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    • 专利摘要:
    The present invention relates to a composition comprising poly lactic acid (PLA) and / or a polymer of the family of polyhydroxyalkanoates (PHA), said composition further comprising polybutylene succinate (PBS), and at least one type of organically modified lamellar nanofillers. This composition can be used for the manufacture, preferably, of a biodegradable flexible packaging. The present invention also relates to a method of manufacturing granules formulated from the composition, the granules can be used for the manufacture of a flexible biodegradable packaging.
    公开号:FR3014885A1
    申请号:FR1362793
    申请日:2013-12-17
    公开日:2015-06-19
    发明作者:Epouse Tighzert Thi Hoang Lan Nguyen；Francoise Berzin；Sophie Estelle Risse；Mario Vitofrancesco
    申请人:GAIA BIOPACKAGING；Universite de Reims Champagne Ardenne URCA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of polymeric materials having an agro-sourced origin. The term "agro-sourced" is used in the following description to mean a material of vegetable origin from which monomers are obtained, which monomers then make it possible to obtain polymers of vegetable origin. The present invention will find its application mainly in the field of the manufacture of packaging products including flexible tubes. The invention more particularly relates to an agro-sourced polymer material which also has the property of being biodegradable, that is to say capable of degrading under a biological activity, for example under the action of enzymes and / or of microorganisms, by reducing its molecular weight. The by-products of this degradation are generally carbon dioxide, new biomass, water and / or methane. Traditionally, the plastic materials used to manufacture packaging such as flasks, tubes, jars, etc., used in particular in the field of cosmetics, are derived from petroleum resources. These include polypropylene (PP), polyethylene terephthalate (PET) or polyethylene (PE) in various forms, such as low density polyethylene (LDPE), linear low density polyethylene (LDPE) or polyethylene Medium Density 25 (MDES). In the case of certain applications requiring barrier properties, for example for gases or small molecules, which is particularly the case for certain food packaging or for cosmetic or hygiene products, multilayer structures are used. Such multilayer structures may in particular consist of PE / EVOH, EMA / PE or EAA / EVOH / adhesive, the denominations EVOH, EMA and EAA respectively corresponding to copolymer ethylene vinyl alcohol, ethylmethacrylate and graft copolymer ethylene acrylic acid .
    [0002] However, as already mentioned above, these materials are of fossil origin, and are more particularly derived from petroleum, which has several drawbacks, in particular from the point of view of their production and their elimination.
    [0003] On the one hand, oil is known to be a renewable resource with relatively slow speed and limited reserves. It is therefore necessary to find an alternative to the materials that come from it to mitigate a possible shortage of raw material.
    [0004] On the other hand, most materials of petroleum origin are not biodegradable or compostable; the disposal of waste containing such materials is therefore tedious. This is usually done by burial or incineration. In some cases, recycling is possible but it involves a preliminary sorting step that can be tedious and expensive. In addition, in the case of materials having a multilayer structure, the possibility of recycling is limited because of the combination of materials of different nature. In order to overcome the various disadvantages of materials derived from petroleum, it is sought to develop, in the field of packaging, new materials derived from agro-resources, that is to say from resources that are rapidly and easily renewable. The agro-plastic materials that can be substituted for the most widespread petrochemical derivatives at the present time are poly lactic acid (PLA), polyhydroxyalkanoates (PHA) and polybutylene succinate (PBS). All these materials also have the advantage of being biodegradable. Such materials are used on an industrial scale to make food packaging. More particularly, the PLA allows the manufacture of trays including fruit or vegetables, jars of yoghurt or bottles. The PHA is used for the manufacture of disposable products for hygiene. However, the biosourced or agro-sourced polymers currently used, and in particular PLA and PHA, have a number of disadvantages, in particular as regards their mechanical properties or their barrier properties. In addition, the aging resistance of the products obtained from these materials also remains to be improved, as well as their resistance to the manufacturing process for certain applications, especially when it comes to flexible tubes for cosmetics. In particular, as regards the manufacture of flexible tubes, the PLA has the disadvantage of having too much initial mechanical hardness and which is not suitable for the manufacture of this type of packaging. In addition, PLA, like all polyesters, is sensitive to hydrolysis, which has the negative consequence of reducing its mechanical properties during its aging, under severe conditions, over a short period of time, typically a few weeks. This results in a material that hardens and cracks after a few weeks, for example after 4 to 6 weeks after its manufacture. Hydrolysis is also responsible for reducing the barrier properties of materials made from PLA. These become more permeable during aging, especially at 45 ° C and in the presence of an aqueous solution. By way of illustration and comparison, a tube made especially from PLA containing an aqueous formulation has a mass loss of this formulation of between 10 and 14% after 6 weeks of storage at 45 ° C, whereas for a tube made of PE, this loss of mass is limited to 1% in the same period of time. Such an increase in the permeability of the products is particularly problematic, especially when they are intended to be filled with aqueous compounds, which is the case of cosmetics which should be able to be kept for periods of at least several months. up to two years at room temperature. To remedy this, it has been devised in patent document WO 2010 145 045 a multilayer material comprising two support layers, for example PLA, and a barrier layer, for example polypropylene carbonate (PPC), or PPC modified, which is located between each of the two support layers. However, such a material does not have optimal mechanical characteristics for the manufacture of particularly flexible packaging. In addition, the barrier layers are likely to delaminate during aging of the package, causing an increase in the permeability of the latter. This may, for example, reduce the shelf life of the product contained in said package, for example when it consists of a cosmetic or dermatological composition, or even when the packaged product consists of a food. The PHA exhibits interesting performance in terms of barrier properties. However, a material made from PHA is likely, during aging, to suffer a decrease in its mechanical characteristics, and in particular a loss of flexibility. Thus, patent document CN 101 469 11 20 discloses a biodegradable material comprising, in addition to PHA, vegetable fibers of wool type, bast fibers or wood flour, intended to improve the physical properties of the material. However, the barrier properties of this type of material remain insufficient, and the material is here rather intended for the manufacture of rigid objects and is not suitable for the manufacture of flexible tubes. The mechanical performance and the barrier properties of the products obtained from bioplastic / agro-plastic materials are still affected by the extrusion process used for the manufacture of many packages, because of the thermal sensitivity of PLA and PHA. . This low resistance to the usual extrusion process is problematic because it is used for the manufacture of many packaging products, including flexible tubes intended to contain in particular cosmetic products.
