improve the degradability and the physical and / or mechanical characteristics of plastic articles comprising polyester and biological entities having a polyester degradation activity by using a liquid composition of biological entities with a specific polysaccharide carrier. during the production process, compared to the use of solid or liquid compositions of biological entities in the art.
[0037] [0037] A way was found to reduce the surface roughness and, eventually, the thickness of the plastic article without going through heavy and expensive grinding operations of a solid composition. In addition, the spraying of the constituents of said liquid composition is reduced in comparison to the solid composition and, therefore, reduces the risks of inhalation of particles of the solid composition during the plastic article production process. It was found that the production of plastic articles with biological entities with a specific carrier, preferably in a liquid composition, leads to plastic articles with an increased homogeneity of the dispersion of biological entities in the plastic article compared to plastic articles produced with biological entities in a solid or liquid form of the technique, thus leading to a plastic article with intensified physical properties.
[0038] [0038] It is, therefore, an objective of the invention to provide a biodegradable plastic article, comprising at least one polyester and biological entities having a polyester degradation activity, in which the biological entities are able to degrade said polyester and are homogeneously dispersed in the plastic article.
[0039] [0039] It is also another object of the invention to provide a method for homogenizing the dispersion of biological entities of degradation of polyester in a plastic article comprising at least one polyester and said biological entities, said method comprising the introduction during the production process of that plastic article, biological entities with a specific carrier, preferably in a liquid composition.
[0040] [0040] The homogeneity of the dispersion of biological entities in the plastic article of the invention can be assessed by those skilled in the art, according to methods known per se in the art. For example, and in 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 tension, tension at maximum tension, impact resistance and biodegradability.
[0041] [0041] Turbidity is defined as the percentage of incident light dispersed by more than 2.5 ° through the plastic article. Turbidity is caused by impurities contained in the plastic article (such as accumulation of small particles in the article or very small defects on the surface) or its level of crystallinity. The lower the Turbidity value, the greater the translucency of the article. Turbidity has no specific unit, expressed in%. If the Turbidity value is greater than 30%, the article will be disseminated. 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 2155-9 (August 1989). In particular, the plastic article of the invention produced from a liquid composition of biological entities may exhibit a lower turbidity value than the same plastic article produced from a solid composition of biological entities.
[0042] [0042] Young's modulus of the plastic article, also known as elastic modulus or tensile modulus, is a measure of the stiffness of a solid material. It is a mechanical property of linear elastic solid materials. It defines the relationship between stress (force per unit area) and elastic deformation (proportional deformation) in a material. The result must be expressed in pascal or megapascal (MPa).
[0043] [0043] Elongation at break or deformation at break of the plastic article is related to the ability of a plastic article to resist shape changes without cracking. Elongation at break is also known as fracture deformation or elastic elongation at break.
[0044] [0044] The tensile strength at break, also known as tensile strength or tensile strength at break of the plastic article, is defined as the tensile stress at which the specimen breaks. The tensile stress also known as final tensile stress or maximum stress corresponds to the maximum tensile stress supported by the specimen during the tensile test. The result must be expressed in force per unit area, usually megapascals (MPa).
[0045] [0045] Deformation at maximum stress or deformation in the traction is the deformation in the traction 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 measured length of the plastic article and multiplying by 100.
[0046] [0046] Young's modulus, elongation at break, tensile strength at break, maximum stress, strain at maximum stress, of plastic articles can be measured according to ASTM D882-12 or NF EN ISO 527-3 for plastic articles with a thickness below 1mm. It can be measured particularly in two different directions: machine direction or transverse direction. The determination of these criteria for plastic articles with a thickness of 1mm to 14mm is made with ASTM D638-14 or NF EN ISO 527-2.
[0047] [0047] In particular, the plastic article of the invention obtained by the use of a liquid composition of biological entities may exhibit a greater elongation at break than the same plastic article produced from a solid composition of biological entities. Typically, the plastic article of the invention is a plastic film and shows an elongation at break, in at least one direction selected in the machine direction or in the transverse direction, 10% greater, preferably 20%, 50%, 100% greater or more , than the elongation at rupture of a plastic article produced with a solid composition of biological entities.
[0048] [0048] In particular, the plastic article of the invention produced with a liquid composition of biological entities may exhibit a greater tensile stress at break than the same plastic article produced from a solid composition of biological entities. Typically, the plastic article of the invention is a plastic film and shows a tensile stress at break 20% greater, preferably 30%, 40%, 50% greater or more than the tensile stress of a plastic article produced with a solid composition of biological entities.
[0049] [0049] In particular, the plastic article of the invention produced from a liquid composition of biological entities may exhibit a higher Young modulus than the same plastic article produced from a solid composition of biological entities. Typically, the plastic article of the invention is a plastic film and shows a Young module 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 selected direction of the machine direction or the transversal direction. Typically, the plastic article of the invention is a plastic film and shows a Young modulus of about 20 MPa larger, preferably 30 MPa, 50 MPa, 100 MPa higher, or more, than the Young module of a plastic article produced from of a solid composition of biological entities, in at least one selected direction of the machine direction or the transversal direction.
[0050] [0050] The dynamic friction coefficient or sliding friction coefficient or kinetic friction coefficient (also abbreviated as µD) occurs when two objects move in relation to each other and rub together (like a slip on the ground). According to the invention, µD is measured when a plastic article slides over another plastic article. The sliding friction coefficient is defined as the ratio between the dynamic frictional force by the plastic article (force necessary to overcome the friction) and the normal force N acting perpendicular to the plastic articles.
[0051] [0051] The surface roughness of the plastic article can be assessed by a visual test by a user panel. The plastic article of the invention shows no visible defects on its surface, it is smooth. 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 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.
[0052] [0052] 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 the fracture. For rigid plastic articles, the impact resistance can be measured according to the NF EN ISO 179 standard, using plastic specimens produced with the same material as this plastic article and having a thickness of 4 mm and a total length of 80 mm. The determination of the impact resistance for rigid plastic articles with a thickness below 4 mm can also be measured directly on this plastic article, according to the standard NF EN ISO 6603-
[0053] [0053] It has also been shown that the introduction of biological entities by means of liquid or solid compositions comprising biological entities and a carrier selected, preferably by liquid composition, during the production process of a plastic article of the invention does not affect Technical performance plastic articles compared to plastic articles that do not contain biological entities.
[0054] [0054] The invention also provides a method for increasing the biodegradability of a plastic article of the invention, said method comprising introducing, during the production process of the plastic article, the composition of biological entities with a selected carrier. Biodegradability is further increased by introducing, during the production process of the plastic article, a liquid composition of biological entities with a selected carrier. The biodegradability of the plastic article is defined as the release of monomers, dimers or water and carbon dioxide over 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 the lactic acid dimer. In particular, the plastic article of the invention obtained by using a liquid composition of biological entities may exhibit greater biodegradability than the same plastic article produced from a solid or liquid composition of biological entities in the art. Typically, the plastic article of the invention shows a biodegradability of about 100% greater, preferably 25%, 30%, 40% greater than the biodegradability of a plastic article produced from a solid or liquid composition of biological entities in the art after 2 days.
[0055] [0055] In a particular embodiment, the plastic article of the invention is a plastic film, comprising at least one polyester and biological entities capable of degrading said polyester.
[0056] [0056] According to a preferred embodiment, 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 µm.
[0057] [0057] In particular, the plastic film of the invention shows a lower Turbidity value of about 3%, 4%, 5% or more, compared to the turbidity value of a plastic film produced from a solid composition of biological entities. Therefore, the Turbidity value of the plastic film is between 80% and 95%, preferably between 85% and 93%. Alternatively, the Turbidity value of the plastic film is above 30%, preferably above 50%, more preferably above 70%, even more preferably above 85%. Otherwise, the Turbidity value of the plastic film is below 98%, preferably below 96%, more preferably below 95%, even more preferably below 94%. In another embodiment, the Turbidity value of the plastic film is below 60%.
[0058] [0058] In another specific embodiment, the Young's modulus of the film is preferably above 200 MPa in both directions (machine or transverse) and / or the tensile stress of the film at break is preferably above 15 MPa in both directions (machine or transversal), and / or the elongation of the film at break is preferably above 130% in the machine direction and above 300% in the transversal direction. In another specific 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 and / 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 with a high PLA content. It also has a modulus of elasticity greater than 200 MPa in the longitudinal direction and greater than 150 MPa transverse, measured according to EN ISO 527-3 and / or maximum stress greater than 15 MPa in the longitudinal direction and greater than 13 MPa in the transverse direction , measured according to EN ISO 527-3.
[0059] [0059] In another particular embodiment, the plastic article of the invention is a rigid plastic article, comprising at least one polyester and biological entities capable of degrading said polyester.
[0060] [0060] In a specific embodiment, the rigid plastic article of the invention shows an impact resistance above 17kJ / m2, preferably above 20kJ / m2 according to NF EN ISO 179. In another specific 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 at break is above 40 MPa, preferably above 55 MPa.
[0061] [0061] According to a particular embodiment, the rigid plastic article of the invention is a sheet with a thickness below 800 µm, preferably below 450 µm. The sheet of the invention shows an impact resistance above 1 J, preferably above 1.5 J, more preferably above 2 J, according to NF EN ISO 7765-1.
[0062] [0062] In another particular embodiment, the plastic article of the invention is a non-woven fabric, comprising at least one polyester and biological entities capable of degrading said polyester.
[0063] [0063] Advantageously, the plastic article is a biodegradable plastic article that meets at least one of the relevant standards and / or labels known to a person skilled in the art, such as the standard EN 13432, standard NFT51800, standard ASTM D6400, Biodegradation in Soil OK (Label TÜV Austria), Biodegradation in Water OK (Label TÜV Austria), Compostability OK (Label TÜV Austria), Home Compostability OK (Label TÜV Austria).
[0064] [0064] A biodegradable plastic article refers to a plastic 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 and biomass. For example, the plastic article is biodegradable in water. Preferably, about 90% by weight of the plastic article is biodegraded in water in less than 90 days, more preferably in less than 60 days, even more preferably in less than 30 days. Most preferably, the plastic article can be biodegraded when exposed to humidity and temperature conditions that occur in the landscape.
[0065] [0065] The invention also provides a method for increasing the biodegradability of a plastic article comprising at least one polyester, wherein the method comprises the step of mixing a polyester with both suitable biological entities to degrade said polyester and the antacid filler for obtaining a plastic composition and the step of making a plastic article with said plastic composition.
[0066] [0066] It is an object of the invention to provide a plastic article, comprising at least one polyester, selected from copolymers of lactic acid and / or succinic acid and / or terephthalic acid or a mixture thereof.
[0067] [0067] Advantageously, the plastic article comprises at least one polyester selected from polylactic acid (PLA) (such as poly (L-lactic acid) (PLLA), poly (D-lactic acid) (PDLA), poly (D acid, L-lactic) (PDLLA) or PLA stereocomplex (scPLA)), polyglycolic acid (PGA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate tereftalate (PBAT derivatives) or combinations / mixtures thereof. In a preferred embodiment, the plastic article comprises at least PLA and / or PCL and / or PBAT, more preferably at least PLA. In another embodiment, the polyester is selected from copolymers of lactic acid and / or succinic acid and / or terephthalic acid.
[0068] [0068] Preferably the polyester has a melting temperature above 140 ° C.
