EP4359315A1 - Multilayer material useful as packaging, comprising a layer of cellulosic material and a layer of material comprising at least one moins one casein and/or at least one caseinate - Google Patents

Multilayer material useful as packaging, comprising a layer of cellulosic material and a layer of material comprising at least one moins one casein and/or at least one caseinate

Info

Publication number
EP4359315A1
EP4359315A1 EP22744270.4A EP22744270A EP4359315A1 EP 4359315 A1 EP4359315 A1 EP 4359315A1 EP 22744270 A EP22744270 A EP 22744270A EP 4359315 A1 EP4359315 A1 EP 4359315A1
Authority
EP
European Patent Office
Prior art keywords
layer
casein
multilayer
caseinate
packaging
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22744270.4A
Other languages
German (de)
French (fr)
Inventor
Bastien BESSAIRE
kheirdine MELLOUKI
Elodie CHEVALIER
Fannie CHIROUSSEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lactips
Original Assignee
Lactips
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lactips filed Critical Lactips
Publication of EP4359315A1 publication Critical patent/EP4359315A1/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/22—Proteins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/50—Proteins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper

Definitions

  • MULTILAYER MATERIAL THAT CAN BE USED AS PACKAGING, COMPRISING A LAYER OF CELLULOSIC MATERIAL AND A LAYER OF MATERIAL COMPRISING AT LEAST ONE CASEIN AND/OR AT LEAST ONE CASEINATE
  • This disclosure relates to the field of multilayer materials that can be used as packaging.
  • the present disclosure relates to a multilayer material comprising a layer of cellulosic material A and a layer of material B comprising at least one casein and/or at least one caseinate.
  • paper packaging 17% is provided with a layer of plastic, to provide a barrier to gases, fats or water (in PE, PP, PET, PVDC, EVOH, or PVOH) to show the food inside, or to allow sealability (closing the package).
  • a layer of plastic to provide a barrier to gases, fats or water (in PE, PP, PET, PVDC, EVOH, or PVOH) to show the food inside, or to allow sealability (closing the package).
  • recycled paper cannot be used in direct contact with food, due to the migration of mineral oils from the inks used in the previous paper, for example in newspapers.
  • a layer of plastic must again be used as a barrier for consumer safety. This prevents widespread use of recycled paper in food packaging.
  • the present invention aims to satisfy at least one of the following objectives.
  • One of the objectives of the present invention is to provide a recyclable material that can be used as packaging.
  • One of the objectives of the present invention is to provide a bio-based recyclable material that can be used as packaging.
  • One of the objectives of the present invention is to provide a recyclable material that can be used as packaging in the food sector.
  • One of the objectives of the present invention is to provide a biodegradable material that can be used as packaging.
  • Another object of the present invention is to provide a material based on cellulosic materials, having improved barrier properties.
  • One of the objectives of the present invention is to provide a recyclable material that can be easily produced.
  • the subject of the present disclosure is a multilayer material comprising: i) At least one layer of cellulosic material A, and ii) At least one layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b).
  • the present disclosure also relates to a multilayer material obtained:
  • a solution S comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b);
  • the present disclosure also relates to a packaging comprising a multilayer material.
  • the present disclosure also relates to a product packaged by packaging comprising a multilayer material.
  • the present disclosure also relates to a method for manufacturing a multilayer material, said method being carried out
  • a solution comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b);
  • a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), possibly by means of a binder, the assembly being preferably carried out by lamination or lamination.
  • this multilayer material could be used as packaging. Indeed, this multilayer material can be recycled in recycling centers without modifying lines or processes because the layer of material B is water-soluble. Recycling centers will be able to recover nearly 100% of cellulosic material fibers through simple mechanical filtration. The residues of material B resulting from its solubilization will be biodegraded in the water treatment infrastructures already in place within the recycling plants. The fact that the residues of material B are biodegradable makes it possible to avoid pollution linked to microplastics.
  • a layer of material B makes it possible to improve the barrier properties of the multilayer material, in particular the barrier properties to greases and to oxygen, which makes it possible to envisage use in the field food packaging.
  • the multilayer material according to the invention also has good weldability properties, and in particular heat-sealability.
  • the multilayer material according to the invention combines good recyclability, improved barrier properties and good weldability properties, which allows it to be used as packaging, in particular in the food sector.
  • material B is safe for food contact, 100% renewable, compostable and biodegradable in the marine environment, which is not the case for most polymers. used in packaging. Casein is an existing ingredient, documented in the food industry, and easily industrialisable. The multilayer material can therefore be produced easily.
  • packing is meant an object intended to contain and protect goods, to allow their handling and their transport from the producer to the consumer or to the user, and to ensure their presentation, their conservation, their protection and /or their use.
  • cellulosic material is meant, for example, a material which can be derived from a cellulose pulp.
  • This cellulose pulp can be produced by chemical and/or mechanical treatment, which is well known to those skilled in the art.
  • This cellulose pulp can be derived from any suitable source such as wood, recycled wood, annual plants, agricultural residues (bagasse, straws, %), grasses (eg sugar cane, bamboo ) or boxes.
  • thermoplastic is meant, for example, a material which becomes malleable and bendable above a given temperature, the glass transition temperature Tg, but which below this Tg becomes hard again, these transformations being reversible.
  • biodegradable is meant, for example, a material which can be decomposed under the action of microorganisms (bacteria, fungi, algae, etc.). 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 and/or standard NF T 51-800.
  • water-soluble means, for example, which dissolves in water.
  • the water solubility of a material can be measured in the following way: 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 10 minutes after which the particles are passed through a 0.5 mm sieve to check the particle size. When there are no particles in the sieve, the film is considered water-soluble.
  • plasticizer is meant, for example, a substance making it possible to lower the glass transition temperature Tg of the material.
  • hydrophobic is meant, for example, a compound having little affinity with water and having a tendency not to dissolve therein. Typically, it is a predominantly apolar compound.
  • hydrophilic is meant, for example, a compound having an affinity with water and having a tendency to dissolve therein. Typically, it is a compound having polar groups capable of forming hydrogen bonds.
