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    • 专利摘要:
    The present invention relates to a thermoplastic, biodegradable material based on casein and / or caseinate. In particular, the present invention relates to a thermoplastic, biodegradable material, comprising a) between 50 and 80% of casein and / or caseinate, preferably between 55 and 70%; b) between 4 and 12% of water, preferably between 5 and 11%; c) between 10 and 35% of at least one plasticizer other than b), preferably between 15 and 28%; d) between 0.1 and 8% of a hydrophobic agent, preferably between 1 and 4%; e) between 0.5 and 6% of at least one surfactant, preferably between 2 and 4%
    公开号:FR3075215A1
    申请号:FR1762549
    申请日:2017-12-19
    公开日:2019-06-21
    发明作者:Basak Yilin Colak；Marie-Helene Gramatikoff；Maxime Dememe；Kheirdine Mellouki；Frederic Prochazka
    申请人:Lactips；
    IPC主号:
    专利说明:

    BIODEGRADABLE THERMOPLASTIC MATERIAL BASED ON
    CASEIN AND / OR CASEINATE
    Technical area
    The field of the invention is that of thermoplastic, biodegradable and biobased materials, more precisely that of casein and / or caseinate thermoplastics.
    In particular, the present invention relates to a thermoplastic, biodegradable material, comprising
    a) between 50 and 80% of casein and / or caseinate, preferably between 55 and 70%;
    b) between 4 and 12% of water, preferably between 5 and 11%;
    c) between 10 and 35% of at least one plasticizer other than b), preferably between 15 and 28%;
    d) between 0.1 and 8% of a hydrophobic agent, preferably between 1 and 4%;
    e) between 0.5 and 6% of at least one surfactant, preferably between 2 and 4%.
    The subject of the invention is also the thermoplastic material, biodegradable in various different forms, in particular in the form of granules constituting a raw material for its transformation into various objects, such as films, wires or molded articles ...
    The invention also relates to a packaging film obtained from this thermoplastic material, and, more specifically, a packaging for hygroscopic products, such as detergent tablets, made from this film.
    Technological background
    The decrease in non-renewable resources, such as petroleum, and the increase in pollution linked to these resources are leading to the development of less polluting and more environmentally friendly alternative solutions.
    In the field of plastics, new biodegradable materials are being developed. These new materials can be made from naturally occurring polymers or synthetic polymers. For example, vegetable proteins, such as corn and soy proteins, or animal proteins can be used to make packaging.
    Among animal proteins, casein is particularly interesting. Indeed, this protein from milk is accessible in large quantities and casein-based films have good transparency and good biodegradability.
    The document FR2963013 describes biodegradable thermoplastic granules based on casein and / or caseinate and their manufacturing process. These granules can be used to make thermoplastic films. However, these thermoplastic films are not easily exploitable industrially. For example, the film is sometimes sticky, it is therefore difficult, if not impossible, to unwind the film reels using industrial equipment because the different layers stick together. Furthermore, when these films are used to package detergent tablets and these tablets are stored in conditions of low relative humidity (for example 30%), they can sometimes become brittle and tear, to the point of no longer playing then their role in packaging.
    Goals
    In this context, the present invention aims to satisfy at least one of the following objectives.
    One of the essential objectives of the invention is the supply of a thermoplastic, biodegradable material, based on casein and / or caseinate which can be used industrially, that is to say in particular convertible into semi-finished product or finished product. , simple or complex form, by techniques such as injection, extrusion, extrusion-inflation, solvent (in English "solvent cast"), thermoforming or machining.
    Another essential objective of the invention is the supply of a film of thermoplastic, biodegradable material, based on casein and / or caseinate which can be reeled and which can be unwound.
    Another essential objective of the invention is the supply of a film of thermoplastic, biodegradable material, based on casein and / or caseinate, which can be used, in particular, for packaging hygroscopic products, such as detergent tablets.
    Brief description of the invention
    The invention relates first of all to a biodegradable thermoplastic material characterized in that it comprises
    a) between 50 and 80% of casein and / or caseinate, preferably between 52 and 75%, and, more preferably still, between 55 and 70%;
    b) between 4 and 13% of water, preferably between 4.5 and 12%, and, more preferably still, between 5 and 11%;
    c) between 10 and 35% of at least one plasticizer other than b), preferably between 12 and 32%, and, more preferably still, between 15 and 28%;
    d) between 0.1 and 8% of a hydrophobic agent, preferably between 0.5 and 6%, and, more preferably still, between 1 and 4%;
    e) between 0.5 and 6% of at least one surfactant, preferably between 1 and 5%, and, more preferably still, between 1.5 and 4.5%.