[0069] [0069] In another specific embodiment, the plastic article comprises at least two polyesters selected from polylactic acid (PLA), polyglycolic acid (PGA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate
[0070] [0070] In a particular embodiment, the plastic article can additionally comprise at least one natural polymer. Natural polymers can be selected from the group of lignin, polysaccharides, such as cellulose or hemicellulose, starch, chitin, chitosan and derivatives thereof or combinations / mixtures thereof. In a specific embodiment, natural polymers are plasticized (for example, by a plasticizer, such as water or glycerol) before being used in the production of the masterbatch composition. This plasticization step modifies the chemical structure of natural polymers, allowing their use through a plastic production process. Preferably, the plastic article additionally comprises at least one natural polymer, selected from cellulose, starch, flour, gums and derivatives. More preferably, the plastic article of the invention additionally comprises at least starch or flour, even more preferably plasticized starch or flour (a).
[0071] [0071] The plastic article of the invention further comprises a carrier selected from polysaccharides, a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C and mixtures thereof.
[0072] [0072] Preferably, the plastic article of the invention additionally comprises a polysaccharide carrier and, optionally, a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C.
[0073] [0073] More preferably, the plastic article of the invention further comprises a polysaccharide carrier and a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C.
[0074] [0074] The polysaccharide carrier is preferably selected from starch derivatives, natural gums, marine extracts, microbial and animal polysaccharides.
[0075] [0075] In a specific embodiment, the carrier polymer with a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C is a polyester, preferably selected from polycaprolactone (PCL), polybutylene adipate succinate (PBSA), polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoate (PHA), polylactic acid (PLA) or copolymers. In another particular embodiment, the carrier polymer is a natural polymer, preferably selected from starch. In another specific embodiment, the carrier polymer is 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).
[0076] [0076] Preferably, the carrier polymer as defined above has a melting temperature below 120 ° C and / or a glass transition temperature below 30 ° C.
[0077] [0077] In a particular embodiment, the plastic article of the invention comprises PLA and at least one additional polyester selected from PBAT and / or PCL, and at least one natural polymer selected from plasticized starch or flour (a).
[0078] [0078] According to another particular embodiment, the plastic article of the invention may additionally comprise one (a) or more charges. The load can be selected from any conventional load used in the plastics industry. The charge can be natural or synthetic. The charge can be selected from mineral or organic charges. In a preferred embodiment, the mineral filler is chosen from the group consisting of, without limitation, calcite, carbonate salts or metal carbonate, such as calcium (or limestone), potassium carbonate, magnesium carbonate, carbonate aluminum, zinc carbonate, copper carbonate, chalk, dolomite, silicate salts, such as hydrated magnesium silicate, such as talc or soapstone, calcium silicate (volastonite), potassium silicate, magnesium silicate (talc) ), aluminum silicate (kaolin) or mixture thereof, such as mica, smectite, such as montmorillonite, vermiculite, and paligorskite-sepiolite, sulphate salts, such as barium sulphate or calcium sulphate (plaster), mica, salt metal hydroxide or hydroxide, such as calcium hydroxide or potassium hydroxide (potash) or magnesium hydroxide or aluminum hydroxide or sodium hydroxide (caustic soda),
[0079] [0079] According to another particular embodiment, the plastic article of the invention may additionally comprise one or more additive (s). In general, additives are used in order to enhance specific properties in the final product (i.e., the final plastic article made with said masterbatch composition). For example, additives can be selected from the group consisting of, without limitation, plasticizers, colorants, processing aids, anti-slip additives, rheological agents, antistatic agents, anti-UV agents, toughness agents, impact modifiers, anti-fog agents, compatibilizers, flame retardant agents, antioxidants, light stabilizers, oxygen removers, paints, adhesives, fertilizers and phytosanitary products. Advantageously, the plastic article comprises at least one additive selected from plasticizers, anti-slip additives and light stabilizers. 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.
[0080] [0080] 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, as defined above, - from 0 to 30% of a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C, as defined above, and - of 0.01 to 10% of biological entities having PLA degradation activity.
[0081] [0081] Preferably, the plastic article comprises at least 3% of a carrier polymer, more preferably at least 4% of a carrier polymer. In another preferred embodiment, the plastic article comprises from 0.1% to 1% of the polysaccharide carrier. In another preferred embodiment, the plastic article comprises less than 1% of biological entities having a PLA-degrading activity, preferably less than 0.5%, preferably about 0.25%.
[0082] [0082] In a particular embodiment, the plastic article comprises from 0.1 to 0.5% of enzymes having a PLA degradation activity, preferably about 0.25%.
[0083] [0083] In a specific embodiment, the plastic article of the invention comprises, based on the total weight of the plastic article: - from 10 to 94% of a polyester, as defined above, particularly polylactic acid (PLA), - from 0.1 to 5% of a polysaccharide carrier, as defined above, - from 4 to 20% of a carrier polymer with a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C, as defined above, and - from 0.01 to 1% of biological entities having PLA degradation activity.
[0084] [0084] Other compositions of the invention are described here below. Although not mentioned, they all fulfill the characteristic that they all include less than 5% of a polysaccharide carrier as defined above, particularly between 0.1 to 1% of a polysaccharide carrier and that the second polyester and / or natural polymer can match to the carrier polymer or additional polymer. In addition, a carrier polymer as defined above can also be included and may be referred to as a second polyester or a third polyester.
[0085] [0085] In a specific embodiment, the plastic article of the invention comprises, based on the total weight of the plastic article: - from 10 to 98% PLA
[0086] [0086] In a specific embodiment, the plastic article of the invention comprises, based on the total weight of the plastic article: - from 10 to 98% PLA - from 0 to 50% of a second polyester, preferably selected from PBAT - from 0.1 to 10% of a third polyester, preferably selected from a polymer with a melting temperature below 140 ° C - from 0 to 40% of natural polymer - from 1 to 20% of additives - from 0 to 40% of at least one charge - from 0.01 to 10% of biological entities having PLA degradation activity.
[0087] [0087] In a particular embodiment, the plastic article is a plastic film. Preferably, the plastic film of the invention comprises, based on the total weight of the plastic film: - 10 to 60% PLA, preferably 20 to 40%
[0088] [0088] In another specific embodiment, the plastic film of the invention comprises, based on the total weight of the plastic film: - from 10 to 60% of PLA, preferably from 20 to 40% - from 10 to 60% of a second polyester, preferably selected from PBAT, preferably from 20 to 40% - from 1 to 20% of additives, preferably selected from plasticizers or compatibilizers - from 0.01 to 10% of biological entities having a PLA degradation activity .
[0089] [0089] In another specific embodiment, the plastic film of the invention comprises, based on the total weight of the plastic film: - from 10 to 60% of PLA, preferably from 20 to 40% - from 10 to 60% of a second polyester, preferably selected from PBAT, preferably from 20 to 40% - from 0 to 10% of a third polyester - from 1 to 20% of additives, preferably selected from plasticizers or compatibilizers - from 0.01% to 10 % of biological entities with PLA degradation activity
[0090] [0090] In another particular embodiment, the plastic film of the invention comprises, based on the total weight of the plastic film: - from 10 to 60% of PLA, preferably from 20 to 40% - from 10 to 60% of a second polyester, preferably selected from PBAT, preferably from 20 to 40% - from 0 to 10% of a third polyester, preferably selected from PCL - from 1 to 40% of natural polymer, preferably selected from starch, preferably from 10 to 30% - from 1 to 20% of additives, preferably selected from plasticizers or compatibilizers - from 0.1 to 10% of at least one filler, preferably selected from calcium carbonate - from 0.01 to 10% of biological entities having PLA degradation activity
[0091] [0091] In a specific embodiment, the film of the invention has a thickness between 15 µm and 30 µm and comprises at least 10% to 40% PLA based on the total weight of the plastic film, from 5% to 15% PCL, from 40% to 70% PBAT.
[0092] [0092] In a specific embodiment, the rigid plastic article of the invention comprises, based on the total weight of the plastic article: - from 10 to 98% of PLA - from 0 to 60% of a second polyester - from 0 to 20 % of additives - from 0 to 40% of at least one charge - from 0.01 to 10% of biological entities having PLA degradation activity.
[0093] [0093] In a preferred embodiment, the plastic article of the invention is produced from a rigid plastic sheet of the invention. Preferably, the rigid plastic sheet of the invention comprises, based on the total weight of the plastic article: - from 10 to 98% PLA, preferably from 50 to 95% - from 0 to 30% of a second polyester, preferably, selected from PCL, which improves impact resistance - from 0 to 20% of additives, preferably selected from plasticizers, impact modifier and nucleating agent
[0094] [0094] In a specific embodiment, the rigid plastic article of the invention comprises, based on the total weight of the plastic article: - from 10 to 98% PLA - from 0 to 50% of a second polyester - from 0 to 20 % of a third polyester - from 0 to 40% of natural polymer - from 0 to 20% of additives - from 0 to 40% of at least one charge - from 0.01 to 10% of biological entities having a degradation activity of PLA.
[0095] [0095] In a specific embodiment, the rigid plastic article of the invention comprises more than 90% PLA based on the total weight of the plastic article, and exhibits an impact resistance above 1 J. In another specific embodiment, the plastic article of the invention is obtained by using a liquid composition of biological entities and a masterbatch comprising 80% PCL. Thus, this plastic article contains at least 4% PCL and exhibits an impact resistance above 2 J and an elongation at break above 6%, preferably above 15%, maintaining good rigidity in relation to the application, above 1.6 GPa.
[0096] [0096] According to the invention, the plastic article comprises biological entities suitable for degrading at least one polyester contained in said plastic article. In another particular embodiment, the plastic article comprises biological entities suitable for degrading at least two polyesters contained in said plastic article.
[0097] [0097] In a preferred embodiment, biological entities comprise at least one enzyme with polyester degradation activity and / or at least one microorganism that expresses, and optionally excretes, an enzyme having polyester degradation activity. In a preferred embodiment, the biological entities consist of at least one enzyme with polyester degrading activity. In another particular embodiment, biological entities comprise or consist of at least two enzymes with polyester degrading activity. Examples of suitable enzymes having a polyester degrading activity for use in the invention include, without limitation, depolymerase, esterase, lipase, cutinase, carboxylesterase, protease or polyesterase. In a particular embodiment, biological entities comprise or consist of an enzyme with a PLA-degrading activity. Biological entities are preferably a protease 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 enzyme known to degrade such as Savinaseâ, Esperaseâ, Everlaseâ, Protexâ, Optimaseâ, Multifectâ or any enzymes of the subtilisin family CAS 9014-01-1 or any functional variant thereof.
[0098] [0098] Enzymes can be in pure or enriched form, or in a mixture with other excipients or diluents. A combination of enzymes can also be used.
[0099] [0099] In an alternative embodiment, biological entities comprise microorganisms that produce such enzymes, either naturally or as a result of specific engineering (for example, recombinant microorganisms).
[00100] [00100] In a particular embodiment, biological entities comprise enzymes encapsulated in nanocapsules, enzymes encapsulated in cage molecules, and aggregated enzymes. The term "cage molecule" means a molecule that can be inserted into the structure of said enzymes to stabilize them and make them resistant to high temperatures. Encapsulation techniques are well known to those skilled in the art and include, for example, nanoemulsions.