  • surfactant is meant, for example, an amphiphilic molecule, that is to say a molecule possessing both hydrophilic and hydrophobic properties.
  • HLB hydrophilic-lipophilic balance
  • fatty acid is meant, for example, an aliphatic monocarboxylic acid.
  • biobased we mean, for example, a product made from materials of biological origin.
  • binder is meant, for example, an agent making it possible to create a bonding layer between the layer of cellulosic material A and the layer of material B.
  • the binder used in the present invention can be a binder conventionally used in the manufacture of multilayer materials and in particular of multilayer films.
  • hot-melt glues thermoofusibles in French.
  • the invention relates firstly to a multilayer material comprising: i) At least one layer of cellulosic material A, and ii) At least one layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b).
  • the present disclosure also relates to a multilayer material obtained:
  • a solution comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b);
  • a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), optionally by means of a binder, the assembly being preferably carried out by lamination or lamination.
  • the multilayer material is preferably recyclable and/or biosourced.
  • the multilayer material can be recyclable according to directive 2018/852/EU of May 30, 2018.
  • the multilayer material is compostable, preferably according to standard NF T 51-800.
  • the multilayer material may have a thickness of between 0.01 and 100 mm, preferably between 0.05 and 50 mm.
  • the cellulosic material A is preferably chosen from paper and cardboard. According to one embodiment, cellulosic material A has a basis weight of between 20 and 500 g/m 2 , preferably between 50 and 450 g/m 2 . According to one embodiment, the cellulosic material A is chosen from papers having a weight of between 20 and 225 g/m 2 , and cardboard having a weight of between 225 and 500 g/m 2 .
  • the layer of cellulosic material A may have a thickness of between 0.01 and 50 mm, preferably between 0.05 and 20 mm.
  • the cellulosic material A comprises cellulose, preferably at least 80% by weight, and preferably at least 90% by weight.
  • the cellulosic material A can be colored and comprise a pigmentary layer.
  • the cellulosic material A can comprise a mineral layer, for example of the kaolin type.
  • the material B and/or the solution S comprise: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b).
  • Casein is a protein derived from milk which is poorly soluble in water. It is mainly obtained by precipitation by adding an acid (acid casein) or rennet (rennet casein) to the milk, or by filtration (miscellar casein). Casein consists of a mixture of a-casein, b-casein and k-casein with molar masses between 19,000 and 25,000 g/mol.
  • caseinate is meant, for example, a casein salt whose counter cation is chosen from the group comprising—preferably consisting of—calcium, potassium, ammonium, sodium and magnesium.
  • a) comprises at least one caseinate, for example a sodium caseinate, or a mixture of caseinates.
  • a) comprises a mixture of casein and at least one caseinate.
  • 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 material B and/or the solution S can comprise gelatin d).
  • Gelatin is a protein which has a high level of glycine and proline. It is obtained by partial hydrolysis of collagen, mainly from collagen contained in the skins and bones of animals. It can be type A (it then comes from an acid treatment of the collagen) or type B (it then comes from a basic treatment of the collagen). It can also be obtained by enzymatic treatment of collagen.
  • the gelatin used has preferably not been chemically modified. According to one embodiment of the invention, the gelatin used is commercially available food gelatin or type B, it can be in the form of sheets, powder or granules. Advantageously, the gelatin used is of type B.
  • the ratio of the quantities a): d), when d) is present, can be between 90:10 and 20:80, preferably between 75:25 and 25:75, and preferably between 60:40 and 40 :60. According to a particular embodiment, the ratio a):d) is 50:50. According to a particular embodiment, the ratio a):d) is between 55:45 and 45:55.
  • the plasticizer c) can be chosen from polyols, glycerol acetates, glycerol propionates and mixtures thereof.
  • polyols examples include glycerol, hexanetriol, glycols, including ethylene glycol, and sugars and their derivatives.
  • sugars mention may be made of disaccharides such as maltose, lactose, sucrose and monosaccharides such as fructose.
  • sugar derivatives mention may be made of their hydrogenated derivatives such as sorbitol, maltitol, mannitol, and xylitol, or even the transformation products of these hydrogenated derivatives such as sorbitan.
  • the plasticizer c) is chosen from glycerol, sorbitol, mannitol, ethylene glycol and mixtures thereof.
  • the plasticizer c) is chosen from glycerol, sorbitol, and mixtures thereof.
  • the plasticizer c) is glycerol.
  • the 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.
  • the plasticizer c) is a hydrophilic plasticizer.
  • the material B and/or the solution S may also comprise a hydrophobic agent e).
  • the hydrophobic agent e) can be chosen from:
  • C3-C33 carboxylic acids, preferably C4-C28 fatty acids, and even more preferably C6-C28 unsaturated fatty acids;
  • the polycarboxylic acid esters can be derived from at least one polycarboxylic acid and from at least one alcohol, preferably a C1-C18 alcohol.
  • polycarboxylic acids preferably retained in the context of the invention, mention may be made of citric acid, hydroxycitric acid, tartaric acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid.
  • C2-C6 alcohols such as for example ethanol, n-propanol, G/so-propanol, n-butanol and tert-butanol. .
  • the hydrophobic agent e) is chosen from triethyl citrate, tributyl O-acetyl citrate, tributyl citrate and mixtures thereof.
  • the hydrophobic agent e) is a C3-C33 carboxylic acid, preferably a C4-C28 fatty acid, and even more preferably an Ob-C28 unsaturated fatty acid.
  • 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 mixtures thereof.
  • C6-C28 unsaturated fatty acids mention may be made of palmitoleic acid, oleic acid, linoleic acid, and mixtures thereof.
  • the material B and/or the solution S may also comprise at least one surfactant f), preferably chosen from zwitterionic surfactants whose HLB is between 2 and 8.
  • polysorbates are fatty acid esters of polyoxyethylene sorbitan.
  • polysorbate 20 polysorbate 40, polysorbate 60, and polysorbate 80.
  • the ratio of the quantities of f) to e) is greater than or equal to 1.
  • this ratio may be between 1.3 and 3; preferably between 1.5 and 2.5.
  • the material B and/or the solution S may also comprise a polysaccharide g).