    [0005] As a result, the substitution of petrochemical derivatives by biosourced or agro-sourced products remains limited to certain applications, for example in the field of packaging. This substitution also remains partial within the polymer compositions, or even non-existent especially for certain applications where the characteristics in terms of mechanical flexibility and barrier properties are crucial, as is particularly the case for the cosmetic tubes.
    [0006] The invention offers the possibility of overcoming the various drawbacks of the state of the art by proposing a composition based on PLA and / or PHA, making it possible to obtain a material of agro-sourced origin and completely biodegradable, all by presenting improved characteristics in terms of mechanical properties and barrier, compared to materials currently existing in the state of the art. One of the aims of the present invention is to enable the manufacture of flexible packaging, for example flexible tubes, in particular intended for the cosmetic industries for the packaging of their products, these packages having a limited permeability during their storage and storage. their usage. For this purpose, the present invention relates to a composition comprising biodegradable polymers and of renewable origin, characterized in that it comprises poly lactic acid (PLA) and / or a polymer of the family of polyhydroxyalkanoates (PHA), said composition comprising in addition polybutylene succinate (PBS), and at least one type of organically modified lamellar nanofillers.
    [0007] Advantageously, such a composition may further comprise at least one antioxidant. Preferably, the polymer of the PHA family may be chosen from polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH) and poly (3-hydroxybutyrate-co 4-hydroxybutyrate) (P3HB4HB).
    [0008] Advantageously, the composition may comprise between 19 and 73% by weight of P3HB4HB, preferably between 40 and 50%, relative to the total mass of the composition, PBS, an antioxidant, and organically modified lamellar nanofillers. More precisely, said composition may comprise, in addition to P3HB4HB: between 18 and 78% by weight of PBS, relative to the total mass of the composition; between 0.3 and 2.0% by weight of an antioxidant, relative to the total mass of the composition; between 2.7 and 7.0% by weight of organically modified lamellar nanofillers, relative to the total mass of the composition.
    [0009] Most preferably, P3HB4HB and PBS may be present in said composition in equivalent proportions. In a different embodiment, the composition according to the invention may comprise between 18 and 65% by weight of PLA, preferably between 40 and 50%, relative to the total mass of composition, PBS, an antioxidant, nanofillers organically modified lamellar and a plasticizer. In this case, preferentially, said composition may comprise, in addition to PLA: between 16 and 74% by weight of PBS, relative to the total mass of the composition; between 0.3 and 2.0% by weight of an antioxidant, relative to the total mass of the composition; between 2.7 and 7.0% by weight of organically modified lamellar nanofillers, relative to the total mass of the composition; between 5.0 and 10% by weight of plasticizer relative to the total mass of the composition. Advantageously, PLA and PBS may be present in said composition in equivalent proportions.
    [0010] In an interesting embodiment, the plasticizer consists of triethyl citrate. Preferably, the lamellar nanofillers are organically modified with a quaternary ammonium.
    [0011] As regards the organically modified lamellar nanofillers, these may advantageously consist of montmorillonite. The composition according to the present invention can be used in particular for the manufacture of a biodegradable flexible packaging. The invention also relates to a process for the production of granules formulated from the composition according to the invention, which comprises lactic acid polyacid (PLA) and / or a polymer of the family of polyhydroxy-alkanoates (PHA), said composition further comprising polybutylenesuccinate (PBS), and at least one type of organically modified lamellar nanofillers, the process comprising the following steps: PLA polymer and / or PHA and PBS polymer granules are dried at a temperature between 50 and 70 ° C for 11 to 13h, the lamellar nanofillers are dried at a temperature between 70 and 90 ° C for 11 to 13h, the components are introduced into a twin-screw extruder 25 to obtain the formulated granules. The present process may also advantageously comprise the following steps: The formulated granules are placed in a single screw extruder equipped with a flexible packaging product calibration device; at the end of the second extrusion, the biodegradable flexible packaging products constituted by said composition of the invention are recovered at the outlet of the die.