[00101] [00101] In a particular embodiment, the plastic article comprises less than 11% by weight, preferably between 0.01% and 10% by weight of biological entities, based on the total weight of the plastic article.
[00102] [00102] Biological entities can be supplied in liquid or solid form. For example, biological entities can be in the form of dust. In a specific embodiment, the biological entities used to prepare the plastic article are a liquid composition of enzymes and / or microorganisms mixed with a diluent or carrier, such as a stabilizing (s) and / or solubilizing component (s) (s). For example, the composition can be a solution comprising enzymes and / or microorganisms suspended in water and, optionally, additional components, such as, glycerol, sorbitol, dextrin, starch, glycol, such as propanediol, salt etc.
[00103] [00103] According to the invention, the biological entities used to prepare the plastic article are supplied in a liquid composition comprising said biological entities having a degradation activity of polyester, a carrier and an aqueous solvent, wherein the carrier is a polysaccharide selected from starch derivatives, natural gums, marine extracts, microbial and animal polysaccharides.
[00104] [00104] The invention also provides a process for the preparation of a plastic article comprising at least one polyester and biological entities having a polyester degradation activity dispersed homogeneously in the plastic article, said process comprising a step (a) of mixing between 0 , 01% and 10% by weight of biological entities having a polyester degradation activity with at least one polyester and a step (b) of molding said mixture from step (a) into a plastic article, in which the biological entities are mixed during step (a) in an appropriate form to allow homogeneous dispersion of said biological entities in the plastic article, said form being selected from - a liquid composition comprising biological entities having a polyester degradation activity, a polysaccharide carrier and water, or - a masterbatch comprising biological entities having a degradation activity of polyester and a polymer carrier sweetener having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C.
[00105] [00105] Preferably, step (a) of the mixing is carried out at a temperature at which the polyester is partially or fully melted and / or in an extruder.
[00106] [00106] Polyester, biological entities and carriers are defined above and in the examples, as well as their proportions in the plastic article, the person skilled in the art being able to adjust the proportion of each of the ingredients to be used in the process to obtain such final proportions .
[00107] [00107] In a first embodiment, biological entities are provided in the form of a liquid composition.
[00108] [00108] Preferably, the liquid 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 an aqueous solvent - of 3% to 80%, by weight, of a polysaccharide carrier.
[00109] [00109] Particularly, biological entities retain a degradation activity of polyester in the plastic composition and / or in the final plastic article.
[00110] [00110] The liquid composition is suitable to be extruded with a polymer. Preferably, the composition is suitable to be extruded 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.
[00111] [00111] In a preferred embodiment, the aqueous solvent is water. In such an embodiment, the composition comprises, based on the total weight of the composition, from 15% to 95% water, and from 5% to 85% of other components, such as at least 0.01% to 35% of biological entities and 3% to 80% of a carrier.
[00112] [00112] In a specific embodiment, the liquid composition comprises, 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 an aqueous solvent - from 4% to 80% by weight of a polysaccharide carrier.
[00113] [00113] In a preferred embodiment, the liquid 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 20% by weight of biological entities.
[00114] [00114] In a particular preferred embodiment, the liquid 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 weight total 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. In a preferred embodiment, the aqueous solvent is water.
[00115] [00115] In a particularly preferred embodiment, the liquid composition comprises more than 5% by weight of polysaccharide carrier, preferably more than 10%, even more preferably than 15%.
[00116] [00116] 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 a solvent aqueous - from 15% to 70%, by weight, of a polysaccharide carrier.
[00117] [00117] In another preferred embodiment, the composition comprises less than 70% vehicle weight, preferably less than 60%. In a particular embodiment, the composition comprises 5% and 70% carrier, preferably 10% to 60%. In another particular embodiment, the composition comprises 10% to 50% carrier.
[00118] [00118] In another specific embodiment, 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.
[00119] [00119] In another specific embodiment, 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.
[00120] [00120] In another specific embodiment, the composition comprises, based on the total weight of the composition: - from 0.01% to 35% of the biological entities - from 40% to 60% of water - from 20% to 45% of a carrier.
[00121] [00121] In another particular embodiment, the composition comprises about 50% water and 0.01% to 35% biological entities, and 20% to 50% carrier.
[00122] [00122] In another particular embodiment, the composition comprises about 40% water, and 0.01% to 35% biological entities, and 20% to 60% carrier.
[00123] [00123] In a specific embodiment, the weight ratio of polysaccharide / aqueous solvent is below 4.
[00124] [00124] In a specific embodiment, the amount of polysaccharide 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.
[00125] [00125] Alternatively or in addition, the amount of polysaccharide carrier in the composition is 4% to 100% of the maximum carrier solubility in the composition, that is, 4% to 100% of the carrier's saturation concentration in the composition.
[00126] [00126] According to the invention, the presence of polysaccharide carriers in the composition allows to protect and stabilize biological entities not only in the composition, but also during a heat treatment, such as an extrusion process in which the composition is introduced into a partially or fully fused polymer.
[00127] [00127] In a particular embodiment, the carrier is in a solid form at room temperature.
[00128] [00128] 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 specific embodiment, the amount of maltodextrin in the composition is
[00129] [00129] In a particular embodiment, the carrier is a natural gum. Preferably, the carrier is selected from gum arabic, guar gum, tragacanth gum, caraia gum, more preferably, the carrier is gum arabic.
[00130] [00130] In another particular embodiment, the carrier is a marine extract. Preferably, the carrier is selected from carrageenan or alginate.
[00131] [00131] In another particular embodiment, the carrier is a microbial polysaccharide. Preferably, the carrier is xanthan.
[00132] [00132] In another particular embodiment, the carrier is an animal polysaccharide. Preferably, the carrier is chitosan.
[00133] [00133] In a particular embodiment, the liquid composition comprises at least two carriers selected from starch derivatives, natural gums, marine extracts, microbial polysaccharides and animals. In another particular embodiment, the carrier / biological entities ratio is between 0.8 and 1.2, preferably about 1. In another particular embodiment, the carrier / biological entities ratio is above 1, out of preferably above 2. According to the invention, the liquid composition can additionally comprise sugars, proteins, lipids, organic acids, salts and vitamins originating from the culture supernatant of a polyester degrading microorganism used as biological entities in the composition. This supernatant can be treated preliminarily (for example, mechanically or physically or chemically) to increase the concentration of enzymes and / or remove other components, such as (such as) DNA or cellular debris.
[00134] [00134] 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 stabilizing 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.
[00135] [00135] According to a specific embodiment, the liquid composition can comprise non-soluble components with a particle size below 20µm.
[00136] [00136] Alternatively or in addition, the composition additionally comprises mineral components, such as,
[00137] [00137] Advantageously, the liquid composition of the invention is stable, that is, chemically and biologically stable.
[00138] [00138] In another specific 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.
[00139] [00139] In another specific embodiment, the composition comprises, based on the total weight of the composition: - from 0.01% to 35% of PLA degradation enzymes
[00140] [00140] In another particular embodiment, the composition comprises about 50% water, and 0.01% to 35% PLA degrading enzymes, and 20% to 50% arabic gum.
[00141] [00141] In another particular embodiment, the composition comprises about 40% water, and 0.01% to 35% PLA degrading enzymes, and 20% to 60% arabic gum.
[00142] [00142] All of the compositions defined above optionally comprise from 0% to 20% of other components, preferably selected from proteins, salts, polyols, preferably from 0% to 5%. In addition, the PLA-degrading enzymes of such compositions are preferably selected from proteases.
[00143] [00143] In a specific embodiment, the liquid 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% protease - from 10% to 50% by weight of gum arabic, preferably from 15% to 35%.
[00144] [00144] In a specific 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% protease - from 10% to 50% by weight of gum arabic, preferably from 15% to 35% - from 0% to 20% by weight of other components, preferably selected from proteins, salts, polyols.
[00145] [00145] In a specific 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% protease - from 10% to 50% by weight of maltodextrin, preferably from 15% to 40%.
[00146] [00146] In a specific 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
[00147] [00147] Advantageously, the liquid composition is in liquid form at least at room temperature. Preferably, the liquid composition is in liquid form at the temperature at which said composition is introduced into a polymer that is in a partially or fully molten state.
[00148] [00148] Advantageously, in all the compositions mentioned above, the amount of carrier and biological entities is expressed as dry matter, that is, the amount after complete dehydration or evaporation of water or removal of water.
[00149] [00149] In a specific embodiment, a liquid composition of biological entities is introduced into a first carrier polymer that has a low melting point (below 140 ° C, preferably below 120 ° C) and / or a low glass transition temperature (below 70 ° C), such as, PCL, PBSA, PBAT to prepare a masterbatch.
[00150] [00150] The masterbatch in molten or solid form is also part of the invention.
[00151] [00151] The invention thus provides a masterbatch comprising biological entities having a polyester degrading activity and a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C.
[00152] [00152] Biological entities and carrier polymer are defined above and in the examples and all definitions and precision on the nature, compositions and properties of said components defined for the plastic article also apply to the definition of the masterbatch.
[00153] [00153] The masterbatch comprises in particular 50% to 95% by weight of carrier polymer based on the total weight of the masterbatch, preferably from 70% to 90% by weight of carrier polymer.
[00154] [00154] The masterbatch advantageously comprises from 5% to 50% by weight of the composition of biological entities based on the total weight of the masterbatch, more than 10% to 30% of the composition of biological entities.
[00155] [00155] The masterbatch is advantageously prepared with a liquid composition of the biological entities comprising a polysaccharide carrier as defined above.
[00156] [00156] Therefore, the masterbatch of the invention also comprises a polysaccharide carrier as defined above. In particular, it comprises from 1% to 30% of the polysaccharide carrier based on the total weight of the masterbatch, preferably from 1% to 15%.
[00157] [00157] Advantageously, the residence time of the liquid composition and, therefore, of the biological entities in the carrier polymer at a temperature above 100 ° C is as short as possible and, preferably, is between 5 seconds and 10 minutes, more preferably less than 5 minutes, 3 minutes, 2 minutes.
[00158] [00158] Below are descriptions of processes for the preparation of a plastic article, as described above, using a masterbatch, with or without a step in which the masterbatch is in solid state, conditioned for later use in a method to manufacture an article of according to the invention.
[00159] [00159] For example, the process comprises the steps of: a) preparing a masterbatch comprising biological polyester degradation entities and a carrier polymer by (i) heating the carrier polymer; and (ii) introducing 5% to 50% by weight of biological entities based on the total weight of the masterbatch during heating of the carrier polymer; and (b) introducing the masterbatch into a polyester-based matrix during the production of the plastic article in which step a) is carried out at a temperature at which the carrier polymer is partially or fully fused and at which biological entities are able to degrade the polyester of the polyester-based matrix and are introduced during step (ii) in the form of a liquid composition defined above, and step b) is carried out at a temperature at which the first polymer and the polyester of the matrix based on polyester are in a partially or fully molten state.
[00160] [00160] Step (a) of preparing the masterbatch can,
[00161] [00161] According to the invention, the carrier polymer is heated to a temperature below 140 ° C, and biological entities are introduced into the first polymer during said heating step. More generally, the masterbatch 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 biological entities are incorporated into the first polymer during extrusion. Preferably, step a) is carried out by extrusion.