  • g) is chosen from pullulan, starch, alginates, and mixtures thereof.
  • the polysaccharide g) can be a water-soluble polysaccharide.
  • the material B and/or the solution S can additionally comprise a bittering agent h), preferably denatonium benzoate.
  • the bittering agent h) can be chosen from denatonium benzoate, derivatives of denatonium benzoate, denatonium saccharide, denatonium chloride, sucrose benzoate, quinine, quinine hydrochloride, sulphate quinine, brucine, brucine sulfate, quassia, quassine, naringin, limonine, phenylthiocarbamide, quebracho, sucrose octaacetate, quercetin, berberine, and mixtures thereof.
  • the material B and/or the solution S also comprise an additive i) chosen from dyes, protein coagulants, anti-caking agents, slip agents and mixtures thereof.
  • coagulants mention may be made of citric acid and acetic acid.
  • anti-caking agents mention may be made of colloidal silica.
  • slip agents mention may be made of polyethylene glycols and compounds with fatty chains, preferably C12-C28, having an amide terminus.
  • the material B and/or the solution S comprise an additive j) chosen from sequestering agents.
  • sequestering agent is meant, for example, ligands which form chemical complexes with metal ions such as copper, iron, nickel, calcium and magnesium.
  • material B comprises between 10 and 80% casein and/or caseinate a), preferably between 20 and 75%, and, even more preferably, between 25 and 70%.
  • material B comprises between 50 and 80% casein and/or caseinate a), preferably between 52 and 75%, and, even more preferably, between 55 and 70%. According to one embodiment, material B comprises between 10 and 55% casein and/or caseinate a), preferably between 20 and 50%, preferably between 25 and 40%, and more preferably still between 30 and 35%.
  • material B comprises between 1 and 55% gelatin d), preferably between 5 and 50%, preferably between 10 and 40%, and more preferably still between 30 and 35%.
  • material B comprises between 30 and 35% casein and/or caseinate a), and between 30 and 35% gelatin d).
  • the material B can comprise between 5 and 15% water b), preferably between 7 and 11%.
  • the amount of water can be between 9 and 10%.
  • Water acts as a plasticizer which must be distinguished from plasticizer c) entering into the composition of material B.
  • the material B can comprise c) between 10 and 35% of at least one plasticizer different from c), preferably between 15 and 30%.
  • the material B can comprise between 0.1 and 8% of a hydrophobic agent e), preferably between 1 and 4%.
  • material B comprises between 0.5 and 6%, preferably between 1 and 3%, of a hydrophobic agent e).
  • the material B can comprise between 0.5 and 6% of at least one surfactant f), preferably chosen from zwitterionic surfactants whose HLB is between 2 and 8.
  • the material B can comprise comprises between 1 and 5% of at least one surfactant f), preferably between 1.5 and 4.5%, and even more preferably between 2 and 4%.
  • the material B can comprise between 2 and 10% of a polysaccharide g), preferably g) is chosen from pullulan, starch, alginates, and mixtures thereof.
  • material B comprises between 4 and 8% of a polysaccharide g).
  • Material B can comprise between 0.001 and 0.5% of a bittering agent h), preferably denatonium benzoate.
  • material B also comprises between 0.05 and 0.15% of a bittering agent h).
  • Material B can comprise between 0.1% and 5% of i). Material B can comprise between 1 and 5% of an additive j) chosen from sequestering agents.
  • Material B can be water-soluble and/or biodegradable. Material B can be biobased. According to one embodiment, material B is a thermoplastic material. Material B can be obtained by extrusion, as mentioned in the examples.
  • the layer of material B is a layer of film of material B, preferably a layer of film of thermoplastic, biodegradable and water-soluble material B.
  • the film layer of material B has a thickness of between 1 and 150 microns, preferably between 2 and 50 microns and more preferably between 2.5 and 20 microns.
  • the proportions of the various constituents of the solution S are expressed in % by weight relative to the total weight of the dry matter in the solution S.
  • the solution S comprises between 0.1 and 90% of dry matter, preferably between 1 and 50% dry matter, preferably between 5 and 25% dry matter, and more preferably between 10 and 20% dry matter.
  • Solution S can be obtained by dissolving material B in water or by dissolving the various components in water.
  • the solution S comprises between 10 and 80% casein and/or caseinate a), preferably between 20 and 75%, and, even more preferably, between 25 and 70%.
  • the solution S comprises between 50 and 80% casein and/or caseinate a), preferably between 52 and 75%, and, even more preferably, between 55 and 70%. According to one embodiment, the solution S comprises between 10 and 55% casein and/or caseinate a), preferably between 20 and 50%, preferably between 25 and 40%, and more preferably still between 30 and 35%.
  • the solution S comprises between 1 and 55% of gelatin d), preferably between 5 and 50%, preferably between 10 and 40%, and even more preferably between 30 and 35%.
  • the solution S comprises between 30 and 35% casein and/or caseinate a), and between 30 and 35% gelatin d).
  • the solution S can comprise c) between 10 and 35% of at least one plasticizer different from c), preferably between 15 and 30%.
  • the solution S can comprise between 0.1 and 8% of a hydrophobic agent e), preferably between 1 and 4%.
  • the solution S comprises between 0.5 and 6%, preferably between 1 and 3%, of a hydrophobic agent e).
  • the solution S can comprise between 0.5 and 6% of at least one surfactant f), preferably chosen from zwitterionic surfactants whose HLB is between 2 and 8.
  • the solution S can comprise comprises between 1 and 5% of at least one surfactant f), preferably between 1.5 and 4.5%, and even more preferably between 2 and 4%.
  • the solution S can comprise between 2 and 10% of a polysaccharide g), preferably g) is chosen from pullulan, starch, alginates, and mixtures thereof.
  • the solution S comprises between 4 and 8% of a polysaccharide g).
  • the solution S can comprise between 0.001 and 0.5% of a bittering agent h), preferably denatonium benzoate.
  • a bittering agent h preferably denatonium benzoate.
  • the solution S further comprises between 0.05 and 0.15% of a bittering agent h).
  • the solution S can comprise between 0.1% and 5% of i).