    [0012] Other characteristics and advantages of the invention will emerge from the following detailed description of non-limiting embodiments of the invention. The composition according to the present invention comprises, among others, at least one polymer which is on the one hand renewable, in particular agro-sourced origin, and, on the other hand, which has the advantage of being biodegradable. Preferably, said composition comprises lactic acid polyacid (PLA) and / or a polymer of the family of polyhydroxyalkanoate (PHA), this family of PHA comprising a plurality of polymers. In other words, the composition comprises either PHA or PLA, or a mixture of these two components. Preferably, however, the composition is based on either PHA or PLA in combination with other components. In one embodiment, a composition is chosen which is based on PHA because it has good performance in terms of barrier properties, while retaining satisfactory mechanical properties. Preferably, the composition according to the invention comprises PHA chosen from polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH) and poly (3-hydroxybutyrate). co-4-hydroxybutyrate) (P3HB4HB). More particularly, as regards the PHA, use will preferably be made of a particular copolymer, that is to say a polymer resulting from the polymerization of at least two types of chemically different monomers; this copolymer consists of poly (3-hydroxybutyrate-co-4-hydroxybutyrate), which will be designated in the following description by P3HB4HB. This P3HB4HB copolymer is particularly advantageous because it allows an improvement in the ductility of the material obtained from the composition according to the invention, especially with respect to another polymer of the PHA family, P3HB. In other words, P3HB4HB allows an increase in the ability of the material to deform plastically without breaking.
    [0013] The composition also comprises, in addition to P3HB4HB, a second biodegradable and, preferably, agro-sourced polymer, polybutylene succinate, designated by PBS in the following description.
    [0014] PBS consists of a semi-crystalline polymer that has thermomechanical properties similar to those of polyethylene (PE). This last component, the PE, has indeed interesting mechanical properties but it comes from petroleum resources, and it is necessary to find an alternative to such a component. The crystallization of PBS is particularly rapid, especially in comparison with the crystallization rates of P3HB4HB and PLA. Consequently, the presence of PBS makes it possible to promote the crystallization of these polymers, by acting as a nucleant. Thus, the addition of PBS to a composition comprising either P3HB4HB or PLA, or possibly both, makes it possible to obtain materials which have a certain degree of crystallinity and properties close to those of PE. The degree of crystallinity obtained by adding PBS is particularly interesting, since all the properties of a polymer-based material depend on this degree of crystallinity. In particular, a material comprising crystalline or semi-crystalline polymers has satisfactory barrier properties. The composition also comprises, in addition to P3HB4HB and PBS, at least one type of organically modified lamellar nanofillers. Preferably, said composition further comprises at least one antioxidant. In an advantageous embodiment, the composition according to the invention comprises a proportion of P3HB4HB copolymer of between 19 and 73% by weight relative to the total mass of said composition. Even more advantageously, this proportion of P3HB4HB copolymer is between 40 and 50% relative to the total mass of the composition. Even more preferably, the proportion of P3HB4HB is of the order of 46% relative to the total mass of the composition. More particularly, in addition to P3HB4HB as defined above, the composition according to the invention also comprises: between 18 and 78% by weight of PBS; between 0.3 and 2.0% antioxidant; between 2.7 and 7.0% by weight of organically modified lamellar nanofillers. All the above proportions, as well as in the following 15 description are expressed as a percentage by mass of the component in question, relative to the total mass of the composition according to the invention. According to a particular embodiment, the proportions of P3HB4HB and PBS in the composition according to the invention are equivalent. In other words, the ratio of P3HB4HB to PBS is 1: 1. Thus, advantageously, the formulation of the composition based on P3HB4HB is as follows: 7% of organically modified lamellar nanofillers; 0.3% of antioxidant the rest of the composition comprises P3HB4HB and PBS in a proportion 1: 1, ie of the order of 46% by weight of P3HB4HB and of the order of 46% by weight of PBS . Such an embodiment, however, should not be considered as being limiting. Indeed, we have seen above that said lamellar nanofillers were present in the composition in a proportion of between 2.7 and 7.0% and that the antioxidant was preferably in a proportion of 0.3 to 2%. , 0%. The remainder of the composition then advantageously comprises P3HB4HB and PBS in a proportion of 1: 1, irrespective of the proportion of organically modified lamellar nanocharges and optionally of antioxidant, in the ranges proposed above. The composition according to the invention may also comprise, in a particular embodiment, PLA instead of P3HB4HB. In this embodiment, said composition comprises a proportion of between 18 and 65% by weight of PLA, relative to the total mass of the composition. Most advantageously, this proportion ranges from 40 to 50% by weight, and still more preferably, the proportion of PLA is of the order of 43%. The composition also comprises PBS, an antioxidant, and organically modified lamellar nanofillers. Most preferably, a composition according to the invention based on PLA also comprises, in addition to the constituents mentioned above, a plasticizer. The presence of such a plasticizer promotes an improvement in the flexibility of a plastic material obtained from the composition according to the invention comprising PLA. The plasticizer 20 included in said composition may preferably be of natural origin, which makes it possible to advantageously