    The biodegradable thermoplastic material as described above can be used industrially. Indeed, this material makes it possible to obtain a film which can be reeled and then easily unwound.
    This suitability for winding / unwinding at an industrial rate is a key parameter of the film produced from the casein thermoplastic material and according to the invention.
    Furthermore, this film can be used to package various products such as hygroscopic products, such as detergent tablets, because even when the tablets are stored in conditions of low relative humidity, the film retains its integrity.
    In addition, in some cases, the film produced is edible. It can therefore be used for different applications such as the packaging of products, ingredients or food additives, edible packaging, single doses of food ingredients to be dissolved, single doses of food additives. It can also be used as a separation sheet.
    Brief description of the figures
    Figures IA and IB are photos of a roll of film that cannot be unwound according to Comparative Example 1.
    Figures 2A, 2B and 2C are photos of a reel of roll-up film according to Example 4.
    Figures 3A and 3B are photos of detergent tablets wrapped in film according to Comparative Example 1 after a 5-day conditioning test.
    Figure 4 is a photo of a detergent tablet wrapped in film according to Example 4 after a 5-day conditioning test.
    Photos 5A and 5B are photos of detergent tablets wrapped in a film printed according to Example 5 after a 5-day conditioning test.
    Figure 6 is a photo of the unwinding test facility used for the evaluation of films made from casein thermoplastic materials in the examples.
    Definitions
    By "thermoplastic" is meant, for example, a material which becomes malleable and pliable above a given temperature, the glass transition temperature Tg, but which below this Tg becomes hard again, these transformations being reversible.
    By "biodegradable" is meant, for example, a material which can be decomposed under the action of microorganisms (bacteria, fungi, algae ...). The result of this decomposition is the formation of water, CO2 and / or methane and possibly by-products (residues, new biomass) that are not toxic to the environment. It is, for example, a biodegradable material according to European standard EN NF 13432.
    By "between x and y", we mean, for example, that the limits x and y are included in the interval [x, j].
    By "water soluble" is meant, for example, that dissolves in water. The water solubility of a film can be measured as follows: a piece of film (5 cm x 5 cm, cut with a cookie cutter) is fixed on a slide holder then is immersed in a beaker of 1000 ml capacity , containing 600 ml of distilled water at 20 ° C with stirring, with a magnetic bar, at 300 rpm. The time it takes for the film to break through is measured. The disintegration of the film leads to the formation of film particles. The test lasts 5 minutes after which the particles are passed through a 0.5 mm sieve to check the size of the particles. When there are no particles in the sieve, the film is considered to be water-soluble.
    By "plasticizer" is meant, for example, a substance making it possible to lower the glass transition temperature Tg of the material.
    By "detergent" is meant, for example, a composition which has cleaning properties. Detergents include products in the form of powder or compacted powder for dishwashers and detergents.
    By "hydrophobic" is meant, for example, a compound which has little affinity with water and tends not to dissolve therein. Typically, this is a predominantly nonpolar compound.
    By "hydrophilic" is meant, for example, a compound having an affinity for water and a tendency to dissolve therein. Typically, it is a compound having polar groups capable of forming hydrogen bonds.
    By "surfactant" is meant, for example, an amphiphilic molecule, that is to say a molecule having both hydrophilic and hydrophobic properties.
    By "HLB" is meant, for example, the hydrophilic-lipophilic balance (in French: hydrophilic-lipophilic balance). The HLB value can be calculated according to the following method: HLB = 20 x (Molar mass of the hydrophobic part) / (Molar mass of the molecule).
    By "sequestering agent" is meant, for example, ligands which form chemical complexes with metal ions such as copper, iron, nickel, calcium and magnesium.
    By "fatty acid" is meant, for example, an aliphatic carboxylic monoacid.
    The proportions of the various constituents a), b), c), d) e), and optionally f) and g), are expressed in% by mass relative to the total mass of the thermoplastic material at room temperature.
    Detailed description of the invention
    The biodegradable thermoplastic material can be water-soluble. The biodegradable thermoplastic material can be printable and / or printed.
    The thermoplastic material comprises a) between 50 and 80%, preferably between 52 and 75%, and more preferably still between 55 and 70%, or better still between 60 and 65%, of casein and / or caseinate.
    Casein is a milk protein that is sparingly soluble in water. It is mainly obtained by precipitation by adding an acid (acid casein) or rennet (rennet casein) to milk. Casein consists of a mixture of casein a, casein β and casein κ having molar masses between 19,000 and 25,000g / mol. By caseinate is meant, for example, a casein salt, the contranion of which is chosen from the group comprising - preferably composed of - calcium, potassium, ammonium, sodium and magnesium.