  • the solution S can comprise between 1 and 5% of an additive j) chosen from sequestering agents.
  • the solution S can also contain a preservative and/or a biocide.
  • concentration of preservative and/or a biocide can be between 0.1 and 5%.
  • Packaging comprising multi-layer material
  • the present disclosure also relates to a packaging comprising a multilayer material.
  • the packaging includes other layers than the multilayer material, in other cases the packaging consists of the multilayer material.
  • the present disclosure also relates to the use of a multilayer material for packaging various products (pharmaceuticals, food, chemicals, cosmetics, etc.).
  • the present disclosure also relates to a product packaged by packaging comprising a multilayer material.
  • the product can be in solid, liquid or gel form.
  • the packaged product can be any object, for example it can be a mechanical part, a do-it-yourself object, a gardening object, a magazine, a newspaper, or disposable dishes.
  • the packaged product can for example be chosen from among pharmaceutical, food, chemical and cosmetic products.
  • the packaged product is a food product, such as for example meat, fish, vegetables, fruits, pastries, pastries, chocolate, confectionery, food additives, ingredients, dry preparations, food powders, ready meals.
  • the packaged product is a cosmetic product.
  • the packaged product is a detergent.
  • the detergents can be in the form of liquid or powder, compact or not.
  • it may be a detergent tablet.
  • Detergent tablets include dishwasher detergent tablets and laundry detergent tablets. It can also be liquid detergent, such as liquid laundry detergent.
  • the multilayer material can be manufactured by lamination, coating, lamination, co-extrusion or coating extrusion processes well known to those skilled in the art.
  • the present disclosure also relates to a method for manufacturing a multilayer material, characterized in that it is carried out - either by coating a layer of cellulosic material A with a solution S comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b);
  • a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), possibly by means of a binder, the assembly being preferably carried out by lamination or lamination.
  • the manufacture of the multilayer material is carried out by coating.
  • the layer of cellulosic material A is coated with a solution S. This can be done using a coating material well known to those skilled in the art. After coating, the coated cellulosic material A can be dried, for example in an oven, in order to obtain the multilayer material.
  • the manufacture of the multilayer material is carried out by assembling a layer of cellulosic material A and a layer of material B.
  • the assembly can be carried out by lamination or lamination .
  • the lamination can be carried out cold or hot. In the case of cold lamination, a binder can be used. In the case of hot lamination, this step can be carried out without a binder.
  • the complexation can be carried out by a step of lamination, co-extrusion or coating extrusion, with or without a binder.
  • the assembly can for example be carried out by coating one of the faces of one of the materials A or B with a binder, then by bringing the two materials into contact. so that the binder is found between the two materials.
  • This assembly can be carried out by means of a calender.
  • the cellulosic materials used are as follows:
  • thermoplastic granules used for the coating were prepared by extrusion from sodium caseinate.
  • the extruder used is a Clextral® BC 21 co-rotating twin-screw extruder, with a diameter of 25 mm, a center distance of 21 mm and a length of 900 mm. This extruder has at least 4 zones: a first introduction zone, a second introduction zone, a third degassing zone, and a fourth die zone.
  • the rotational speed of the twin screws is between 175 and 320 rpm and the temperatures of the different zones are between 30 and 120°C.
  • the first zone of the extruder is a powder introduction zone: caseinate and lecithin.
  • the liquids are introduced into the second zone.
  • the extruder further comprises a degassing zone in the open air and a final zone consisting of a cylindrical rod die with a diameter of 4 mm.
  • the auger profile is as follows: 750 mm direct pitch auger, 50 mm mixing auger, 100 mm reverse pitch auger.
  • the rod On leaving the extruder, the rod is dried and introduced into a granulator to give granules 2 to 3 mm in diameter.
  • the final composition of the pellets is as follows:
  • thermoplastic granules Dissolution of the thermoplastic granules in water with stirring, to obtain an 11%, 18% or 19% dry matter solution.
  • the coating of the papers with the solution was carried out with laboratory coating equipment, an Elcometer which allows the translation of a threaded bar in order to spread and dose a solution on the surface of a paper. 2 coating passes on the same face of each of the papers were carried out, so as to obtain a layer weight of 9 or 14 g/m 2 .
  • Table 1 The results obtained are shown in Table 1.
  • the coated sheets of paper are then dried in an oven at 55°C and then under a half-moon dryer at 80°C. They are then placed under a heavy metal plate.
  • the characterization of the support papers without coating and of the coated papers was carried out under standardized conditions at 23° C.-50% RH (NF EN 20 187, 1993).
  • the weight measurement was carried out according to the method described in the NF EN ISO 536, 2012 standard, and the thickness measurement according to the method described in the NF EN ISO 534, 2011 standard. The results obtained are in line with the expected values and correspond to the different deposits made on the 2 papers.
  • the adhesion was then tested according to the Finat 3 method:
  • the coated support is glued using tape to a plate.
  • the specimens prepared in this way are produced in compliance with the Finat 3 method, namely: maintenance for 20 hours at 23° C. under a pressure of 6.86 kPa (70 g/cm2) of the plate/tape/coated paper assembly.
  • the Finat method 1 no delamination between the coated layer and the paper backing was observed. Indeed, the delamination occurred at the level of the tape.
  • Grease barriers Method for measuring the Cobb index with oil
  • the measurement of the Cobb index is carried out on a surface of 25 cm 2 and its duration is fixed here at 60 sec. ISIO 4 oil colored with Sudan red III is used, which makes it possible to visualize the defects when they are present. A method derived from the SCAN-P 37 standard is used. The measurement of the Cobb index makes it possible to determine the quantity of oil that the surface of a paper or cardboard can absorb for a given time, here 60s. The lowest possible Cobb index is sought.
  • the measurements are carried out on 5 different samples. We then calculate the mean and the standard deviation. The measurements are carried out at 23° C. / 50% RH after the samples have remained under these conditions for at least 12 hours. The results are shown in Table 2.