preserve an agro-sourced origin for the composition according to the invention. Said plasticizer of natural origin consists, in a particular but non-limiting embodiment, of triethyl citrate. The plasticizer may also consist of vegetable oils (flax, soybean, etc.), as well as substances of agro-resource origin, such as glycerol, sorbitol, etc. It has been mentioned that the presence of such a plasticizer within the composition allows an increase in the flexibility of the material. However, it has been demonstrated by the Applicant that the plasticizer could, on the other hand, be capable of causing an increase in permeability. It is therefore appropriate to accurately dose the proportion plasticizer to avoid such a pitfall. Thus, interestingly, the plasticizer is present in the composition in a proportion of between 5.0 and 10% by weight relative to the total weight of said composition. Preferably, this proportion is of the order of 7% by weight. It has further been demonstrated that it may be advantageous to add polybutylene succinate (PBS) to a composition comprising in particular PLA in order to make the final material more ductile and less brittle. The presence of PBS also makes it possible to maintain the mechanical performance, in particular the improved flexibility, provided by the plasticizer. Most preferably, PBS is biodegradable and is also advantageously agro-sourced. It is also advantageously the same when the PBS is included in the composition comprising P3HB4HB. According to one particular embodiment, the composition according to the invention, based on PLA, comprises a proportion of PBS comprised between 16 and 74% by weight of PBS relative to the total mass of said composition. According to a particular embodiment, the proportions of PLA and PBS in the composition according to the invention are identical. In other words, the ratio between PLA and PBS is preferably 1: 1. With regard now to the antioxidant proportion of the PLA composition, it is preferably from 0.3 to 2.0% by weight of antioxidant, based on the total weight of the composition. As regards the organically modified lamellar nanofillers, these are incorporated in the composition in a mass proportion of between 2.7 and 7.0% relative to the total mass of the composition. Thus, advantageously, the formulation of the PLA-based composition is as follows: 7% of organically modified lamellar nanofillers; - 7 plasticizer, preferably triethylcitrate; - 0.3% of antioxidant - the rest of the composition comprises PLA and PBS in a ratio 1: 1, ie of the order of 43% by weight of PLA and of the order of 43% by weight of PBS.
    [0015] Such an embodiment should however not be considered as being limiting. Indeed, we have seen above that the organically modified lamellar nanofillers were present in the composition in a proportion of between 2.7 and 7.0% and that the antioxidant was preferably in a proportion of 0.3 at 2.0%. As for the plasticizer, the proportion ranges from 5.0 to 10%. The remainder of the composition then advantageously comprises PLA and PBS in a proportion of 1: 1, irrespective of the proportion of lamellar nanocharges, of plasticizer and optionally of antioxidant, in the ranges proposed above. Returning now to organically modified lamellar nanofillers, their presence in a composition according to the invention, whether it is based on PLA polymer or based on P3HB4HB polymer, is particularly interesting.
    [0016] In fact, these organically modified lamellar nanofillers promote the reduction of the permeability, in particular of water vapor and oxygen, of a package obtained from the composition according to the invention. Obtaining organically modified lamellar nanofillers is done by contacting said nanofillers with a quaternary ammonium and then heating. This results in a cation exchange of lamellar nanofillers, said cations being inorganic, and which are replaced by quaternary ammoniums, having one or more organic group (s). Thus, the organic modifier present in the nanofillers advantageously improves their compatibility with the polymer, hence their dispersion in the polymer matrix. Preferably, the quaternary ammonium used to modify the lamellar nanofillers organically consists of methyl-n-alkylbis-2-hydroxyethylammonium chloride, in which n-alkyl contains on the order of 65% of C18, of the order of 30%. of C16 and of the order of 5% of C14. More specifically, said lamellar nanofillers are in the form of sheets, the latter having a nanometric thickness and dimensions in length and width of several microns. The addition of organically modified lamellar nanofillers in the composition according to the invention for the manufacture of a flexible package advantageously makes it possible to limit the mass transfer between the container and the contents, and the gas exchanges with the environment. ; in fact, a package made from a composition according to the invention comprising organically modified lamellar nanofillers has improved impermeability compared to a package which does not contain any. In particular, the composition based on P3HB4HB according to the invention makes it possible to obtain a package whose water vapor impermeability is improved by up to 42%, relative to a composition containing no fillers. The impermeability to oxygen is, in turn, improved by 32%. With regard to the PLA-based composition according to the invention, the imperviousness to water vapor and oxygen were respectively improved by 50% and 40%, with respect to a composition not comprising nanofillers. As a remark, these results were obtained from values measured on films and tubes made from a composition according to the invention. It has already been indicated above that the composition according to the invention preferably comprises a proportion of organically modified lamellar nanofillers of between 2.7 and 7.0%. It has indeed been demonstrated by the applicant that an addition of such lamellar nanofillers should be limited to avoid an increase in the hardness of the material obtained from the composition according to the invention. Advantageously, the organically modified lamellar nanofillers added in the composition consist of lamellar silicates, for example montmorillonite.