    According to one embodiment of the thermoplastic material, a) comprises at least one casein.
    According to another embodiment of the thermoplastic material, a) comprises at least one caseinate, for example a sodium caseinate, or a mixture of caseinates.
    According to another embodiment of the thermoplastic material, a) comprises a mixture of casein and at least one caseinate. In this case, the mass ratio between the casein and the caseinate (s) can be between 5/95 and 95/5, 20/80 and 80/20 or 40/60 and 60/40.
    The thermoplastic material comprises b) between 4 and 13% of water, preferably between 4.5 and 12%, and, more preferably still, between 5 and 11%, or better still between 7 and 10.5%, water. Water acts as a plasticizer which must be distinguished from the plasticizer c) used in the composition of the thermoplastic material according to the invention.
    The latter in fact comprises c) between 10 and 35%, preferably between 12 and 32%, and, more preferably still, between 15 and 28%, or better still between 20 and 25%, of at least one plasticizer c) different from b).
    This plasticizer c) can be chosen from polyols, glycerol acetates, glycerol propionates and their mixtures.
    Examples of polyols include glycerol, hexanetriol, glycols, including ethylene glycol, and sugars and their derivatives.
    As examples of sugars, mention may be made of disaccharides, such as maltose, lactose, saccharose and monosaccharides such as fructose.
    Among the sugar derivatives, there may be mentioned their hydrogenated derivatives such as sorbitol, maltitol, mannitol, and xylitol, or alternatively the transformation products of these hydrogenated derivatives such as sorbitan.
    According to one embodiment of the thermoplastic material, the plasticizer c) is chosen from glycerol, sorbitol, mannitol, ethylene glycol and their mixtures. Preferably, the plasticizer c) is glycerol.
    Plasticizer c) may contain residual water.
    The plasticizer c) makes it possible to lower the viscosity of the product by increasing the mobility of the molecular chains.
    Advantageously, the plasticizer c) is a hydrophilic plasticizer.
    The thermoplastic material comprises d) between 0.1 and 8%, preferably between 0.5 and 6%, and more preferably still between 1 and 4%, or better still between 1 and 3%, of a hydrophobic agent d).
    The hydrophobic agent d) can be chosen from polycarboxylic acid esters;
    C3-C33 carboxylic acids, preferably C4C28 fatty acids, and even more preferably C6-C28 unsaturated fatty acids and their mixtures.
    The polycarboxylic acid esters can be derived from at least one polycarboxylic acid and from at least one alcohol, preferably a C1-Cl8 alcohol.
    Among the polycarboxylic acids preferably used in the context of the invention, mention may be made of citric acid, hydroxycitric acid, tartaric acid, malic acid, oxalic acid, malonic acid, acid succinic, glutaric acid, adipic acid, maleic acid, fumaric acid.
    Among the alcohols preferred in accordance with the invention, mention may be made of C2C6 alcohols, such as for example ethanol, zz-propanol, zso-propanol, // - butanol and tertbutanol.
    According to one embodiment of the thermoplastic material, the hydrophobic agent d) is chosen from triethyl citrate, tributyl O-acetyl citrate, tributyl citrate and their mixtures.
    According to one embodiment, the hydrophobic agent d) is a C3C33 carboxylic acid, preferably a C4-C28 fatty acid, and even more preferably a C6-C28 unsaturated fatty acid.
    Among the C4-C28 fatty acids used in the context of the invention, mention may be made of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and their mixtures.
    Among the unsaturated C6-C28 fatty acids which are particularly interesting, mention may be made of palmitoleic acid, oleic acid, linoleic acid and their mixtures.
    The thermoplastic material comprises e) between 0.5 and 6%, preferably between 1 and 5%, and, more preferably still, between 1.5 and 4.5%, or better still between 2 and 4%, of at least minus one surfactant.
    According to one embodiment of the thermoplastic material, the surfactant e) is chosen from zwitterionic surfactants whose HLB is between 2 and 8.
    Among the preferred surfactants, mention may be made of lecithin and / or its analogs such as diacetylene phosphonates.
    According to one embodiment of the thermoplastic material, the ratio of the quantities of e) to d) is greater than or equal to 1. For example, this ratio can be between 1.3 and 3; preferably between 1.5 and 2.5.
    According to one embodiment of the thermoplastic material, said material comprises between 1 and 5% of an additive f) chosen from sequestering agents. Examples of sequestering agents include diammonium citrate, EDTA, phosphates, citric acid, pyrophosphates, and mixtures thereof.