[00162] [00162] In the preferred embodiment, the masterbatch is prepared by (i) extruding a carrier polymer, wherein said carrier polymer has a melting temperature below 140 ° C and (ii) introducing biological entities during extrusion of the first polymer, before introducing said masterbatch in a polyester-based matrix to prepare the plastic article.
[00163] [00163] In a specific embodiment, the carrier polymer is a polyester, preferably selected from polycaprolactone (PCL), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoate (PHA), polylactic acid (PLA) or copolymers. In another particular embodiment, the first polymer is a natural polymer, preferably
[00164] [00164] The masterbatch comprises a first polymer that has a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C. Preferably, the first polymer of the masterbatch has a melting temperature below 120 ° C and / or a glass transition temperature below 30 ° C. For example, this first polymer is selected from the group consisting of PCL, PBAT, PLA and EVA. Preferably, this first polymer is selected from the group consisting of PCL, PBAT and PLA. The advantage of such an embodiment is to reduce the heating of biological entities during the masterbatch production process.
[00165] [00165] The masterbatch comprises between 5% and 50% by weight of biological entities, based on the total weight of the masterbatch, in which the biological entities are supplied in the form of the liquid composition defined above. Preferably, the biological entities represent between 10% and 40% by weight, more preferably between 10% and 30% by weight, based on the total weight of the masterbatch. In a particular embodiment, the masterbatch comprises about 20%
[00166] [00166] The masterbatch can additionally comprise one or more additional compound (s). In particular, the masterbatch may additionally comprise one or more additive (s). In general, additives are used in order to enhance specific properties in the final product.
[00167] [00167] In a specific embodiment, the masterbatch composition comprises, based on the total weight of the masterbatch: - from 50 to 95% by weight of a carrier polymer; - 5 to 50% by weight of biological polyester degradation entities; and optionally - at least one additive.
[00168] [00168] In another specific embodiment, the masterbatch comprises, based on the total weight of the masterbatch: - from 70 to 90% by weight of a carrier polymer; - 10 to 30% by weight of biological polyester degrading entities; and optionally - at least one additive.
[00169] [00169] In a specific embodiment, the masterbatch is produced by a process called "aggregation", usually an extrusion granulation process, in which the first polymer is melted and mixed with the biological entities. The aggregation combines mixing and combining techniques during a heating process, in order to guarantee uniformity, homogeneity and dispersion in the masterbatch. Aggregation is a technique known to a person skilled in the art. This composition process can be carried out with an extruder, such as single screw extruders, multiple screw extruders, with co-rotating or counter-rotating configuration, dispersive kneading machines, alternative single screw extruders (co-kneading machines).
[00170] [00170] More generally, step (a) of preparing the masterbatch can be carried out with an extruder, in which the first polymer is heated, melted and mixed with the biological entities. The first polymer can be introduced into the extruder in powder or granulated form, preferably in granulated form.
[00171] [00171] In a preferred embodiment, the extruder used for producing the masterbatch of step (a) is a multiple screw extruder, preferably a twin screw extruder, more preferably a co-rotating twin screw extruder. In a particular embodiment, the extruder additionally comprises, after the screws, a static mixer.
[00172] [00172] In a preferred embodiment, the residence time of the mixture of the first polymer and drug in the extruder is between 5 seconds and 3 minutes, preferably less than 2 minutes. When the masterbatch comprises a polymer with a melting temperature below 120 ° C, the residence time of the mixture in the extruder is between 5 seconds and 10 minutes, preferably less than 5 minutes.
[00173] [00173] One skilled in the art will easily adapt the characteristics of the extruder (for example, the length and diameter of the screw (s), the profile of the screw, the degassing zones, etc.), and the residence time in the first polymer, biological entities and the type of masterbatch desired.
[00174] [00174] As disclosed above, biological entities are preferably introduced into the extruder in the form of a liquid composition described above.
[00175] [00175] In particular, this extruder may contain a main hopper and several successive heating zones, in which the temperature can be controlled and regulated independently, and in which additional components can be added at different times during the process. Vacuum and natural degassing zone are required during extrusion to remove volatile products such as water.
[00176] [00176] The liquid composition of biological entities is introduced with a pump. In a particular embodiment, biological entities are introduced at a late stage of the mixing stage (i.e., in the last heating zones), and more particularly when the first polymer is in a partially or fully molten state. Thus, exposure to high temperatures is reduced. Preferably, the residence time of the composition in the extruder is half the residence time of the first polymer, or less. In another particular embodiment, biological entities are introduced before the polymer in the extruder. Thus, the contact between the composition and the polymer is increased.
[00177] [00177] According to the invention, after step (a) of preparing the masterbatch, said masterbatch can be conditioned in any suitable solid form. In this regard, in a preferred embodiment, the masterbatch is modeled on a rod through a matrix. The stem is then cooled, before being chopped in the form of granules and / or granules of masterbatch and optionally dried. An underwater granulator can also be used. In a further embodiment, said granules of the masterbatch can be sprayed or micronized to produce a powder of said masterbatch. 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 molten state, before step (b).
[00178] [00178] According to the process of the invention, the masterbatch is introduced during step (b) in a polyester-based matrix, in order to produce a plastic article of the invention. The step of introducing the masterbatch into the polyester-based matrix is carried out at a temperature at which the first polymer and at least one polyester of the polyester-based matrix are in a partially or fully molten state. When the masterbatch discharged from step (a) and the polyester-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 masterbatch into the base matrix part polyester.
[00179] [00179] Preferably, the polyester-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.
[00180] [00180] Advantageously, the polyester-based matrix comprises at least one polyester chosen from polylactic acid (PLA), polyglycolic acid (PGA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT) and derivatives or combinations / 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.
[00181] [00181] One skilled in the art is able to choose the polyester (s) of the matrix based on polyester, depending on the nature of the final plastic article.
[00182] [00182] According to the invention, the polyester-based matrix can additionally contain at least one natural polymer and / or at least one filler and / or at least one additive.
[00183] [00183] Natural polymers can be selected from the group of lignin, polysaccharides, such as cellulose or hemicellulose, starch, chitin, chitosan and derivatives thereof or combinations / mixtures thereof. In a specific embodiment, natural polymers are plasticized (for example, by a plasticizer such as water or glycerol) before being used in the production of the masterbatch composition. This plasticization step modifies the chemical structure of natural polymers, allowing their use through a plastic production process.
[00184] [00184] The load can be selected from any conventional load used in the plastics industry. The type and exact quantity of loads can be adapted by a person skilled in the art, depending on the type of composition of the masterbatch and the guidelines provided in this application. Advantageously, the plastic article comprises at least one selected filler of calcium carbonate, talc or silica.
[00185] [00185] It is the purpose of the invention to provide a process in which a polyester-based matrix is mixed with a masterbatch comprising a large number of biological entities to make a plastic article in which the biological entities are accurately added and distributed in a manner homogeneous.
[00186] [00186] According to the invention, after step (a) of mixing and optional conditioning of the mixture in a suitable solid form, the plastic composition produced is (b) modeled on a plastic article.
[00187] [00187] In a particular embodiment, step (b) is carried out using a polyester with a high melting point, that is, with a melting point above 140 ° C. For example, step (b) is performed using PLA.
[00188] [00188] Advantageously, step (b) is implemented at a temperature at which the polyester of the polyester-based matrix and the first polymer are in a partially or fully molten state. For example, step (b) can be performed 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 even above 150 ° C, depending on the nature of the polymer. Typically, this temperature does not exceed 300 ° C.
[00189] [00189] In a particular embodiment, step (b) is carried out at the melting point of the polyester of the matrix based on polyester. The polyester 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 polyester. In another particular embodiment, step (b) is carried out at a temperature above the melting point of said polyester.
[00190] [00190] Typically, said step (b) can be carried out by extrusion, aggregation by extrusion, blow molding and extrusion, extrusion of blown film, extrusion of fused film, calendering and thermoforming, injection molding, compression molding, compression molding, extrusion swelling, rotary molding, hot pressing, coating, laminating, 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 (for example, temperature, residence time, etc.). As an example, the extrusion of blown film is particularly suitable for the production of plastic films. As another example, melt film extrusion is particularly suitable for the production of plastic sheets, and injection molding, thermoforming, blow molding, rotomoulding or 3D printing are particularly suitable for the production of rigid plastic articles.
[00191] [00191] In a particular embodiment, step (b) is implemented with a solid masterbatch in a powder or granular form, preferably in a granular form.
[00192] [00192] In a specific embodiment, 0.5 to
[00193] [00193] In another particular embodiment, 1% to 5% by weight of masterbatch are incorporated and / or mixed with 95% to 99% by weight of a polyester-based matrix in a partially or fully molten state.
[00194] [00194] In another specific embodiment, the present invention relates to a process for preparing a plastic article comprising at least PLA, comprising the steps of a) preparing a masterbatch comprising biological entities of degradation of PLA and PCL by ( i) heating of PCL; and (ii) introducing 5% to 50% by weight of biological entities from PLA degradation based on the total weight of the masterbatch during the heating of PCL; and (b) introduction of the masterbatch in a PLA-based matrix during the manufacture of the plastic article
[00195] [00195] Where step a) is carried out at a temperature at which the PCL is in a partially or fully molten state, preferably above 65 ° C, more preferably about 70 ° C and at which biological entities are introduced during step (ii) in the form of a liquid composition and step b) is carried out at a temperature at which the PCL and PLA are in a partially or fully molten state, preferably above 120 ° C, more preferably about 155 ° C.
[00196] [00196] In another embodiment, the liquid composition of biological entities is directly introduced into the polymer (s) that make up the plastic article.
[00197] [00197] It is also an object of the invention to provide a process for the preparation of a plastic article as described above, comprising: - a step (a) of mixing less than 11%, particularly between 0.1% and 10% by weight of biological entities having a polyester degradation activity, with at least said polyester, and - a step (b) of modeling said mixture from step (a) in a plastic article, in which the biological entities are mixed during step a ) in the form of a liquid composition comprising a polysaccharide carrier.
[00198] [00198] In a specific embodiment, the process additionally comprises a step of mixing at least one additive and / or at least a second polyester and / or a natural polymer with the polyester and the biological entities, prior to step (b ). Alternatively, that additive and / or polyester and / or natural polymer can be mixed in step (a) with the polyester and the biological entities.
[00199] [00199] In a particular embodiment, the polyester used in step (a) is in a granulated form.
[00200] [00200] Step (a) of the mixing is carried out at a temperature at which the polyester is partially or fully melted. Mixing step (a) can therefore be carried out at a temperature equal to or above 40 ° C, particularly at or above 45 ° C, 55 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C, 100 ° C, or even above 150 ° C, depending on the nature of the polyester. Typically, this temperature does not exceed 300 ° C. More particularly, the temperature does not exceed 250 ° C.
[00201] [00201] In a specific embodiment, the plastic composition can be produced from step a) by a process called "aggregation", usually an extrusion granulation process, in which the polyester is melted and mixed with the biological entities . The aggregation combines mixing and mixing techniques during a thermal process, in order to guarantee uniformity, homogeneity and dispersion in the final compound. Composition is a technique known to a person skilled in the art. This aggregation process can be performed with an extruder, such as single screw extruders, multiple screw extruders, co-rotating or counter-rotating configuration, dispersive kneading machines, alternative single screw extruders (co-kneading machines).
[00202] [00202] Preferably, step (a) of the mixing can be carried out with an extruder, in which the polyester is heated and melted and mixed with the biological entities.