    [0017] Montmorillonite more particularly consists of a mineral, composed of aluminum silicate and hydrous magnesium of formula (Na, Ca) 0.3 (Al, Mg) 2 SiO (OH) 2; n1-120. The organically modified lamellar nanofillers may also consist of bentonite, saponite or hectorite. As regards the presence of antioxidant in the composition according to the invention, it advantageously makes it possible to limit the aging of the material obtained from said composition, in particular its oxidation. In addition, the presence of an antioxidant makes it possible to preserve both the mechanical properties, in terms of flexibility, conferred in particular by the presence of plasticizer if appropriate, and the barrier properties which are related to the oxidation. Advantageously, the composition according to the invention comprises polyphenols and / or organophosphites as antioxidants. Preferably, the antioxidant consists of 2,6-ditertbutyl-4-methylphenol or tri (2,4-di-tertbutyl phenyl) phosphite. The present composition may advantageously be used for the manufacture of a flexible or rigid biodegradable packaging, intended in particular to contain a cosmetic product, a hygiene product, a pharmaceutical product or a dermatological product. In particular, the package obtained from the composition according to the invention may be intended to contain toothpaste, cream, etc. However, such an application is not limiting and the composition according to the invention may also allow the manufacture of flexible or rigid biodegradable packaging for containing food or maintenance products. The present invention also consists of a process for producing granules from said composition according to the invention. These granules, called granules formulated in the following description, can then be used for the manufacture of all types of flexible biodegradable packaging. The packages produced may also be rigid packages, such as flasks or rigid boxes. According to the method of the invention, the compounds at the base of said composition are dried, before mixing said compounds.
    [0018] In a different embodiment, these compounds are initially mixed to form the composition, which is then dried. Preferably, the drying is carried out for a period of between 11 and 13 hours, advantageously for 12 hours, and at a temperature of between 50 and 90 ° C. In particular, polymer granules P3HB4HB and / or PLA, and PBS are advantageously dried overnight, about 12 hours, at a temperature of between 50 and 70 ° C, preferably at 60 ° C. As regards the organically modified lamellar nanofillers, preferably montmorillonite, it undergoes a drying step also overnight, that is to say about 12 hours, at a temperature between 70 and 90 ° C. preferably at 80 ° C. The drying of the compounds or of the composition makes it possible to eliminate the residual moisture which could degrade said composition which it is desired to obtain, in particular the polymers, during processing and shaping. Thus, the drying makes it possible to limit the thermo-hydrolysed degradation of the products during the subsequent steps of the process. After drying of the compounds or of said composition, said composition is introduced into an extruder, preferably a twin-screw extruder, which allows mixing and then obtaining the formulated granules.
    [0019] The extruder is a machine for carrying out the extrusion, that is to say a process for shaping materials, in particular plastics. The extrusion consists, more precisely, in a thermomechanical manufacture by which a sheared and compressed material is forced through a die, the latter having the section of the part to obtain. During extrusion, the feed is preferably provided by a hopper. Advantageously, according to the process of the invention, the flow rate of the hopper is adjusted in order to obtain between 5 and 7 kg / hour of said composition, preferably 6 kg / hour. In addition, according to the method of the invention, a rotation speed of the screws, necessary for the mixing process, will preferably be used between 150 and 300 rpm (revolutions per minute), preferably 200 rpm for a composition with P3HB4HB base and 250 rpm for a PLA-based composition, in order to obtain a mixing process suitable for producing the formulated granules. According to the process of the invention, advantageously, the set temperatures in the extruder for mixing and producing the composition are set between 35 and 45 ° C at the inlet and at the end between 120 and 45 ° C. and 130 ° C for P3HB4HB and 140-160 ° C for PLA. After carrying out the steps of the process of the invention mentioned above, said composition produced in the first extruder will be in the form of rod at the die exit. Said composition, in the form of rod, that is to say in the form of single-strand, is then cooled, preferably with cold water. According to the next step of the process according to the invention, said rod-shaped composition, previously cooled, is converted into granules by means of a granulator. This transformation is preferably done continuously. According to one particular embodiment, use will be made of a monobloc-type 2 and 4-section granulator.