    According to one embodiment of the thermoplastic material, said material also comprises an additive g) chosen from dyes, protein coagulants, anti-caking agents, slip agents and their mixtures. Among the coagulants are citric acid and acetic acid. Among the anti-caking agents, there may be mentioned colloidal silica. Among the slip agents, mention may be made of polyethylene glycols. Among the release agents, mention may be made of polyvinyl alcohol. The biodegradable thermoplastic material can comprise between 0.1% and 5% of g).
    According to one embodiment of the biodegradable thermoplastic material, said material comprises
    a) between 50 and 80% of casein and / or caseinate, preferably between 52 and 75%, and, more preferably still, between 55 and 70%, or better still between 60 and 65%;
    b) between 4 and 13% of water, preferably between 4.5 and 12%, and, more preferably still, between 5 and 11%, or better still between 7 and 10.5%;
    c) between 10 and 35% of glycerol, preferably between 12 and 32%, and, more preferably still, between 15 and 28%, or better still between 20 and 25%;
    d) between 0.1 and 8% of a C6-C28 unsaturated fatty acid, preferably between 0.5 and 6%, and more preferably still between 1 and 4%, or even between 1 and 3% ;
    e) between 0.5 and 6% of lecithin, preferably between 1 and 5%, and, more preferably still, between 1.5 and 4.5%, or better still between 2 and 4%.
    According to a particular embodiment, the biodegradable thermoplastic material consists only of components that can be used in the food industry, that is to say of components included in the codex alimentarius. In this case, the biodegradable thermoplastic material is edible, that is, it can be eaten without risk to humans. For example, when the biodegradable thermoplastic material is made
    a) casein and / or caseinate,
    b) water,
    c) glycerol,
    d) oleic acid, and
    e) lecithin, the thermoplastic material is edible.
    Typically the biodegradable thermoplastic material is in the form of granules or in the form of a film. The invention therefore also relates to the granules of the thermoplastic material as described above.
    The invention also relates to a granule (s) comprising:
    a) between 50 and 80% of casein and / or caseinate, preferably between 52 and 75%, and, more preferably still, between 55 and 70%, or better still between 60 and 65%;
    b) between 4 and 13% of water, preferably between 4.5 and 12%, and, more preferably still, between 5 and 11%, or better still between 7 and 10.5%;
    c) between 10 and 35% of at least one plasticizer other than b), preferably between 12 and 32%, and, more preferably still, between 15 and 28%, or better still between 20 and 25%;
    d) between 0.1 and 8% of a hydrophobic agent, preferably between 0.5 and 6%, and more preferably still between 1 and 4%, or even between 1 and 3%;
    e) between 0.5 and 6% of at least one surfactant, preferably between 1 and 5%, and more preferably still between 1.5 and 4.5%, or better still between 2 and 4%.
    According to one embodiment of the granule (s), said granule comprises
    a) between 50 and 80% of casein and / or caseinate, preferably between 52 and 75%, and, more preferably still, between 55 and 70%, or better still between 60 and 65%;
    b) between 4 and 13% of water, preferably between 4.5 and 12%, and, more preferably still, between 5 and 11%, or better still between 7 and 10.5%;
    c) between 10 and 35% of glycerol, preferably between 12 and 32%, and, more preferably still, between 15 and 28%, or better still between 20 and 25%;
    d) between 0.1 and 8% of a C6-C28 unsaturated fatty acid, preferably between 0.5 and 6%, and more preferably still between 1 and 4%, or even between 1 and 3% ;
    e) between 0.5 and 6% of lecithin, preferably between 1 and 5%, and, more preferably still, between 1.5 and 4.5%, or better still between 2 and 4%.
    Typically, the granule is water soluble. The pellet may be edible.
    The invention also relates to an object capable of being obtained after transformation by extrusion into a flat die, blow-molding extrusion, inflation extrusion, solvent route (in English "solvent cast"), calendering, injection, thermoforming or spinning of the thermoplastic material as described above.
    In particular, mention may be made of the films capable of being obtained from the thermoplastic material as described above.
    The invention also relates to a film obtained from the thermoplastic material as described above. The film can be obtained, for example, by swelling extrusion of granules of the thermoplastic material as described above. The film is a biodegradable thermoplastic film. The film can be printed. Typically, the film has a thickness of between 15 and 100 microns, preferably between 30 and 80 microns and more preferably between 40 and 70 microns. The film can be printed directly before winding or in a second step of unwinding, cutting and rewinding by a conventional process of printing in plastics such as flexography.