[00203] [00203] According to a specific embodiment, step (a) of the mixture comprises a first step of introducing the biological entities into a first polymer that has a low melting point (below 140 ° C, preferably below 120 ° C), such as, PCL, PBSA, PBAT; and a second step in which a polyester-based matrix comprising a second polyester having a high melting point, such as PLA, is then added to the mixture resulting 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 the partially molten state. Then, the PLA that has been heated to about 150 ° C to be in a partially molten state is added directly to the mixture.
[00204] [00204] In a preferred embodiment, the extruder used for the production of the plastic composition of step a) is a multiple screw extruder, preferably a twin screw extruder, more preferably a co-rotating twin screw extruder. In a particular embodiment, the extruder additionally comprises, after the screws, a static mixer.
[00205] [00205] 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.
[00206] [00206] One skilled in the art will easily adapt the characteristics of the extruder (for example, the length and diameter of the screw (s), the profile of the screw, the degassing zones etc.) and the residence time in the polyester , in biological entities and the type of plastic composition desired.
[00207] [00207] As disclosed above, biological entities are preferably introduced into the extruder in the form of a liquid composition described above.
[00208] [00208] In particular, this extruder may contain a main hopper and several successive heating zones, in which the temperature can be controlled and regulated independently, and in which additional components can be added at different times during the process. Vacuum and natural degassing zone are required during extrusion to remove volatile products like water.
[00209] [00209] Biological entities in liquid form are introduced with a pump. In a particular embodiment, biological entities are introduced in a last stage of the mixing stage (that is, in the last heating zones), and more particularly when the polyester is in a partially or fully molten state. Thus, exposure to high temperatures is reduced. Preferably, the residence time of the biological entities in the extruder is half that of the polyester, or less. In another particular embodiment, the liquid composition is introduced before the polyester in the extruder. Thus, the contact between the composition and the polyester is increased.
[00210] [00210] According to a specific embodiment, step (a) of the mixing is carried out with two extruders, a main extruder and a second extruder connected to the main extruder, in which the biological entities are mixed with a first polyester having a melting temperature below 140 ° C in the second extruder, and introduced into the main extruder in an area where a polyester-based matrix is already in a partially or fully molten state, that polyester-based matrix comprising at least the polyester to be degraded by biological entities and, eventually, a natural polymer selected from plasticized starch. According to a specific embodiment, the main extruder is selected from single screw extruder or multi screw extruder, and the second extruder is selected from single screw extruders, multi screw extruders or side feeder.
[00211] [00211] According to the invention, after step (a) of mixing, the mixture can be conditioned in any suitable solid form. In this regard, in a preferred embodiment, the mixture emitted from step (a) is modeled on a rod through a matrix. The rod is then cooled, and optionally dried before being chopped in the form of granules of plastic composition. In another embodiment, said granules of plastic composition can be pulverized or micronized to produce a powder of said plastic composition.
[00212] [00212] According to the invention, after step (a) of the mixture, and the optional conditioning of the mixture in a suitable solid form, the plastic composition produced is (b) modeled on a plastic article.
[00213] [00213] Advantageously, step (b) is implemented at a temperature at which the polyester of the plastic composition is in a partially or fully molten state. For example, step (b) can be performed at a temperature of 40 ° C or above, particularly at or above 45 ° C,
[00214] [00214] In a particular embodiment, step (b) is carried out at the melting point of the polyester of the plastic composition. The polyester 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 polyester. In another particular embodiment, step (b) is carried out at a temperature above the melting point of said polyester.
[00215] [00215] Typically, said step (b) can be carried out by extrusion, extrusion aggregation, blow molding and extrusion, blow film extrusion, melt film extrusion, calendering and thermoforming, injection molding, compression molding, extrusion swelling,
[00216] [00216] In a preferred embodiment, step (b) is implemented with a solid plastic composition in a powder or granular form, preferably in a granular form.
[00217] [00217] The plastic article comprises between 0.1% and 10% by weight of biological entities in the form of a liquid composition, based on the total weight of the plastic article. Preferably, the liquid composition of biological entities represents between 0.1% and 5%, more preferably between 0.1% and 3% of the plastic article.
[00218] [00218] According to another embodiment, biological entities in the form of a liquid composition are directly introduced in step (b) of the modeling of this plastic article.
[00219] [00219] In a specific embodiment, the present invention relates to a process for preparing a plastic composition, comprising: - a step (a) of mixing between 0.1% and 10% by weight of proteases with activity of degradation of PLA, based on the total weight of the plastic composition, with PLA and - a step (b) of shaping said mixture from step (a) into a plastic article, where 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 co-rotating twin screw extruder.
[00220] [00220] It is an additional object of the invention to provide a process for the manufacture of a plastic article containing biological entities successively comprising 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 other than the first polymer, where the first polymer has a melting point below 140 ° C and the second polymer has a melting point above 140 ° C.
[00221] [00221] More generally, plastic articles can be produced by any techniques known to a person skilled in the art.
[00222] [00222] It is also another object of the invention to provide a method for increasing the homogeneity of the dispersion of biological entities in a plastic article comprising at least one polyester and said biological polyester degradation entities, said method comprising the introduction during the process of production of that plastic article, biological entities in the form of a liquid composition.
[00223] [00223] Different liquid compositions were prepared using a commercial protease, Savinase® 16L (Novozymes) sold in a liquid form (containing more than 50% by weight of polyols based on the total weight of the liquid composition and water). This enzyme is known for its ability to degrade polylactic acid (Polylactide Degradation by commercial proteases; Y.Oda, A. Yonetsu, T. Urakami and K.
[00224] [00224] The liquid composition A (LC-A) was obtained by ultrafiltration and diafiltration of the commercial Savinase® 16L in the 3.5Kd membrane using 5mM CaCl2 (diafiltration factor of about 50). This process allows the polyols contained in the commercial Savinase® to be removed. As no carrier was added in liquid composition A, the film produced with this composition corresponds to the negative control.
[00225] [00225] The liquid composition B and C (LC-B and LC-C) were also obtained from the commercial liquid form of Savinase® by ultrafiltration and diafiltration on the 3.5 Kd membrane using 5 mM CaCl2 (diafiltration factor of about 50 ).
[00226] [00226] The masterbatch compositions were prepared from polycaprolactone polymer granules (PCL) (CapaÔ 6500 from Perstorp) and compositions of the invention described in Example 1.1. The enzymatic activity of said masterbatch was additionally determined.
[00227] [00227] An aggregation machine, or co-rotating twin screw extruder, was used (Leistritz ZSE 18MAXX). This aggregation machine comprised nine successive heating zones Z1 to Z9, in which the temperature can be controlled and regulated independently. An additional zone Z10 was present after zone Z9, corresponding to the head of the double screw (Z10), which is also a heated part. A suitable screw profile was used to efficiently mix the liquid composition of the invention with the molten polymer. The parameters used for each extruded masterbatch are summarized in Table 2.
[00228] [00228] The molten polymer reached the screw Z10 comprising 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 in solid granules <3 mm.
[00229] [00229] According to this experiment, 80% by weight of the PCL was extruded with 20% by weight of the liquid composition.
[00230] [00230] The enzymatic activity in the masterbatches was determined according to the protocol described below.
[00231] [00231] 50 mg of granules 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, 5 ml of 0.1 M Tris buffer, pH 9.5, was added. Each tube was manually shaken to create an emulsion. The organic and aqueous phases were then separated by centrifugation at 10000G for 5 minutes (Heraeus Multifuge X302-Thermoscientific). The aqueous phase was removed and maintained separately. Another 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 the aqueous phase are mixed. To remove traces of dichloromethane in the 10 mL of the aqueous phase, oxygen was bubbled into the sample for 20 minutes. The protease activity of each sample was determined using a colorimetric test: 20 µL of sample in the correct dilution was mixed with 180 µL of a 5mM pNA solution (N-succinyl-Ala-Ala-Ala-p- Nitroanilide, Sigma Aldrich-CAS 52299-14 -6). The optical density was measured at 30 ° C-420 nm using an absorption spectrophotometer (Clariostar-BMG Labtech). The mass of the active enzyme was thus determined using a calibration curve.
[00232] [00232] The comparison of the mass of the active enzyme and the theoretical mass of the enzyme in the compound allowed to determine the percentage of residual activity in the masterbatches.
[00233] [00233] The residual activities of the produced masterbatches are resumed in Table 3.
[00234] [00234] The masterbatches produced with the liquid compositions LC-B and LC-C demonstrate a higher residual activity compared to the masterbatches produced with a liquid composition that does not contain carrier (LC-A - negative control), indicating greater protection of the enzyme during the extrusion process. The masterbatch produced with the composition comprising gum arabic shows an even better residual activity than the masterbatch produced the composition comprising maltodextrin.
[00235] [00235] The granulated masterbatch compositions of Example 1.2 were used to produce plastic articles based on the biodegradable polylactic acid of the invention through an extrusion process. The biodegradability of said plastic articles was further tested.
[00236] [00236] 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 CaCO3 by OMYA.
[00237] [00237] All materials were dried before extrusion. PLA and PBAT were dried about 16 hours in a desiccator at 60 and 40 ° C, respectively. A vacuum oven was used at 40 ° C-40 mb for 16 h for calcium carbonate.
[00238] [00238] The temperature was set at 185 ° C 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. CaCO3 was introduced into zone 7 in the melted polymers using a gravimetric feeder to obtain the matrix. The resulting extrudate was cooled in a cold water bath before granulation.
[00239] [00239] The MB1-MB2-MB3 masterbatches described in Example 1.2 are used to produce the plastic films of the invention.
[00240] [00240] Before the film blowing extrusion, the masterbatches and the PLA-based matrix were dried in the desiccator for 40 hours at 50 ° C. The combinations were prepared in order to introduce the same amount of enzyme in all films, based on the theoretical enzyme mass in the masterbatch according to Table 4: Table 4: Composition of the films of the invention Films of the Matrix MB1 MB2 MB3 invention (control negative) PCL / LC-B PCL / LC-C PCL / LC-A Film A 97% 3% - - Film B 95% - 5% - Film C 95% - - 5%
[00241] [00241] A LabTech compact film blowing line of type LF-250 with a 20 L / D 20 mm extruder of type LBE20-30 / C was used to produce films. The speed of the screw was 50 rpm. The defined temperatures are detailed in Table 5.
[00242] [00242] Biodegradability tests were carried out, using plastic films produced in Example 1.3, according to the protocol defined below.
[00243] [00243] 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 ° C, 150 rpm in an Infors incubation shaker HT Multitron Pro. Aliquots of 1 mL of buffer were sampled regularly and filtered through a 0.22 µm 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) dimer and lactic acid. The chromatography system used was an Ultimate 3000 UHPLC system (Thermo Fisher Scientific, Inc.
[00244] [00244] The hydrolysis of plastic films was calculated based on the LA and the released LA dimer. The percentage of degradation is calculated in relation to the percentage of PLA in the films.
[00245] [00245] The results of depolymerization of the films of the invention, after 2 days, are shown in Table 6.
[00246] [00246] The films of the invention (MB2 / LC-B and MB3 / LC-C) show a higher depolymerization rate, due to a higher residual activity in comparison with the control film produced with a carrier liquid private composition (MB1 / LC-A - negative control). These results confirm that the use of the liquid composition comprising a carrier leads to greater protection of the enzyme during the extrusion process. The film produced with the gum arabic composition comprises an even better degradability than the film produced with the composition comprising maltodextrin.