    [0020] The formulated granules obtained from said composition are then preferably dried, this drying making it possible to eliminate the residual moisture which is capable of degrading said granule composition. The formulated granules thus obtained from the composition according to the invention can then advantageously be used for the manufacture of a biodegradable flexible packaging product. In this respect, the process according to the invention also comprises a second extrusion step, preferably using a single-screw extruder equipped with a tubular die and a calibration device specific to the packaging product. flexible that one wishes to obtain. According to the method of the invention, the target temperatures within the second extruder can be between 125 ° C. and 135 ° C. at the inlet, preferably 130 ° C., and between 135 ° C. and 145 ° C. at the outlet. die, preferably 140 ° C. This second extrusion will define the final shape of the flexible packaging product obtained by performing the method of the invention. According to a particular embodiment, the tubes obtained may have dimensions close to those used in the field of cosmetics or any other field using tubes, for example food packaging or cleaning products. Advantageously, the tubes that will be obtained may have a length between 10 and 20 cm, preferably 15 cm, an outside diameter of between 30 and 45 mm, preferably 35 mm and a thickness of between 300 and 500 nm, preferably 400 nm. At the end of the complete implementation of the process of the invention, at least one advantageously flexible, biodegradable packaging product obtained from said composition of the invention is recovered. It has also been demonstrated, by tests conducted on tubes obtained from the composition according to the invention, that certain mechanical properties are similar to those of a tube obtained from PE. More particularly, the flexibility, the elongation at break and the tensile strength of a tube obtained according to the invention are equivalent to the results obtained for a PE-based polymer tube. The stiffness / hardness of the material and the tensile strength are respectively defined by the Young's modulus and the tensile stress. In addition, it has been demonstrated by the applicant that the tubes made from the composition according to the invention exhibit a substantial decrease in oxygen permeability with respect to a PE film. On the other hand, it remains higher than that of a commercial PE / EVOH tube (ethylene vinyl alcohol copolymer). Thus, the composition according to the invention prevents an entry of oxygen into the tubes obtained, so that the content inside is less subject to oxidation and is preserved longer. On the other hand, the composition according to the invention also makes it possible to reduce an outlet of the water, contained in the product, outside the tube. The results of the tests which have been carried out are repeated in Example 1 below. EXAMPLE 1 Mechanical Properties, Thermal Properties and Barrier Properties of a Material Obtained by the Composition According to the Invention The Mechanical Properties, the Thermal Properties and the Barrier Properties of a Material Obtained from the Composition According to the Invention the invention have been tested and the results have been compared in particular with different compositions based on PE or not containing some of the constituents of the composition according to the invention. The results are found below: Formulation P3HB4HB / PBS PLA / PBS Composition PLA: 18 - 65% PBS: 16 - 74% Antioxidant: 0.3 - 2% Organically modified lamellar nanofillers: 2.7 - 7 Plasticizer: 5 - 10% P3HB4HB: 19 - 73% PBS: 18 - 78% Antioxidant: 0.3 - 2% Organically modified lamellar nanofillers: 2.7 - 7% Extrusion conditions (twin-screw extruder) Temperature: 60-160 ° C Screw speed: 250 rpm Flow rate: 6 Kg / h Temperature: 40-125 ° C Screw speed: 200 rpm Flow rate: 6 Kg / h Mechanical properties - PLA: poor crystalline, even amorphous, fragile behavior - PBS : semi-crystalline, ductile behavior -P3HB4HB: semi-crystalline, ductile behavior -PBS: semi-crystalline, ductile behavior -PLA / PBS mixture: intermediate behavior according to the mass ratio used. Indeed, the modulus of elasticity varies between 570 and 1480 MPa and the elongation at break varies between 180 and 300%, for PLA / PBS mixtures without lamellar nanofillers. With lamellar nanofillers, the composition with a PLA / PBS ratio of 1: 1 remains. The modulus increases to 1454 MPa (41% increase over the uncharged composition) and the elongation at break decreases to 33% (a drop of 85% compared to the uncharged composition) -Mixture P3HB4HB / PBS: ductile behavior. According to the mass ratio used, the modulus of elasticity varies between 320 and 390 MPa and the elongation at break varies between 370 and 490%, for P3HB4HB / PBS mixtures without lamellar nanofillers. With the lamellar nanofillers, it remains on the composition having a P3HB4HB / PBS ratio of 1: 1. The modulus increases to 512 MPa (58% increase over the uncharged composition) and the elongation at break decreases to 17% (a 95% drop from the unfilled composition) For mixtures containing a quantity of PLA equal to and greater than 50%, the addition of plasticizer serves to make the final material more flexible, for example with 7% triethyl citrate in a PLA / PBS mixture with a ratio 1: 1, modulus of elasticity, stress and elongation at break increased from 1379 to 1058 MPa, from 39.9 to 32.5 MPa and from 46 to 271%, respectively. Note: here the PLA / PBS mixture is compared with a 1: 1 ratio + 7% lamellar nanocharges + 0.3 antioxidant, WITHOUT plasticizer. Thermal Properties - Glass transition temperature: 61 ° C for PLA and 31 ° C for PBS. These are fairly low temperatures that are of interest for shaping (softening temperature) - glass transition temperature: 2.5 and 57 ° C (in DMA) for P3HB4HB and -31 ° C for PBS. These are fairly low temperatures that are of interest for