    The invention also relates to a film comprising
    a) between 50 and 80% of casein and / or caseinate, preferably between 52 and 75%, and, more preferably still, between 55 and 70%, or better still between 60 and 65%;
    b) between 4 and 13% of water, preferably between 4.5 and 12%, and, more preferably still, between 5 and 11%, or better still between 7 and 10.5%;
    c) between 10 and 35% of at least one plasticizer other than b), preferably between 12 and 32%, and, more preferably still, between 15 and 28%, or better still between 20 and 25%;
    d) between 0.1 and 8% of a hydrophobic agent, preferably between 0.5 and 6%, and more preferably still between 1 and 4%, or even between 1 and 3%;
    e) between 0.5 and 6% of at least one surfactant, preferably between 1 and 5%, and more preferably still between 1.5 and 4.5%, or better still between 2 and 4%.
    According to one embodiment of the film, said film comprises
    a) between 50 and 80% of casein and / or caseinate, preferably between 52 and 75%, and, more preferably still, between 55 and 70%, or better still between 60 and 65%;
    b) between 4 and 13% of water, preferably between 4.5 and 12%, and, more preferably still, between 5 and 11%, or better still between 7 and 10.5%;
    c) between 10 and 35% of glycerol, preferably between 12 and 32%, and, more preferably still, between 15 and 28%, or better still between 20 and 25%;
    d) between 0.1 and 8% of a C6-C28 unsaturated fatty acid, preferably between 0.5 and 6%, and more preferably still between 1 and 4%, or even between 1 and 3% ;
    e) between 0.5 and 6% of lecithin, preferably between 1 and 5%, and, more preferably still, between 1.5 and 4.5%, or better still between 2 and 4%.
    Typically, the film is water soluble. The film can be edible. The film can be thermor actab 1 th.
    The invention also relates to the use of a thermoplastic material, for example a film, as described above for packaging various products (pharmaceutical, food, chemical, cosmetic, ...) in particular hygroscopic products. , and more specifically detergents.
    The invention also relates to a product packaged with a thermoplastic material as described above, for example by a film as described above. The packaged product can be chosen from pharmaceutical, food, chemical, cosmetic products.
    According to one embodiment, the packaged product is a food product, such as for example meat, fish, vegetables, fruits, pastries, pastries, food additives, ingredients, dry preparations, food powders . According to a particular embodiment, the thermoplastic material used to package the food product is an edible film. According to another particular embodiment, the packaged product is a detergent tablet.
    The invention also relates to a detergent packed with a thermoplastic material as described above, for example by a film as described above.
    Detergents can be in liquid or powder form, compact or not. For example, it may be a detergent tablet. Detergent tablets include dishwasher tablets and laundry tablets.
    According to another of its aspects, the invention relates to a method of manufacturing the thermoplastic material as described above.
    This process preferably includes the following steps:
    El. Implementation of an extruder preferably twin screw extruder;
    E2. introduction of compounds a) to e), optionally f), into the extruder;
    E3. recovery of at least one extrusion ring of thermoplastic material;
    E4. possibly drying of the rod
    E5. possibly grinding the rod into granules.
    Advantageously, step E1 consists in operating the extruder with the following parameters: rotation speed between 100 and 150 rpm, and at a temperature between 70 and 120 ° C.
    Step E2 preferably consists in introducing, at the same time or successively, preferably successively, initially, at least part of the compounds a) to e), optionally f), which are in solid form, advantageously in the form powder, and, in a second step, at least part of the compounds a) to e), optionally f), in liquid form.
    In a preferred embodiment, the compounds in solid form, advantageously in powder form, are compounds a) &e); while the compounds in liquid form are the compounds b) c) & d).
    According to another of its aspects, the invention relates to a process for packaging a product using a heat-shrinkable film as described above. The heat shrinkage can be carried out by the heat shrinkage techniques known to those skilled in the art. For example, the product to be packaged is wrapped in a piece of film, which is then heat sealed. The product to be packaged can be a compacted powder tablet, such as a detergent tablet.
    The film is heat-shrunk by passing an air flow at a temperature between 80 ° C and 200 ° C, preferably between 100 and 170 ° C, and even more preferably between 130 and 160 ° C, for a time included between 0.05 seconds and 60 seconds, preferably between 1 and 30 seconds, and more preferably between 2 and 10 seconds. The film then follows the shape of the packaged product.
    According to one embodiment, before heat shrinking, the film is moistened with water or an equivalent liquid by means of a fogger and / or a humidifier and / or a vaporizer for a period which can range from 0.01 seconds to 60 seconds, on at least one of the two faces and / or around the tablet.
    Heat shrinking can also be done by placing the film in an oven whose relative humidity can be controlled. The relative humidity can, for example, be between 10 and 80%, between 10 and 40%, or between 20 and 40%, or be greater than or equal to 30%.