[00247] [00247] A liquid LC composition was prepared from a commercial protease, Savinase® 16L (Novozymes).
[00248] [00248] A solid composition was also prepared according to the same protocol using a commercial protease, Savinase® 16L and the protocol defined above. The obtained liquid composition was concentrated, and was then dried by lyophilization to obtain a solid composition called SC.
[00249] [00249] Comparisons of the different compositions are summarized in Table 7.
[00250] [00250] The masterbatches were prepared with granules of polycaprolactone polymer (PCL - CapaÔ 6500 from Perstorp) and the liquid or solid compositions of 2.1, using the same aggregation machine as in Example 1.2.
[00251] [00251] More particularly, a masterbatch comprising PCL and the LC liquid enzymatic composition of Example 2.1 was produced. PCL and LC were introduced separately into the extruder in the feed zone, which is an unheated zone. For feeding, a gravimetric feeder was used for the polymer and a peristaltic pump for the liquid composition. The masterbatch obtained was called MB-L.
[00252] [00252] In parallel, a masterbatch comprising PCL and the solid enzymatic composition SC of Example 2.1 was produced. SC was introduced in Zone 7 using a gravimetric feeder suitable for dosing solids in powder form. The masterbatch obtained was designated MB-S.
[00253] [00253] The parameters used for the extrusion of the masterbatch are detailed in table 8 and table 9. A suitable screw profile was used in order to efficiently mix the corresponding compositions with the polymer.
[00254] [00254] The molten polymer reached the Z10 screw comprising 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 in solid granules <3 mm.
[00255] [00255] Three different matrices were used for the production of the films: two commercial compounds ecovio® F2332 and ecovio® F2223 from BASF, and an aggregate household matrix called Matrix 1.
[00256] [00256] Matrix 1 was manufactured using a CLEXTRAL EV25HT twin screw extruder comprising twelve zones Z1 to Z12, in which the temperature is controlled and regulated independently. The compound consists of 33% pre-plasticized PLA containing 10% by weight of tributylacetyl citrate (CITROFOL® BII from Jungbunzlauer), 32% of PBAT Ecoflex C1200 supplied by BASF, 30% of thermoplastic starch in which the starch is starch of standard corn 171111 supplied by Roquette and 5% calcium carbonate from OMYA.
[00257] [00257] For blowing film, a LabTech compact film blowing line type LF-250 with a 20 mm 30 L / D extruder type LBE20-30 / C was used. The speed rate of the screw used was 60 rpm. The film's blowing ratio was about 5 for a 17 µm lens.
[00258] [00258] Before blowing the film, MB-L (example
[00259] [00259] The films obtained with the PLA-based matrix ecovio® F2332 and ecovio® F2223 were designated as Film 1 and Film 2, respectively, and Table 11 shows the parameters used for the extrusion.
[00260] [00260] The film produced with Matrix 1 was designated as Film 3 and Table 12 shows the parameters used for extrusion.
[00261] [00261] The PLA-based matrix ecovio® F2332 and ecovio® F2223 and Matrix 1 were used to produce films with the masterbatch comprising the solid composition of biological entities and were designated respectively as Film 4, Film 5 and Film 6.
[00262] [00262] Before blowing the film, the matrix based on MB-S and PLA was dried in a desiccator for 40h at 50 ° C. An additional masterbatch comprising only PCL and 70/30 w / w gum arabic was added to the matrix based on the MB-S / PLA mixture to obtain the same concentration of biological entities in all films of the invention.
[00263] [00263] Finally, the films were made using 93%
[00264] [00264] Movies 1 and 4, films 2 and 5 and films 3 and 6, respectively, have the same compositions. Then, MB-S was dry mixed in the PLA-based matrix and introduced into the film blowing extruder.
[00265] [00265] The same process as films 1, 2 and 3 was used to produce the films, except the temperature profile, as shown in table 13: Table 13: Extruder and die temperature settings Film Zone Z1 Z2 Z3 Z4 Matrix # 1 Matrix # 2 Films 4, 5 and 6 T ° C 135 147 147 150 152 150
[00266] [00266] The films of the invention in example 2.3 were analyzed according to the following parameters: A. Turbidity
[00267] [00267] Turbidity is determined using a Perkin Elmer 650S UV Visible spectrometer equipped with a 150 mm integration sphere according to NF EN 2155-9 (August 1989). Values are determined on a 50x30 mm² sample. In each film, measurements are repeated 3 times in 3 different parts of the film.
[00268] [00268] The dynamic friction coefficient (µD) is measured according to the standard NF EN ISO-8295 (December 2004), which fits for plastic film or plastic sheet with a thickness below 0.5 mm. It is determined using a Lloyd Instruments LS5 test machine equipped with a sensor capacity of 20N. The apparatus comprises a horizontal test table on which the first sample is placed, a mass generating the pressing force (1.96 N) and to which the second sample is attached, and a traction mechanism to produce a relative movement between the dough 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%.
[00269] [00269] The dynamic frictional force FD is the average force in the first 6 centimeters of relative motion.
[00270] [00270] The mechanical tensile properties (elongation at break, tensile strength at break, Young's modulus) were determined using a Zwick testing machine equipped with a 50N sensor capacity according to ASTM D882-12 (at 23 ° C and 55% RH). Two film directions: machine direction and cross direction were analyzed with the following parameters: - Adhesion separation rate for Young's modulus
[00271] [00271] The thickness used for tensile analysis was determined based on the weights, dimensions and densities of the film. This choice was made to overcome overestimation of thickness due to the presence of particle aggregates on the surface of the film, especially when solid compositions are used.
[00272] [00272] However, thickness measurement can be done using a Mitutoyo thickness gauge to demonstrate the observed surface roughness for films containing aggregates.
[00273] [00273] The protocol was the same used in Example 1.4.
[00274] [00274] The results obtained for the film of the invention produced with the liquid composition were compared with 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.
[00275] [00275] Table 14 shows the Turbidity results measured in films 1, 2, 4 and 5. The Turbidity values of the films of invention 1 and 2 are respectively lower than those of 4 and 5. Turbidity is caused by impurities contained in the plastic article (such as accumulation of small particles in the article or very small defects on the surface). The lower the Turbidity value, the greater the translucency of the article.
[00276] [00276] Tables 15 and 16 show the dynamic friction coefficient, tensile and thickness properties measured by the Mitutoyo thickness gauge of films produced in
[00277] [00277] In Table 16, the films produced from MB-S are used as a reference and considered 100% of the defined parameter.
[00278] [00278] Friction coefficient is the ratio between the sliding force and the holding force of two surfaces in contact. This coefficient characterizes the difficulty of two materials to slide over each other. This difficulty can be increased in case of surface roughness. The values of the dynamic friction coefficient of the films of the invention 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 during the production process allows to reduce the coefficient of dynamic friction and, thus, to reduce the surface roughness compared to the use of a solid composition of biological entities.
[00279] [00279] This feature was also visible to the naked eye: films 4, 5, 6 show irregularities on the surface due to particle aggregates.
[00280] [00280] The thickness measurement using a Mitutoyo thickness gauge also demonstrates this surface roughness observed for films produced from solid composition of biological entities, leading to aggregates in the film.
[00281] [00281] Young's modulus, tensile strength and final tensile strength measured for the films of the invention are significantly higher than the control films. The liquid composition has a smaller particle size which leads to a fine and homogeneous dispersion of the particles in the film and as a consequence to an improvement of the mechanical properties.
[00282] [00282] The depolymerization test showed that the films of the invention have a significantly higher percentage of depolymerization rate compared to those obtained with the solid enzymatic composition, as shown in Table 17 (ecovio® films F2332), Table 18 (films of ecovio® F2223) and Table 19 (Matrix 1 films). Films produced from MB-S are used as a reference and considered as 100.
[00283] [00283] An injection molding machine was used for the production of rigid plastic articles: KM 50t / 380 type CX ClassiX with MC6 computer controller system.
[00284] [00284] The rigid plastic articles were produced by incorporating the MB-L masterbatch of Example 2.2 in two types of polyester-based matrix. The matrices are chosen between two grades of polylactic acid polymer whose characteristics are shown in Table 20.
[00285] [00285] Before dry mixing, the polyester-based matrix and masterbatch were dried in the desiccator at 50 ° C for 40h. 10% MB-L was then added to the matrix based on polyester. Articles with 100% polyester matrix were also produced for comparison.
[00286] [00286] Parts of 1 mm thick, 60 mm x 60 mm were manufactured by the injection molding process. The parameters were defined depending on the degree of acid in the matrix based on the polyester used.
[00287] [00287] The parameters defined for injection molding are summarized in Table 21.
[00288] [00288] The total residence time of the composition in the barrel was measured and is about 12 minutes for PA1 and PA2 and 13 minutes for PA3 and PA4.
[00289] [00289] The rigid articles produced were subjected to a depolymerization test, according to the protocol described in Example 1.4. The results are shown in Table 22, PA1 and PA3 are used as a reference and considered as 100. They demonstrate that the use of the composition of the invention allows to produce biodegradable rigid plastic articles.
[00290] [00290] The masterbatches were prepared using polycaprolactone polymer granules (PCL) (CapaÔ 6500 from Perstorp) and liquid or solid enzymatic composition described in Table 24. The liquid composition LC-1 and the solid composition SC-1 were prepared in the same way. way as detailed in example 2.1.
[00291] [00291] The MB-LC1 masterbatch comprising PCL and the liquid composition LC-1 was prepared using a Clextral Evolum 25 HT twin screw extruder comprising twelve zones Z1 to Z12, in which the temperature is controlled and regulated independently. The parameters used for the process are as follows: temperature profile at 65 ° C-65 ° C-65 ° C-65 ° C- 65 ° C-65 ° C-65 ° C-65 ° C-65 ° C- 65 ° C-50 ° C, extruder screw speed of 450 rpm, and total flow rate of 40 kg / h.
[00292] [00292] In parallel, an MB-SC1 masterbatch comprising PCL and the solid composition SC-1 was prepared in a co-rotating twin screw extruder (Leistritz ZSE 18MAXX) with the following parameters: 70 ° C-70 ° temperature profile C-70 ° C-70 ° C-70 ° C-65 ° C-65 ° C-65 ° C- 65 ° C-65 ° C, screw speed of 150 rpm, and total flow rate of 2 kg / h. 22% of the solid enzyme composition was introduced into the PCL based on the total weight of the masterbatch using a gravimetric feeder in Zone 7. The cooling and granulation system of both masterbatches was the same as detailed in Example 1.2.
[00293] [00293] The MB-LC1 and MB-SC1 masterbatches thus comprise the same enzyme concentration.
[00294] [00294] Plastic dumbbells with a thickness of 4 mm and a total length of 170 mm were produced using an injection molding machine (KM 50t / 380 CX ClassiX).
[00295] [00295] The dumbbells were produced from an injection of PLA grade NatureWorks® IngeoÔ 3251D and the masterbatch MB-LC1 described in 3.1. The control dumbbells were produced from the same PLA grade and the MB-SC1 masterbatch described in 3.1. 100% PLA dumbbells were also produced for standardized mechanical characterization.