  • Oxygen barrier Characterization OTR measurement at 23°C - 50% RH according to the ASTM F 1927 standard
  • the oxygen measurement is made using a Presens device according to the ASTM F1927 standard. The measurement is carried out at the temperature and humidity of the conditioned room, i.e. 23°C / 50% RH. The measurements were doubled on 4 different samples. The results are shown in Table 3. [0144] [Table 3]
  • the recyclability of the multilayer materials according to the invention has been determined.
  • the recyclability of packaging is assessed within the meaning of Directive 2018/852/EU of May 30, 2018 (amending Directive 94/62/EC).
  • the packaging must have a paper-cardboard structure comprising at least 50% by weight of paper-cardboard material
  • the packaging must be designed with materials or combinations of materials that are compatible with known, relevant and industrially available recycling technologies. It should not negatively affect recycling processes.
  • All the multilayer materials prepared according to the invention contain at least 50% by weight of paper/cardboard material. The first condition is therefore fulfilled.
  • a recycling test was then carried out with the multilayer materials prepared according to the invention in order to evaluate the impact of the presence of the layer of material B comprising sodium caseinate.
  • the different steps performed are presented below.
  • the pulping operation consists in individualizing the cellulosic fibers so as to make the fibrous suspension pumpable with a view to classifying it, using a laboratory pulper.
  • a laboratory pulper For the purposes of the test and more particularly of the resuspension, we manually tore the 60g sample into pieces of about 3 x 3 cm in order to make it compatible with the size of the laboratory pulper.
  • the raw material prepared is then resuspended under the following conditions: - Temperature*: 40°C
  • pulp or fibrous suspension After 15 minutes of disintegration, the disintegrated raw material (called pulp or fibrous suspension) is observed visually in order to verify two points:
  • the paste corresponding to the disintegration of the sample to be tested is then collected and then classified on two Somerville laboratory classification devices mounted in cascade, the first is equipped with a 15/100 mm slotted sieve and the second with a 10/100 mm sieve.
  • the accepted paste passes through the slits of the classifiers while the undesirable elements (such as pieces of plastic) remain on the surface of the classifying sieve.
  • the first classifier is used to retain large contaminants and the second any residual contaminants.
  • the presence of the layer of material B comprising sodium caseinate and glycerol, on a layer A of cellulosic material does not affect the recyclability of this cellulosic material.
  • a multilayer material was prepared according to the procedure described above.
  • the layer weight is 10g/m2.
  • Heat sealability tests were carried out on a Lako Seal Tester SL10 from Lako Sool with the following parameters: - Pressure: 0.2 N/mm 2
  • the dimension of the heat-sealed test pieces was 20 mm * 25.4 mm.
  • the multilayer material according to the invention has good weldability. Indeed the fact of having a cohesive failure, indicates that the failure occurs in the material and not at the level of the seal. Furthermore, the peel forces for seals made at 150°C, 160°C or 170°C are similar and high. Thus, the multilayer materials according to the invention have good heat-seal properties.

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Abstract

The present invention resides in the field of multilayer materials that can be used as packaging. The aim of the invention is to provide a material based on cellulosic materials that is recyclable, biobased/biodegradable, and/or has improved barrier properties and that can be used as packaging, for example in the food sector, and that preferably is easy to produce. In particular, the present invention concerns a multilayer material comprising a layer of cellulosic material A and a layer of material B comprising at least one casein and/or at least one caseinate, water, and at least one plasticizer other than water, and optionally gelatine. The invention also concerns the packaging made from this material, a product packaged with this packaging, and the production of this material.

Description

MATERIAU MULTICOUCHE POUVANT ETRE UTILISE COMME EMBALLAGE, COMPRENANT UNE COUCHE DE MATERIAU CELLULOSIQUE ET UNE COUCHE DE MATERIAU COMPRENANT AU MOINS UNE CASEINE ET/OU AU MOINS UN CASEINATEMULTILAYER MATERIAL THAT CAN BE USED AS PACKAGING, COMPRISING A LAYER OF CELLULOSIC MATERIAL AND A LAYER OF MATERIAL COMPRISING AT LEAST ONE CASEIN AND/OR AT LEAST ONE CASEINATE
Domaine technique Technical area
[0001] La présente divulgation relève du domaine des matériaux multicouches pouvant être utilisés comme emballage. En particulier, la présente divulgation concerne un matériau multicouche comprenant une couche de matériau cellulosique A et une couche de matériau B comprenant au moins une caséine et/ou au moins un caséinate. This disclosure relates to the field of multilayer materials that can be used as packaging. In particular, the present disclosure relates to a multilayer material comprising a layer of cellulosic material A and a layer of material B comprising at least one casein and/or at least one caseinate.
Arrière-plan technologique Technology background
[0002] La diminution des ressources non renouvelables, telles que le pétrole, et l’augmentation de la pollution liée à ces ressources entraînent le développement de solutions alternatives moins polluantes et plus respectueuses de l’environnement. En particulier, en ce qui concerne les emballages, la Commission Européenne souhaite que 100 % des emballages soient réutilisables, mécaniquement recyclables ou compostables d'ici 2030 (Plan d'action pour l'économie circulaire - 2020). [0002] The decrease in non-renewable resources, such as oil, and the increase in pollution linked to these resources lead to the development of alternative solutions that are less polluting and more respectful of the environment. In particular, with regard to packaging, the European Commission wants 100% of packaging to be reusable, mechanically recyclable or compostable by 2030 (Circular Economy Action Plan - 2020).
[0003] Dans le secteur alimentaire, l’utilisation d’emballages en matières cellulosiques potentiellement recyclables, comme les emballages en papier ou en carton, se développe. Cependant, il existe encore des obstacles majeurs à la recyclabilité de ces emballages. Par ailleurs, l’utilisation de papier recyclé dans ces emballages peut également poser des problèmes de sécurité des consommateurs. [0003] In the food sector, the use of packaging made of potentially recyclable cellulosic materials, such as paper or cardboard packaging, is growing. However, there are still major obstacles to the recyclability of such packaging. In addition, the use of recycled paper in such packaging can also pose consumer safety issues.