    According to one embodiment, the method comprises the following steps: wrapping the product to be packaged in a piece of film, heat sealing the film, optionally, moistening the film, heat shrinking the film at a temperature between 80 ° C and 200 ° C.
    EXAMPLES
    Manufacturing of granules and film of thermoplastic material
    The extruder used to carry out the following examples is a BC 21 co-rotating twin screw extruder of the Clextral® brand, with a diameter of 25 mm, with a center distance of 21 mm and a length of 900 mm. This extruder has at least 4 zones:
    - a first introduction area
    - a second introduction area
    - a third degassing zone
    - a fourth sector area.
    The rotational speed of the twin screws is 125 rpm and the temperatures of the different zones are between 70 and 120 ° C.
    The first zone of the extruder is a zone for introducing the powders: caseinate and lecithin. Liquids (plasticizers) are introduced into the second zone. The extruder also has a degassing zone in the open air and a last zone consisting of a cylindrical rod die with a diameter of 4 mm.
    The screw profile is as follows:
    750 mm of direct pitch screw mm of mixing screw
    100 mm reverse pitch screw
    At the exit of the extruder, the rod is dried and introduced into a granulator to give granules of 2 to 3 mm in diameter. The granules are then transformed into a film by extrusion-inflation. The extruder used is of the Diani® brand, it has a diameter of 30 mm and it is equipped with an annular die of 80 mm in diameter. The film produced is approximately 30 cm wide and 50 microns thick. The film obtained is 1200 meters long and is then wound up to form a reel. This reel of film is then used to package detergent tablets. A 107mm x 70mm piece of film is used to wrap a 37mm x 27mm x 15mm tablet. The film is then heat sealed at its ends, longitudinally and transversely. Different film formulations have been tested for packaging tablets.
    Unwinding test
    The installation used in this test is shown in FIG. 6. It comprises a reel (1) of film (2) to be tested (partially shown in FIG. 6). This film (2) passes over a return cylinder (3), before being wound up on an engine cylinder (4) having a diameter of 10 cm and a length of 30 cm, equipped with a force sensor (5) of 50 newtons from the ASA-RT brand. The force sensor (5) is used to measure the tension at the film reel during unwinding. The engine cylinder (4) is rotated at a speed of 5 rpm, in order to unwind the reel (1) of film (2).
    The film (2) has a thickness of 50 micrometers and a width of the film 2 = 30 cm.
    The force sensor (5) makes it possible to quantify the concept of “sticky”, which is an obstacle to exploitation at an industrial rate.
    If the force sensor indicates a force greater than 2 N (0.2 kg-force), then the coil is called "sticky".
    Conditioning test
    The packaged detergent tablets are stored for 5 days at 30 ° C and 30% relative humidity. After that, each packaged tablet is gripped with latex gloves, shaken three times by holding one end with dry gloved fingers and put in the palm of the dry gloved hand and then the dry gloved fingers are closed on the tablet three times for wrinkle. If the film opens or breaks during this test, it is qualified as "brittle".
    Printed film
    The film used for packaging the tablets shown in FIGS. 5A and 5B (according to example 5) is printed directly before the winding by flexography.
    The results are presented in Table 1.
    Ex. Formulation Conditioning Unwinding films caseinate Glycerol Acidoleic Lecithin water 1 comp. 67.4 22.6 0 0 13 brittle tights 2 comp. 66.4 28.6 0 0 5 brittle okay 3 comp. 62.9 27.1 0 0 10 brittle tights 4 62.1 23 4.7 1.2 9 okay okay 5 63 23.5 1.1 2.3 10 okay okay
    Table 1: formulations tested and results of unwinding and conditioning tests.
    Examples 1 to 3 are comparative examples, these films cannot be used industrially, because they do not pass the unwinding test and / or the conditioning test.
    See Figures IA and IB are photos of a roll of film that cannot be unwound according to Example 1.
    Examples 4 and 5 are examples according to the invention, these films pass the conditioning and unwinding tests, they can therefore be used industrially and be used to package detergent tablets.
    Figures 2A, 2B and 2C are photos of a reel of roll-up film according to Example 4.
    These figures show the absence of a sticky effect which results in an unwinding or unwinding force in the unwinding test <200 gf.
    Figures 3A and 3B are photos of detergent tablets wrapped in film according to Example 1 after a 5-day conditioning test.
    The disintegration of the packaging film is evident in these figures.
    Figure 4 is a photo of a detergent tablet wrapped in film according to Example 4 after a 5-day conditioning test.
    The packaging film is intact. It has no cracks.