shaping (softening temperature) - Melting temperature: 158 ° C for PLA and 116 ° C for PBS. These are rather low temperatures, not too far from that of PE (120-130 ° C) which are of interest for the implementation (extrusion and injection) - Melting temperature: 130152 ° C for P3HB4HB and 116 ° C for the PBS. These are rather low temperatures, not too far from that of the PE (120 - 130 ° C) which are of interest for the implementation (extrusion and injection) Barrier properties Oxygen permeability 15 times lower than that of LDPE. Permeability to water vapor 12 times higher than that of LDPE. Oxygen permeability 21 times lower than LDPE Water vapor permeability 7 times greater than LDPE The addition of lamellar nanofillers reduces the permeability to water vapor and oxygen of the water. PLA / PBS matrix. Up to 50% improvement for water vapor permeability and 40% for oxygen permeability (values measured on films). The addition of lamellar nanofillers reduces the permeability to water vapor and oxygen of the P3HB4HB / PBS matrix. Up to 42% improvement for water vapor permeability and 32% for oxygen permeability (values measured on films). Mass loss test (tube containing an aqueous formulation similar to a very fluid cream) at 45 ° C for 2 months Mass losses at 55 days of test: PE: less than 1% PLA / PBS: 24 to 27% PLA / PBS with lamellar nanofillers: 13 to 15% Mass losses at 55 days PE test: less than 1% PHA / PBS: 24 to 30% PHA / PBS with lamellar nanofillers: 17 to 18% -22- The terms " Lamellar nanofillers in the above table relates to lamellar nanofillers that are organically modified, as discussed in the description.
    [0021] In conclusion of the results of these tests, it appears that the composition according to the invention, based on PLA or P3HB4HB, with PBS, allows an improvement of certain mechanical properties of a material obtained with this composition. In particular, the modulus of elasticity is increased.
    [0022] In a composition according to the invention comprising PLA, it has been shown that the addition of plasticizer makes it possible to improve the flexibility of the final material. The permeability to water vapor and oxygen of a material obtained from the composition according to the invention was compared, on the one hand with the permeability of a material obtained from LDPE (low polyethylene density) and also with the same composition with no fillers. In the first place, it results from this comparison that the oxygen permeability of a material obtained from the composition according to the invention is more advantageous than that of a PE monolayer material. Indeed, a material obtained with the present composition based on PLA is 15 times less permeable to oxygen than a PE material. When the composition is based on P3HB4HB, the final product is 21 times less permeable to oxygen. As a result, the content of a tube obtained by the implementation of the composition according to the invention, for example a cosmetic product, will be very little subject to oxidation phenomena. As a result, the preservation of such a cosmetic product, for example, will be significantly improved at room temperature. In a second step, it was also demonstrated that the presence of organically modified lamellar nanofillers in a composition having either a PLA / PBS mixture or a P3HB4HB / PBS mixture resulted in a significant improvement in the impermeability of the product. final, with respect to another product obtained from a polymer blend without nanofillers. In other words, the products obtained from the composition according to the invention will be less permeable, or more impermeable, to water vapor and oxygen. The improvement of the barrier properties also results in a decrease in the mass loss of a tube containing an aqueous formulation, comparable to a fluid cosmetic product. More particularly, the loss of mass of the content is improved, that is to say it is less, with a tube obtained from the composition according to the invention, in comparison with a tube comprising only a mixture of PLA / PBS, ie P3HB4HB / PBS, without lamellar nanofillers.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. Composition comprising biodegradable polymers of renewable origin, characterized in that it comprises poly lactic acid (PLA) and / or a polymer of the polyhydroxyalkanoate (PHA) family, said composition further comprising polybutylene succinate (PBS) ), and at least one type of organically modified lamellar nanofillers.
    [0002]
    2. Composition according to the preceding claim characterized in that it further comprises at least one antioxidant.
    [0003]
    3. Composition according to one of the preceding claims characterized in that the PHA is chosen from polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB).
    [0004]
    4. Composition according to one of the preceding claims characterized in that it comprises between 19 and 73% by weight of P3HB4HB, preferably between 40 and 50%, relative to the total weight of the composition, PBS, an antioxidant , and organically modified lamellar nanofillers.
    [0005]
    5. Composition according to the preceding claim characterized in that it comprises, in addition to P3HB4HB: between 18 and 78% by weight of PBS, relative to the total mass of the composition; between 0.3 and 2.0% by weight of an antioxidant, relative to the total mass of the composition; between 2.7 and 7.0% by weight of organically modified lamellar nanofillers, relative to the total mass of the composition.
    [0006]
    6. Composition according to one of the preceding claims characterized in that P3HB4HB and PBS are present in said composition in equivalent proportions. 5
    [0007]
    7. Composition according to Claim 1 or Claim 2, characterized in that it comprises between 18 and 65% by mass of PLA, preferably between 40 and 50%, relative to the total mass of composition, of PBS, an antioxidant. , Organically modified lamellar nanofillers and a plasticizer.