[0004] En effet, les emballages à usage unique pour les plats à emporter et la restauration rapide ont toujours une couche de plastique comme barrière anti-graisse, généralement en polyamide (PA) ou en substances perfluoroalkylées (PFAS), pour la commodité des consommateurs. Cela représente 65k tonnes jetées en Europe chaque année (pour 2025 millions emballages unitaires produits). [0004] In fact, single-use packaging for takeaway meals and fast food always has a layer of plastic as a grease barrier, generally made of polyamide (PA) or perfluoroalkylated substances (PFAS), for the convenience of consumers. consumers. This represents 65k tons thrown away in Europe each year (for 2025 million unit packaging produced).
[0005] Par ailleurs, 17% des emballages en papier sont pourvus d'une couche de plastique, pour conférer une barrière aux gaz, aux graisses ou à l’eau (en PE, PP, PET, PVDC, EVOH, ou PVOH) pour montrer la nourriture à l'intérieur, ou pour permettre la soudabilité (fermeture de l’emballage). [0005] In addition, 17% of paper packaging is provided with a layer of plastic, to provide a barrier to gases, fats or water (in PE, PP, PET, PVDC, EVOH, or PVOH) to show the food inside, or to allow sealability (closing the package).
[0006] De plus, le papier recyclé ne peut pas être utilisé en contact direct avec les aliments, en raison de la migration des huiles minérales provenant des encres utilisées dans le papier précédent, par exemples dans des journaux. Une couche de plastique doit à nouveau être utilisée comme barrière pour la sécurité des consommateurs. Cela empêche une utilisation généralisée du papier recyclé dans les emballages alimentaires. [0006] In addition, recycled paper cannot be used in direct contact with food, due to the migration of mineral oils from the inks used in the previous paper, for example in newspapers. A layer of plastic must again be used as a barrier for consumer safety. This prevents widespread use of recycled paper in food packaging.
[0007] Lorsque ces emballages sont triés, l'enlèvement de la couche de plastique du papier dans les centres de recyclage est un véritable problème qui se traduit au mieux par la perte de 10 à 20 % des fibres de papier et au pire par la pollution des lots de fibres par des plastiques qui doivent alors être brûlés ou enfouis. [0008] Il est donc nécessaire de développer des emballages pouvant parer à ces désavantages. [0007] When these packages are sorted, the removal of the plastic layer from the paper in the recycling centers is a real problem which results at best in the loss of 10 to 20% of the paper fibers and at worst in the pollution of the batches of fibers by plastics which must then be burned or buried. [0008] It is therefore necessary to develop packaging that can overcome these disadvantages.
[0009] Dans ce contexte, la présente invention vise à satisfaire au moins l’un des objectifs suivants. In this context, the present invention aims to satisfy at least one of the following objectives.
[0010] Un des objectifs de la présente invention est la fourniture d’un matériau recyclable pouvant être utilisé comme emballage. One of the objectives of the present invention is to provide a recyclable material that can be used as packaging.
[0011] Un des objectifs de la présente invention est la fourniture d’un matériau recyclable biosourcé pouvant être utilisé comme emballage. [0011] One of the objectives of the present invention is to provide a bio-based recyclable material that can be used as packaging.
[0012] Un des objectifs de la présente invention est la fourniture d’un matériau recyclable pouvant être utilisé comme emballage dans le secteur alimentaire. One of the objectives of the present invention is to provide a recyclable material that can be used as packaging in the food sector.
[0013] Un des objectifs de la présente invention est la fourniture d’un matériau biodégradable pouvant être utilisé comme emballage. One of the objectives of the present invention is to provide a biodegradable material that can be used as packaging.
[0014] Un autre objectif de la présente invention est la fourniture d’un matériau à base de matières cellulosiques, ayant des propriétés barrières améliorées. Another object of the present invention is to provide a material based on cellulosic materials, having improved barrier properties.
[0015] Un des objectifs de la présente invention est la fourniture d’un matériau recyclable pouvant être produit facilement. [0015] One of the objectives of the present invention is to provide a recyclable material that can be easily produced.
Résumé Summary
[0016] La présente divulgation a pour objet un matériau multicouche comprenant : i) Au moins une couche de matériau cellulosique A, et ii) Au moins une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b). The subject of the present disclosure is a multilayer material comprising: i) At least one layer of cellulosic material A, and ii) At least one layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b).
[0017] La présente divulgation a également pour objet un matériau multicouche obtenu : The present disclosure also relates to a multilayer material obtained:
- soit par enduction d’une couche de matériau cellulosique A avec une solution S comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b) ; - either by coating a layer of cellulosic material A with a solution S comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b);
- soit par assemblage d’une couche de matériau cellulosique A et d’une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b), éventuellement au moyen d’un liant, l’assemblage étant de préférence effectué par complexage ou lamination. [0018] La présente divulgation a également pour objet un emballage comprenant un matériau multicouche. - either by assembling a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), optionally by means of a binder, the assembly being preferably carried out by lamination or lamination. [0018] The present disclosure also relates to a packaging comprising a multilayer material.
[0019] La présente divulgation a également pour objet un produit emballé par un emballage comprenant un matériau multicouche. The present disclosure also relates to a product packaged by packaging comprising a multilayer material.
[0020] La présente divulgation a également pour objet un procédé de fabrication d’un matériau multicouche, ledit procédé étant effectué The present disclosure also relates to a method for manufacturing a multilayer material, said method being carried out
- soit par enduction d’une couche de matériau cellulosique A avec une solution comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b) ; - either by coating a layer of cellulosic material A with a solution comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b);
- soit par assemblage d’une couche de matériau cellulosique A et d’une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b), éventuellement au moyen d’un liant, l’assemblage étant de préférence effectué par complexage ou lamination. - either by assembling a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), possibly by means of a binder, the assembly being preferably carried out by lamination or lamination.