    Photos 5A and 5B are photos of detergent tablets wrapped in a film printed according to Example 5 after a 5-day conditioning test.
    Again the packaging film is intact and free from cracks. The print on the film is not damaged.
    heat shrinkage
    A 5 cm x 5 cm piece of film according to Example 5 is heat-shrunk in an oven, the relative humidity of which can be controlled, at 100 ° C. for 30 seconds. The rate of retraction in the longitudinal and transverse directions is then measured. The results are presented in Table 2.
    These results show that the film according to Example 5 according to the invention is heat-shrinkable.
    % Relative humidityin the oven Withdrawal rateLongitudinal direction Withdrawal rateTransverse direction 10% 12% 6% 30% 16% 6%
    Table 2: withdrawal rate
    权利要求:
    Claims (20)
    [1" id="c-fr-0001]
    1. Biodegradable thermoplastic material characterized in that it comprises (in% by mass)
    a) between 50 and 80% of casein and / or caseinate, preferably between 52 and 75%, and, more preferably still, between 55 and 70%;
    b) between 4 and 13% of water, preferably between 4.5 and 12%, and, more preferably still, between 5 and 11%;
    c) between 10 and 35% of at least one plasticizer other than b), preferably between 12 and 32%, and, more preferably still, between 15 and 28%;
    d) between 0.1 and 8% of a hydrophobic agent, preferably between 0.5 and 6%, and, more preferably still, between 1 and 4%;
    e) between 0.5 and 6% of at least one surfactant, preferably between 1 and 5%, and, more preferably still, between 1.5 and 4.5%.
    [2" id="c-fr-0002]
    2. Material according to claim 1 characterized in that the plasticizer c) is chosen from polyols, glycerol acetates, glycerol propionates, and mixtures thereof, preferably c) is glycerol.
    [3" id="c-fr-0003]
    3. Material according to claim 1 or 2 characterized in that the hydrophobic agent d) is chosen from polycarboxylic acid esters;
    C3-C33 carboxylic acids, preferably C4C28 fatty acids, and even more preferably C6-C28 unsaturated fatty acids;
    - and their mixtures.
    [4" id="c-fr-0004]
    4. Material according to any one of the preceding claims, characterized in that the hydrophobic agent d) is a C6-C28 unsaturated fatty acid, preferably chosen from palmitoleic acid, oleic acid, linoleic acid, and their mixtures.
    [5" id="c-fr-0005]
    5. Material according to any one of the preceding claims, characterized in that the surfactant e) is chosen from zwitterionic surfactants whose HLB is between 2 and 8.
    [6" id="c-fr-0006]
    6. Material according to any one of the preceding claims, characterized in that the ratio of the quantities of e) to d) is greater than or equal to 1.
    [7" id="c-fr-0007]
    7. Material according to any one of the preceding claims, characterized in that it comprises between 1 and 5% by mass of an additive f) chosen from sequestering agents.
    [8" id="c-fr-0008]
    8. Material according to any one of the preceding claims, characterized in that it comprises an additive g) chosen from dyes, protein coagulants, anti-caking agents, slip agents and their mixtures.
    [9" id="c-fr-0009]
    9. Material according to any one of the preceding claims, characterized in that it is water-soluble.
    [10" id="c-fr-0010]
    10. Material according to any one of the preceding claims, characterized in that it is edible.
    [11" id="c-fr-0011]
    11. Granules of the material according to one of claims 1 to 10.
    [12" id="c-fr-0012]
    12. Object capable of being obtained after transformation by extrusion into a flat die, blow-molding extrusion, inflation extrusion, solvent route, calendering, injection, thermoforming or spinning of the thermoplastic material according to any one of claims 1 to 10 or of granules according to claim 11.
    [13" id="c-fr-0013]
    13. Object according to claim 12 characterized in that it is a film.
    [14" id="c-fr-0014]
    14. Film according to claim 13 characterized in that it is printed.
    [15" id="c-fr-0015]
    15. Film according to claim 13 or 14, characterized in that it is heat-shrinkable.
    [16" id="c-fr-0016]
    16. Product, characterized in that it is wrapped by a film according to one of claims 13 to 15.
    [17" id="c-fr-0017]
    17. Product according to claim 16, characterized in that it is a detergent tablet.
    [18" id="c-fr-0018]
    18. Product according to claim 16, characterized in that it is a food product.
    [19" id="c-fr-0019]
    19. A method of manufacturing a thermoplastic material according to any one of claims 1 to 10, characterized in that it comprises the following steps: El implementation of an extruder preferably twin screw extruder;
    E2 introduction of the compounds a) to e), optionally f), into the extruder; E3 recovery of at least one extrusion rod of thermoplastic material; E4 possibly drying of the rod;
    E5 possibly grinding the rod into granules;
    step E2 preferably consisting in introducing, at the same time or successively, preferably successively, initially, at least a portion of the compounds a) to e), optionally f), which is in solid form, advantageously in the form powder, and, in a second step, at least a portion of the compounds a) to e), optionally f), in liquid form.