    [0008]
    8. Composition according to the preceding claim, characterized in that it comprises, in addition to PLA: between 16 and 74% by weight of PBS, relative to the total mass of the composition; between 0.3 and 2.0% by weight of an antioxidant, relative to the total mass of the composition; between 2.7 and 7.0% by weight of organically modified lamellar nanofillers, relative to the total mass of the composition; between 5.0 and 10% by weight of plasticizer relative to the total mass of the composition. 25
    [0009]
    9. Composition according to one of claims 7 or 8 characterized in that PLA and PBS are present in said composition in equivalent proportions.
    [0010]
    10. Composition according to any one of claims 7 to 9, characterized in that the plasticizer consists of triethyl citrate.
    [0011]
    11. Composition according to any one of the preceding claims, characterized in that the lamellar nanofillers are organically modified with a quaternary ammonium.
    [0012]
    12.Composition according to any one of the preceding claims, characterized in that the organically modified lamellar nanofillers consist of montmorillonite.
    [0013]
    13.Composition according to any one of the preceding claims for the manufacture of a biodegradable flexible packaging.
    [0014]
    14.Procédé for the manufacture of granules formulated from the composition according to any one of the preceding claims, the latter comprising lactic acid polyacid (PLA) and / or a polymer of the family of polyhydroxy-alkanoates (PHA), said composition further comprising polybutylene succinate (PBS), and at least one type of organically modified lamellar nanofillers, the process comprising the following steps: - the PLA and / or PHA and PBS polymer granules are dried at a temperature of between 50 and 70 ° C for 11 to 13 hours, - said lamellar nanofillers are dried at a temperature between 70 and 90 ° C for 11 to 13 hours, - the components are introduced into a twin-screw extruder to obtain the formulated granules.
    [0015]
    15.Procédé for the manufacture of a biodegradable flexible packaging from formulated granules obtained according to the preceding claim, said method comprising the following additional steps: - the formulated granules are placed in a second single-screw extruder provided with a calibration device of flexible packaging product; - At the end of the second extrusion, at the outlet of the die, the biodegradable flexible packaging products constituted by said composition are recovered.
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    同族专利:
    公开号 | 公开日
    WO2015092257A1|2015-06-25|
    FR3014885B1|2017-04-14|
    引用文献:
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    EP0980894A1|1998-03-05|2000-02-23|Mitsui Chemicals, Inc.|Polylactic acid composition and film thereof|
    US20100076099A1|2006-08-11|2010-03-25|Board Of Trustees Of Michigan State University|Biodegradable polymeric nanocomposite compositions particularly for packaging|
    WO2011158240A2|2010-06-17|2011-12-22|Tipa Corp. Ltd|Biodegradable sheet and an array of separable pouches for liquids|FR3040389A1|2015-08-27|2017-03-03|Icci Sea|FOOD-CONTACTABLE BIODEGRADABLE PLASTIC COMPOSITION, DERIVANT ARTICLES, METHODS AND USES THEREOF|
    FR3055336A1|2016-08-29|2018-03-02|Icci Sea|RECYCLABLE, BIODEGRADABLE AND / OR COMPOSTABLE PLASTIC COMPOSITION WITH FOOD CONTACT, RIGID ARTICLES THEREOF, PROCESSES AND USES THEREOF|
    FR3060014A1|2016-12-13|2018-06-15|Institut National Des Sciences Appliquees De Lyon|BIODEGRADABLE POLYMERIC MATERIAL AND BIOSOURCE|
    CN112110036A|2019-06-21|2020-12-22|Gdk化妆品有限公司|Facial mask set packaged by biodegradable packaging material|WO2003022927A1|2001-09-06|2003-03-20|Unitika Ltd.|Biodegradable resin composition for molding and molded object obtained by molding the same|
    KR100843593B1|2005-08-30|2008-07-03|주식회사 엘지화학|Biodegradable polyester compositon having barrier property|
    WO2011043676A1|2009-10-07|2011-04-14|Auckland Uniservices Limited|Reactive polymeric mixture|CN111825964A|2019-08-09|2020-10-27|苏州市工达高分子材料有限公司|Degradable PBST/P34HB blend and preparation method thereof|
    法律状态:
    2016-05-30| PLFP| Fee payment|Year of fee payment: 3 |
    2017-06-20| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-18| PLFP| Fee payment|Year of fee payment: 5 |
    2019-12-24| PLFP| Fee payment|Year of fee payment: 7 |
    2020-12-21| PLFP| Fee payment|Year of fee payment: 8 |
    2021-12-28| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362793A|FR3014885B1|2013-12-17|2013-12-17|COMPOSITION BASED ON AGRO-SOURCE AND BIODEGRADABLE POLYMERS|FR1362793A| FR3014885B1|2013-12-17|2013-12-17|COMPOSITION BASED ON AGRO-SOURCE AND BIODEGRADABLE POLYMERS|
    PCT/FR2014/053357| WO2015092257A1|2013-12-17|2014-12-16|Composition based on agro-based biodegradable polymers|
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