[0021] Les inventeurs ont découvert qu’un tel matériau multicouche pouvait être utilisé comme emballage. En effet, ce matériau multicouche peut être recyclé dans les centres de recyclage sans modification de lignes ou de procédé car la couche de matériau B est hydrosoluble. Les centres de recyclage pourront récupérer près de 100 % des fibres de matériau cellulosique grâce à une simple filtration mécanique. Les résidus du matériau B issus de sa solubilisation seront biodégradés dans les infrastructures de traitement de l’eau déjà en place au sein des usines de recyclage. Le fait que les résidus du matériau B soient biodégradables permet d’éviter la pollution liée aux microplastiques. [0021] The inventors have discovered that such a multilayer material could be used as packaging. Indeed, this multilayer material can be recycled in recycling centers without modifying lines or processes because the layer of material B is water-soluble. Recycling centers will be able to recover nearly 100% of cellulosic material fibers through simple mechanical filtration. The residues of material B resulting from its solubilization will be biodegraded in the water treatment infrastructures already in place within the recycling plants. The fact that the residues of material B are biodegradable makes it possible to avoid pollution linked to microplastics.
[0022] De plus, la présence d’une couche de matériau B permet d’améliorer les propriétés barrières du matériau multicouche, en particulier les propriétés barrières aux graisses et à l’oxygène, ce qui permet d’envisager une utilisation dans le domaine de l’emballage alimentaire. [0022] In addition, the presence of a layer of material B makes it possible to improve the barrier properties of the multilayer material, in particular the barrier properties to greases and to oxygen, which makes it possible to envisage use in the field food packaging.
[0023] Le matériau multicouche selon l’invention possède également de bonnes propriétés de soudabilité, et notamment de thermoscellabilité. The multilayer material according to the invention also has good weldability properties, and in particular heat-sealability.
[0024] Ainsi, le matériau multicouche selon l’invention combine une bonne recyclabilité, des propriétés barrières améliorées et de bonnes propriétés de soudabilité, ce qui permet de l’utiliser comme emballage, notamment dans le domaine alimentaire. Thus, the multilayer material according to the invention combines good recyclability, improved barrier properties and good weldability properties, which allows it to be used as packaging, in particular in the food sector.
[0025] Par ailleurs, le matériau B est sans danger pour le contact alimentaire, renouvelable à 100%, compostable et biodégradable en milieu marin, ce qui n’est pas le cas de la plupart des polymères utilisés dans les emballages. La caséine est un ingrédient existant, documenté de l'industrie alimentaire, et facilement industrialisable. Le matériau multicouche peut donc être produit facilement. [0025] Furthermore, material B is safe for food contact, 100% renewable, compostable and biodegradable in the marine environment, which is not the case for most polymers. used in packaging. Casein is an existing ingredient, documented in the food industry, and easily industrialisable. The multilayer material can therefore be produced easily.
Description détaillée detailed description
[0026] Sauf mention contraire, dans tout le présent document, les % sont exprimés en % en poids. [0026] Unless otherwise stated, throughout this document, the % are expressed in % by weight.
[0027] Par « emballage », on entend un objet destiné à contenir et à protéger des marchandises, à permettre leur manutention et leur acheminement du producteur au consommateur ou à l’utilisateur, et à assurer leur présentation, leur conservation, leur protection et/ou leur utilisation. [0027] By "packaging" is meant an object intended to contain and protect goods, to allow their handling and their transport from the producer to the consumer or to the user, and to ensure their presentation, their conservation, their protection and /or their use.
[0028] Par “matériau cellulosique” on entend, par exemple, un matériau qui peut être dérivé d’une pâte de cellulose. Cette pâte de cellulose peut être produite par un traitement chimique et/ou mécanique, qui est bien connu de l’homme du métier. Cette pâte de cellulose peut être dérivée de toute source appropriée telle que du bois, du bois recyclé, des plantes annuelles, des résidus agricoles (bagasse, pailles, ...), des herbes (par exemple, la canne à sucre, le bambou) ou des cartons. [0028] By “cellulosic material” is meant, for example, a material which can be derived from a cellulose pulp. This cellulose pulp can be produced by chemical and/or mechanical treatment, which is well known to those skilled in the art. This cellulose pulp can be derived from any suitable source such as wood, recycled wood, annual plants, agricultural residues (bagasse, straws, ...), grasses (eg sugar cane, bamboo ) or boxes.
[0029] Par « thermoplastique », on entend, par exemple, une matière qui devient malléable et pliable au-dessus d’une température donnée, la température de transition vitreuse Tg, mais qui en dessous de cette Tg redevient dure, ces transformations étant réversibles. [0029] By "thermoplastic" is meant, for example, a material which becomes malleable and bendable above a given temperature, the glass transition temperature Tg, but which below this Tg becomes hard again, these transformations being reversible.
[0030] Par « biodégradable », on entend, par exemple, un matériau qui peut être décomposé sous l’action de micro-organismes (bactéries, champignons, algues...). Le résultat de cette décomposition est la formation d’eau, de CO2 et/ou de méthane et éventuellement de sous-produits (résidus, nouvelle biomasse) non toxiques pour l’environnement. Il s’agit, par exemple, d’un matériau biodégradable selon la norme européenne EN NF 13432 et/ou la norme NF T 51-800. [0030] By "biodegradable" is meant, for example, a material which can be decomposed under the action of microorganisms (bacteria, fungi, algae, etc.). 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 and/or standard NF T 51-800.
[0031] Par « entre x et y », on entend, par exemple, que les bornes x et y sont incluses dans l’intervalle [x, y]. [0031] By “between x and y”, it is meant, for example, that the limits x and y are included in the interval [x, y].
[0032] Par « hydrosoluble », on entend, par exemple, qui se dissout dans l’eau. L’hydrosolubilité d’un matériau peut être mesurée de la façon suivante : un morceau de film (5 cm x 5 cm, découpé avec un emporte-pièce) est fixé sur un porte diapositive puis est plongé dans un bêcher de 1000 ml de capacité, contenant de 600 ml d'eau distillée à 20°C sous agitation, avec un barreau magnétique, à 300 tr/min. Le temps que met le film à se percer est mesuré. Le délitement du film entraîne la formation de particules de film. Le test dure 10 minutes au bout desquelles les particules sont passées dans un tamis de 0,5 mm pour vérifier la taille des particules. Lorsqu’il n’y a pas de particules dans le tamis, le film est considéré comme hydrosoluble. [0032] The term "water-soluble" means, for example, which dissolves in water. The water solubility of a material can be measured in the following way: 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 10 minutes after which the particles are passed through a 0.5 mm sieve to check the particle size. When there are no particles in the sieve, the film is considered water-soluble.