    [20" id="c-fr-0020]
    20. A method of packaging a product using a film according to claim 15, characterized in that it comprises the following steps:
    wrap the product to be packaged in a piece of film,
    - heat seal the film,
    - optionally, moisten the film,
    - heat shrink the film at a temperature between 80 ° C and 200 ° C.
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    同族专利:
    公开号 | 公开日
    EP3728477A1|2020-10-28|
    JP2021507982A|2021-02-25|
    FR3075215B1|2020-11-20|
    US20210079223A1|2021-03-18|
    CN111868174A|2020-10-30|
    WO2019122726A1|2019-06-27|
    KR20200096646A|2020-08-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4076846A|1974-11-22|1978-02-28|Sumitomo Bakelite Company Limited|Protein-starch binary molding composition and shaped articles obtained therefor|
    CA1061163A|1974-11-22|1979-08-28|Ryuzo Nakatsuka|Protein-starch binary molding composition and shaped articles obtained therefrom|
    WO1999043497A1|1998-02-25|1999-09-02|Campina Melkunie B.V. Kaasgroep|Biodegradable laminate and packaging foil comprising such a laminate|
    EP1075188A1|1998-05-05|2001-02-14|Natural Polymer International Corporation|Biodegradable protein/starch-based thermoplastic composition|
    EP2336235A1|2009-12-18|2011-06-22|Actega Artistica S.A.|Water-based dispersion of thermoplastic polymer and non-thermoplastic elastomer|
    FR2963013A1|2010-07-23|2012-01-27|Univ Jean Monnet|THERMOPLASTIC GRANULE BASED ON CASEIN AND / OR CASEINATE, COMPOSITION AND METHOD OF MANUFACTURE|FR3113066A1|2020-07-31|2022-02-04|Eurotab Operations|New coated detergent tablet|
    NL2022746B1|2019-03-15|2020-09-22|Carl Schubert Robbert|A method of packaging a plant, and a plastic carrier|
    GB2586015A|2019-07-25|2021-02-03|Beldi London Ltd|A Fluid Dispenser|
    FR3102366B1|2019-10-29|2021-12-03|Lactips|emulsion which can be used in particular as a technological aid in the field of plastics, or as an active encapsulation system, its preparation process and its applications|
    FR3107529A1|2020-02-21|2021-08-27|Lactips|Thermoplastic material based on casein and / or caseinate associated with a water-soluble polymer|
    WO2022017974A1|2020-07-24|2022-01-27|Basf Se|Casein based multilayer film with improved barrier properties|
    法律状态:
    2018-10-30| PLFP| Fee payment|Year of fee payment: 2 |
    2019-06-21| PLSC| Publication of the preliminary search report|Effective date: 20190621 |
    2019-10-28| PLFP| Fee payment|Year of fee payment: 3 |
    2020-10-27| PLFP| Fee payment|Year of fee payment: 4 |
    2021-10-28| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1762549|2017-12-19|
    FR1762549A|FR3075215B1|2017-12-19|2017-12-19|BIODEGRADABLE THERMOPLASTIC MATERIAL BASED ON CASEIN AND / OR CASEINATE|FR1762549A| FR3075215B1|2017-12-19|2017-12-19|BIODEGRADABLE THERMOPLASTIC MATERIAL BASED ON CASEIN AND / OR CASEINATE|
    CN201880082005.XA| CN111868174A|2017-12-19|2018-12-19|Biodegradable thermoplastics based on casein and/or caseinate|
    US16/956,364| US20210079223A1|2017-12-19|2018-12-19|Biodegradable thermoplastic material made from casein and/or caseinate|
    JP2020554944A| JP2021507982A|2017-12-19|2018-12-19|Casein and / or caseinate-based biodegradable thermoplastics|
    PCT/FR2018/053423| WO2019122726A1|2017-12-19|2018-12-19|Biodegradable thermoplastic material made from casein and/or caseinate|
    EP18842781.9A| EP3728477A1|2017-12-19|2018-12-19|Biodegradable thermoplastic material made from casein and/or caseinate|
    KR1020207020778A| KR20200096646A|2017-12-19|2018-12-19|Casein and/or casein salt-based biodegradable thermoplastics|
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