[00296] [00296] Before manufacturing the rigid articles, the PLA and MB-LC1 were dried using a desiccator for 40h at 50 ° C and the MB-SC1 was dried in a vacuum oven at 50 ° C for 48h. Rigid plastic articles were made using 95% by weight of the PLA-based matrix and 5% by weight of a masterbatch.
[00297] [00297] The injection molding parameters for each article are detailed in Table 25: Table 25: Injection molding parameters for dumbbell production Composiç Define Press Press Cycle Temperatures in temperatures in the area of barrel zones, inje reten moldag mold from the tion zone in (s) (° C) of supply (bar) (bar) to the front zone (° C) RA 95% PLA 40/145/150/150/16 1000 850 70 30 - + 5% MB- 0/160 LC LC1 1 RA 95% PLA 40/145/150/150/16 1005 900 70 30 - + 5% MB- 0/160 SC SC1 1
[00298] [00298] The tensile and impact properties of the rigid plastic article of the invention and the control plastic article made of a solid composition were characterized.
[00299] [00299] Tensile tests were performed using a Zwick Roell test 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
[00300] [00300] The rigid article produced from a masterbatch from a liquid composition shows no significant difference in the measured mechanical characteristics, showing that the use of a liquid composition does not have a severe impact on the modulus of elasticity, maximum stress, strain deformation maximum, stress at break and stress at break of the rigid article of the invention.
[00301] [00301] The tests were performed 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 cutting pliers. The dimensions of the bars are 4 mm * 10 mm * 80 mm. The test results are shown in Table 27.
[00302] [00302] The rigid article of the invention produced from a liquid composition of biological entities shows better resistance to impact than those produced from a solid composition of biological entities. This is certainly due to the good distribution of biological entities in the plastic article.
[00303] [00303] Biodegradability tests were performed on the injected rigid article RA-LC1 produced from the liquid composition. First, the rigid article was coarsely ground, immersed in liquid nitrogen and then ground using the ZM 200 RETSCH Ultra Centrifugal Mill equipped with a 500 µm grid. 100 mg of this powder was weighed,
[00304] [00304] The eluent was 5 mM H2SO4. The injection was 20 µL of the sample. LA was measured according to 20 standard curves prepared from commercial LA.
[00305] [00305] The depolymerization level of the rigid article reached about 10% after 48 hours, showing that the biological entities retain a degrading activity of polyester in the final plastic article.
[00306] [00306] The masterbatch composition was prepared from polycaprolactone polymer (PCL) granules (CapaÔ 6500 from Perstorp) and the liquid enzymatic composition LC-1 described in example 3.1. The masterbatch was manufactured using a CLEXTRAL EV25HT co-rotating twin screw extruder comprising twelve zones Z1 to Z12, in which the temperature is controlled and regulated independently.
[00307] [00307] The PCL is introduced in zone 1 at 16 kg / h and the liquid composition in zone 5 at 4 kg / h using a peristaltic pump, in which the zones are heated according to Table 27. 20% of the liquid composition LC was entered into the PCL based on the total weight of the masterbatch. This masterbatch is designated as MB-LC2.
[00308] [00308] The enzymatic activity in the masterbatch was determined according to the protocol described in the Example
[00309] [00309] A thermoforming PLA grade Luminy® LX175 Total Corbion was used to manufacture 450 µm thick plastic sheets to be subjected to additional standardized impact, tensile characterization and biodegradability testing.
[00310] [00310] For the manufacture of plastic sheets, a FAIREX extruder comprising four zones Z1 to Z4, in which the temperature is controlled and regulated independently with a diameter of 45, a flat matrix of 220 mm equipped with a rim adjustable to 1.5 mm of nominal aperture and a three-cylinder calender was used.
[00311] [00311] Before extrusion and calendering, MB-LC2 and PLA were dried and mixed. The MB-LC2 was dried 20 hours at 40 ° C in a vacuum oven and the PLA was dried 4 hours at 40 ° C in dryers.
[00312] [00312] The leaves obtained from 0% (negative control), 5% or 10% of MB-LC2 added to the PLA were respectively designated S0, S5 and S10. The extrusion and calendering parameters are detailed in Table 28.
[00313] [00313] In order to assess the biodegradability of plastic sheets, a depolymerization test was carried out following the protocol already described in Example 3.4.
[00314] [00314] After 8 days, the powder from leaves S0, S5 and S10 shows, respectively, a PLA depolymerization rate of 0.08%, 0.77% and 13.0%, showing that biological entities retain an activity of polyester degradation in the final plastic article of the invention (S5 and S10).
[00315] [00315] The impact tests were performed according to the NF EN ISO 7765-1 standard, using the step method. According to this standard, the sample was cut directly into the plastic sheet. The tests were performed using a Labthink BMC-B1 dart test machine and the results are shown in Table 29.
[00316] [00316] The results of the impact test show that the sheets of the invention produced from the liquid composition (S5 and S10) show an improvement in impact resistance compared to the S0 control made of 100% PLA.
[00317] [00317] Tensile tests were performed using a Zwick Roell test machine equipped with a 20 kN force sensor. The tests were performed according to the NF EN ISO 527-1 standard. The measured tensile properties are shown in Table 30.
[00318] [00318] Comparing to a pure PLA sheet (S0), the sheets produced from a masterbatch itself produced from a liquid and PCL composition, show an improvement in flexibility with the increase of the incorporation of that masterbatch in sheets based on PLA, maintaining sufficient rigidity necessary for the intended application.
[00319] [00319] Different liquid compositions were prepared using a commercial protease, Savinase® 16L (Novozymes) sold in a liquid form.
[00320] [00320] The liquid composition D, E, F and G was obtained according to the method described in Example 1.1: ultrafiltration and diafiltration of the commercial Savinase® 16L on the 3.5 Kd membrane and in which gum arabic is added as a carrier. The commercial Savinase® 16L sold in liquid form, corresponds to liquid composition H and is used as a negative control. This composition comprises more than 50% by weight of polyols, such as carrier, based on the total weight of the liquid composition and water.
[00321] [00321] The description of the different liquid compositions is taken up in Table 31.
[00322] [00322] The masterbatch compositions were prepared from polycaprolactone polymer (PCL) granules (CapaÔ 6500 from Perstorp) and compositions described in Example 3.1, using the same aggregation machine as in Example 1.2.
[00323] [00323] According to this experiment, 80% by weight of the PCL was extruded with 20% by weight of the liquid composition. The parameters used for each extruded masterbatch are summarized in Table 32.
[00324] [00324] The enzymatic activity of said masterbatch was further determined using the protocol described in Example 1.2. The comparison of the mass of the active enzyme and the theoretical mass of the enzyme in the masterbatch allowed to determine the percentage of residual activity in the masterbatches. The residual activities of the produced masterbatches are shown in Table 33.
[00325] [00325] All masterbatches produced with liquid compositions (LC-D to LC-G) demonstrate a high residual activity. On the contrary, MB8 containing Savinase 16L and corresponding to the negative control, does not show any residual activity.
[00326] [00326] This result confirms the interest in the process of extrusion of liquid compositions comprising a specific carrier in comparison with the commercial formulation already described.
[00327] [00327] 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.
[00328] [00328] Additionally, MB4, produced from the composition that contains the largest amount of water, compared to the compositions used to produce MB5,
[00329] [00329] The granulated masterbatch compositions MB4, MB5 and MB6 of Example 5.2 were used to produce plastic articles based on the biodegradable polylactic acid of the invention through an extrusion process. The biodegradability of said plastic articles was further tested.
[00330] [00330] 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 CaCO3 by OMYA. All materials were dried before extrusion. PLA and PBAT were dried for about 5 hours in a desiccator at 60 and 40 ° C, respectively. A vacuum oven at 40 ° C-40 mb was used for 16 h for calcium carbonate.
[00331] [00331] The temperature was set at 185 ° C 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. CaCO3 was introduced into zone 7 in the melted polymers using a gravimetric feeder to obtain the PLA-based matrix. The resulting extrudate was cooled in a cold water bath before granulation.
[00332] [00332] The MB4-MB5-MB6 masterbatches described in Example 5.2 are implanted to produce the plastic films of the invention.
[00333] [00333] Before the film extrusion, the masterbatches and the PLA-based matrix were dried in a vacuum oven at 50 ° C - 40 mb for 15 h. The combinations were prepared in order to introduce the same amount of enzyme in all films, based on the theoretical mass of enzymes in the masterbatch and according to Table 34. For films E and F, it was necessary to add PCL 6500 (also dry following the same conditions) in order to obtain identical composition in all films.
[00334] [00334] The blowing was performed using the same machine and the parameters described in example 1.3.
[00335] [00335] Biodegradability tests were performed on plastic films produced in Example 5.3, according to the protocol described in example 1.4.
[00336] [00336] The hydrolysis of plastic films was calculated based on the LA and the released LA dimer. The percentage of degradation is calculated in relation to the percentage of PLA in the films.
[00337] [00337] The results of depolymerization of the films, after 4 days, are shown in Table 35.
[00338] [00338] All films of the invention show a high depolymerization rate, indicating the presence of active enzyme. The more the liquid formulation contains dry matter, the yield of more degradation achieved is high in the film of the invention. This result confirms that a greater dry matter in the composition of the invention results in a greater protection of biological entities during the extrusion processes (production of masterbatch and production of plastic article).
[00339] [00339] The LC-1 liquid composition of Example 3.1 and two degrees of polylactic acid (PLA) were used to manufacture masterbatches: a Total Corbion amorphous grade LX930U (melting temperature below 140 ° C) and a NatureWorks 4043D IngeoÔ semi-crystalline biopolymer (melting temperature above 140 ° C).
[00340] [00340] The polylactic acid-based masterbatches designated as MB-PLA1, MB-PLA2 and MB-PLA3 were prepared in a co-rotating twin screw extruder (Leistritz ZSE 18MAXX) with a screw speed of 150 rpm and a total flow of 2 kg / h. The extrusion temperatures are detailed in Table 36 below. The PLA was introduced in the unheated feed zone (Z0), and the LC-1 was introduced in the Z6 using a Brabender pump. The cooling and granulation system of both masterbatches was the same as that detailed in Example 1.2. The composition of the masterbatches is also shown in Table 36.
[00341] [00341] Table 36: Temperature profile and process parameters of the aggregation process Composition Z10 Zone Z1 Z2 Z3 Z4 Z5 Z6 Z7 Z8 Z9 (matrix) 80% PLA MB 135 135 135 135 135 120 120 120 120 LX930U + Temperature 120 ° C PLA1 ° C ° C ° C ° C ° C ° C ° C ° C ° C 20% LC-1 90% PLA MB- 135 135 135 135 135 120 120 120 120 LX930U + Temperature 120 ° C PLA2 ° C ° C ° C ° C ° C ° C ° C ° C ° C 10% LC-1 90% PLA MB- 145 145 145 145 145 130 130 130 130 4043D + Temperature 130 ° C PLA3 ° C ° C ° C ° C ° C ° C ° C ° C ° C 10% LC-1
[00342] [00342] Biodegradability tests were performed, using masterbatches produced above, according to the protocol defined in Example 3.4, and the level of depolymerization after 24 h is shown in table 37.
[00343] [00343] Masterbatches based on PLA LX930U with lower melting point (MB-PLA1 and MB-PLA2) showed higher levels of depolymerization than MB-PLA3 based on
[00344] [00344] MB-PLA1 or MB-PLA2 and PLA-based matrix of Example 1.3 (42.3% by weight of NatureWorks PLA 4043D, 51.7% by weight of PBAT PBE006 by NaturePlast and 6% by weight of CaCO3 from OMYA) were used for film production. Before the film blowing extrusion, the masterbatches and the PLA-based matrix were dried in a vacuum oven at 60 ° C for 5h. The compositions of the prepared mixtures are shown in Table
[00345] [00345] The film blowing line used and the set temperatures are the same as in Example 1.3. The set screw speed rate was 60 rpm. The amplitude of the cooling air and the extraction speed were adjusted to obtain a bubble width of 200 mm and a film thickness between 15 and 20 µm.
[00346] [00346] Biodegradability tests were performed on the films produced above according to the protocol established in Example 1.4 and the level of depolymerization after 26 days is shown in table 39.
[00347] [00347] The films produced from a masterbatch comprising PLA with a melting temperature below 140 ° C and the composition of the invention showed degradation in aqueous medium. Film 7 and film 9 must contain the same amount of biological entities, but Film 7 based on the most concentrated masterbatch (MB-PLA1 produced from 20% of LC-1) shows a higher level of degradation than Film 9 based on MB-PLA2 produced from 10% LC-1. However, the results show that the liquid composition of the invention is also suitable to be introduced into a partially or fully melted polymer having a melting point above 140 ° C and that biological entities still preserve the polymer's degradation activity in the masterbatch .
[00348] [00348] The liquid composition LC-1 of example 3.1 was used for the preparation of masterbatches. The same extruder and the same parameters as in Example 1.2 were used to prepare a masterbatch composed of 90% PCL (CapaÔ 6500 from Perstorp) and 10% of the LC-1 liquid composition designated as MB9, a screw speed of 150 rpm and a total flow of 2 kg / h were defined.
[00349] [00349] The enzymatic activity in the masterbatch was determined according to the protocol described in the Example
[00350] [00350] A PLA-based filament was manufactured using NatureWorks 4043D IngeoÔ Biopolymer. Before the extrusion of the filament, masterbatch MB9 and PLA were dried for 15h at 50 ° C in a vacuum oven. The masterbatch was dry mixed with PLA in the ratio of 30% / 70% by weight and then extruded in a single screw extruder (Scamex - Rheoscam, Ø 20 - 11 L / D) at 100 ° C-170 ° C-190 ° C fixed in the three zones of the extruder and 180 ° C in the die. 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.
[00351] [00351] A Cartesian type printer was used.
[00352] [00352] Depolymerization tests were performed on 100 mg of 5A micronized specimen (1 mm grid) using the same protocol as in the Example
3.4. The depolymerization of the specimens reaches 11% in pH 9.5 buffer at 45 ° C after 8 days (dialysis system). The results of depolymerization confirm that biological entities retain the degradation activity of the polymer 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 (45)
[1]
1. Biodegradable plastic article characterized by the fact that it comprises at least one polyester and biological entities having a polyester degradation activity, in which it comprises a carrier selected from polysaccharides and, optionally, a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C, the biological entities being able to degrade said polyester and being homogeneously dispersed in the plastic article.
[2]
2. Plastic article according to claim 1, characterized by the fact that the polyester has a melting temperature above 140 ° C.
[3]
3. Plastic article according to claim 2, characterized by the fact that the polyester is selected from copolymers of lactic acid and / or succinic acid and / or terephthalic acid.
[4]
4. Plastic article according to any one of claims 1 to 3, characterized by the fact that the polysaccharide carrier is selected from starch derivatives, natural gums, marine extracts, microbial and animal polysaccharides and mixtures thereof.
[5]
5. Plastic article according to claim 4, characterized by the fact that the starch derivative is maltodextrin.
[6]
6. Plastic article, according to claim 4, characterized by the fact that the natural gum is selected from gum arabic, guar gum, tragacanth gum, caraia gum and mixtures thereof.
[7]
7. Plastic article according to claim 4, characterized by the fact that the natural gum is gum arabic.
[8]
8. Plastic article according to any one of claims 1 to 7, characterized in that it comprises a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C selected from a polyester, starch, EVA and mixtures thereof.
[9]
9. Plastic article according to claim 8, characterized by the fact that the carrier polymer has a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C and is a polyester selected from polycaprolactone (PCL), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polydioxanone (PDS), polyhydroxyalkanoate (PHA), polylactic acid (PLA) and mixtures thereof.
[10]
10. Plastic article according to claim 8, characterized by the fact that the polymer has a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C and is selected from polycaprolactone (PCL) , EVA, PBAT, PLA and mixtures thereof.
[11]
11. Plastic article according to any one of claims 1 to 10, characterized in that the biological entities having a polyester degradation activity represent less than 11% by weight of the total weight of the plastic article.
[12]
Plastic article according to any one of claims 1 to 11, characterized in that the biological entities having a polyester degradation activity comprise at least one enzyme having a polyester degradation activity.
[13]
13. Plastic article according to any one of claims 1 to 12, characterized in that it comprises, based on the total weight of the plastic article: - from 10 to 98% of a polyester, particularly polylactic acid (PLA) - from 0.01 to 10% of a polysaccharide carrier - 0 to 30% of a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C, and - from 0, 01 to 10% of biological entities having PLA degradation activity.
[14]
14. Plastic article according to any one of claims 1 to 13, characterized in that it comprises at least 3% of a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C.
[15]
15. Plastic article according to any one of claims 1 to 14, characterized in that it comprises 0.1% to 1% polysaccharide.
[16]
16. Plastic article according to any one of claims 1 to 15, characterized by the fact that it is a plastic film with a thickness below 250 µm.
[17]
17. Plastic article according to any one of claims 1 to 16, characterized in that it is a rigid article.
[18]
18. Process for preparing a plastic article comprising at least one polyester and biological entities having a polyester degradation activity homogeneously dispersed in the plastic article, said process characterized by the fact that it comprises a step (a) of mixing between 0.01% and 10% by weight of biological entities having a polyester degradation activity with at least one polyester and a step (b) of shaping said mixture from step (a) into a plastic article, in which the biological entities are mixed during step (a) in an appropriate form to allow homogeneous dispersion of said biological entities in the plastic article, selected from - a liquid composition comprising the biological entities having a polyester degradation activity, a carrier and water, or - a masterbatch comprising the biological entities having a polyester degrading activity and a carrier polymer having a melting temperature below 14 0 ° C and / or a glass transition temperature below 70 ° C.
[19]
19. Process according to claim 11, characterized by the fact that step (a) of mixing is carried out at a temperature at which the polyester is in the partially or fully molten state and / or in an extruder.
[20]
20. Process according to either of Claims 18 or 19, characterized in that the polyester has a melting temperature above 140 ° C.
[21]
21. Process according to any one of claims 18 to 20, characterized in that the polyester is selected from copolymers of lactic acid and / or succinic acid and / or terephthalic acid.
[22]
22. Process according to any one of claims 18 to 21, characterized by the fact that the polysaccharide carrier is selected from starch derivatives, natural gums, marine extracts, microbial and animal polysaccharides and mixtures thereof.
[23]
23. Process according to claim 22, characterized by the fact that the starch derivative is maltodextrin.
[24]
24. Process according to claim 22, characterized by the fact that natural gum is selected from arabic gum, guar gum, tragacanth gum, caraia gum and mixtures thereof.
[25]
25. Process according to claim 22, characterized by the fact that the natural gum is gum arabic.
[26]
26. Process according to any of claims 18 to 25, characterized in that the polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C is selected from among polyester, starch, EVA and mixtures thereof.
[27]
27. Process according to claim 26, characterized by the fact that the carrier polymer that has a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C is a polyester selected from polycaprolactone ( PCL), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polydioxanone (PDS), polyhydroxyalkanoate (PHA), polylactic acid (PLA) and mixtures thereof.
[28]
28. Process according to claim 26, characterized by the fact that the carrier polymer which has a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C is selected from polycaprolactone (PCL) , PBAT, PLA, EVA and mixtures thereof.
[29]
29. Plastic composition in a granulated form characterized by the fact that it comprises a polyester and said biological polyester degrading entities, and is produced from a process as defined in any one of claims 18 to 28.
[30]
30. Method for increasing the homogeneity of dispersion of biological entities in a plastic article as defined in any of claims 1 to 17, the method characterized by the fact that it comprises introducing biological entities in the form of production of that plastic article in the form of a liquid composition comprising biological entities having a polyester degradation activity, a polysaccharide and water carrier, or in the form of a masterbatch comprising biological entities having a polyester degradation activity and a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C.
[31]
31. Masterbatch characterized by the fact that it comprises biological entities having a polyester degradation activity, a carrier selected from polysaccharides and a carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° Ç.
[32]
32. Masterbatch according to claim 31, characterized by the fact that the carrier polymer that has a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C is selected from a polyester, starch , EVA and mixtures thereof.
[33]
33. Masterbatch, according to claim 32, characterized by the fact that the polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C is a polyester selected from polycaprolactone (PCL) , polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polydioxanone (PDS), polyhydroxyalkanoate (PHA), polylactic acid (PLA) and mixtures thereof.
[34]
34. Masterbatch according to claim 32, characterized by the fact that the polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C is selected from polycaprolactone (PCL), EVA , PBAT, PLA and mixtures thereof.
[35]
35. Masterbatch according to any one of claims 31 to 34, characterized in that it comprises from 50% to 95% by weight of carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° C based on the total weight of the masterbatch.
[36]
36. Masterbatch according to claim 35, characterized in that it comprises from 70% to 90% by weight of carrier polymer having a melting temperature below 140 ° C and / or a glass transition temperature below 70 ° Ç.
[37]
37. Masterbatch according to any one of claims 31 to 36, characterized by the fact that the biological entity comprises at least one enzyme having a polyester degradation activity.
[38]
38. Masterbatch according to any one of claims 31 to 37, characterized in that it comprises from 5% to 50% by weight of biological entities based on the total weight of the masterbatch.
[39]
39. Masterbatch, according to claim 38, characterized by the fact that it comprises 10% to 30% of biological entities.
[40]
40. Masterbatch according to any one of claims 31 to 39, characterized by the fact that the polysaccharide carrier is selected from starch derivatives, natural gums, marine extracts, microbial and animal polysaccharides and mixtures thereof.
[41]
41. Masterbatch, according to claim 40, characterized by the fact that the starch derivative is maltodextrin.
[42]
42. Masterbatch, according to claim 40, characterized by the fact that natural gum is selected from gum arabic, guar gum, tragacanth gum, caraia gum and mixtures thereof.
[43]
43. Masterbatch, according to claim 40, characterized by the fact that natural gum is gum arabic.
[44]
44. Masterbatch according to any one of claims 31 to 43, characterized in that it comprises from 1% to 30% of polysaccharide carrier.
[45]
45. Masterbatch, according to claim 44, characterized by the fact that it comprises from 1% to 15% of polysaccharide carrier.

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US20200199354A1|2020-06-25|

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CA3073791A1|2019-03-07|

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EP3676329A1|2020-07-08|

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WO2019043134A1|2019-03-07|

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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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EP17188781.3|2017-08-31|

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EP17188781|2017-08-31|

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PCT/EP2018/073416|WO2019043134A1|2017-08-31|2018-08-31|Biodegradable polyester article comprising enzymes|

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