[0033] Par « plastifiant », on entend, par exemple, une substance permettant d’abaisser la température de transition vitreuse Tg du matériau. [0033] By "plasticizer" is meant, for example, a substance making it possible to lower the glass transition temperature Tg of the material.
[0034] Par « hydrophobe », on entend, par exemple, un composé ayant peu d’affinité avec l’eau et ayant tendance à ne pas s’y dissoudre. Typiquement, il s’agit d’un composé majoritairement apolaire. [0035] Par « hydrophile », on entend, par exemple, un composé ayant une affinité avec l’eau et ayant tendance à s’y dissoudre. Typiquement, il s’agit d’un composé ayant des groupements polaire capables de former des liaisons hydrogène. [0034] By "hydrophobic" is meant, for example, a compound having little affinity with water and having a tendency not to dissolve therein. Typically, it is a predominantly apolar compound. By “hydrophilic” is meant, for example, a compound having an affinity with water and having a tendency to dissolve therein. Typically, it is a compound having polar groups capable of forming hydrogen bonds.
[0036] Par « tensioactif » , on entend, par exemple, une molécule amphiphile, c’est-à-dire une molécule possédant à la fois des propriétés hydrophiles et hydrophobes. By “surfactant” is meant, for example, an amphiphilic molecule, that is to say a molecule possessing both hydrophilic and hydrophobic properties.
[0037] Par « HLB », on entend, par exemple, l’équilibre hydrophile-lipophile (en anglais : hydrophilic- lipophilic balance). La valeur de la HLB peut être calculée selon la méthode suivante : HLB=20 x (Masse molaire de la partie hydrophobe) / (Masse molaire de la molécule). By "HLB" is meant, for example, the hydrophilic-lipophilic balance (in English: hydrophilic-lipophilic balance). The HLB value can be calculated using the following method: HLB=20 x (Molar mass of the hydrophobic part) / (Molar mass of the molecule).
[0038] Par « acide gras », on entend, par exemple, un monoacide carboxylique aliphatique. [0038] By "fatty acid" is meant, for example, an aliphatic monocarboxylic acid.
[0039] Par « biosourcé », on entend, par exemple, un produit fabriqué à partir de matières d’origine biologique. [0039] By “biobased”, we mean, for example, a product made from materials of biological origin.
[0040] Par « liant », on entend, par exemple, un agent permettant de créer une couche de liaison entre la couche de matériau cellulosique A et la couche de matériau B. Le liant utilisé dans la présente invention peut être un liant classiquement utilisé dans la fabrication de matériaux multicouches et en particulier, de films multicouches. Parmi les liants on peut citer les colles hot-melt (thermofusibles en français). By “binder” is meant, for example, an agent making it possible to create a bonding layer between the layer of cellulosic material A and the layer of material B. The binder used in the present invention can be a binder conventionally used in the manufacture of multilayer materials and in particular of multilayer films. Among the binders we can mention hot-melt glues (thermofusibles in French).
Matériau multicouche Multi-layer material
[0041] L’invention concerne en premier lieu un matériau multicouche comprenant : i) Au moins une couche de matériau cellulosique A, et ii) Au moins une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b). The invention relates firstly to a multilayer material comprising: i) At least one layer of cellulosic material A, and ii) At least one layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b).
[0042] La présente divulgation a également pour objet un matériau multicouche obtenu : The present disclosure also relates to a multilayer material obtained:
- soit par enduction d’une couche de matériau cellulosique A avec une solution comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b) ; - either by coating a layer of cellulosic material A with a solution comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b);
- soit par assemblage d’une couche de matériau cellulosique A et d’une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b), éventuellement au moyen d’un liant, l’assemblage étant de préférence effectué par complexage ou lamination. - either by assembling a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), optionally by means of a binder, the assembly being preferably carried out by lamination or lamination.
[0043] Le matériau multicouche est de préférence recyclable et/ou biosourcé. Le matériau multicouche peut être recyclable selon la directive 2018/852/UE du 30 mai 2018. Selon un mode de réalisation, le matériau multicouche est compostable, de préférence selon la norme NF T 51-800. [0043] The multilayer material is preferably recyclable and/or biosourced. The multilayer material can be recyclable according to directive 2018/852/EU of May 30, 2018. According to one embodiment, the multilayer material is compostable, preferably according to standard NF T 51-800.
[0044] Le matériau multicouche peut avoir une épaisseur comprise entre 0,01 et 100 mm, de préférence entre 0,05 et 50 mm. The multilayer material may have a thickness of between 0.01 and 100 mm, preferably between 0.05 and 50 mm.
[0045] Le matériau cellulosique A est de préférence choisi parmi les papiers et les cartons. Selon un mode de réalisation, le matériau cellulosique A a un grammage compris entre 20 et 500 g/m2, de préférence compris entre 50 et 450 g/m2. Selon un mode de réalisation, le matériau cellulosique A est choisi parmi les papiers ayant un grammage compris entre 20 et 225 g/m2, et les cartons ayant un grammage compris entre 225 et 500 g/m2. The cellulosic material A is preferably chosen from paper and cardboard. According to one embodiment, cellulosic material A has a basis weight of between 20 and 500 g/m 2 , preferably between 50 and 450 g/m 2 . According to one embodiment, the cellulosic material A is chosen from papers having a weight of between 20 and 225 g/m 2 , and cardboard having a weight of between 225 and 500 g/m 2 .
[0046] La couche de matériau cellulosique A peut avoir une épaisseur comprise entre 0,01 et 50 mm, de préférence entre 0,05 et 20 mm. The layer of cellulosic material A may have a thickness of between 0.01 and 50 mm, preferably between 0.05 and 20 mm.
[0047] Le matériau cellulosique A comprend de la cellulose, de préférence au moins 80% en poids, et préférentiellement au moins 90% en poids. The cellulosic material A comprises cellulose, preferably at least 80% by weight, and preferably at least 90% by weight.
[0048] Le matériau cellulosique A peut être coloré et comprendre une couche pigmentaire. Le matériau cellulosique A peut comprendre une couche minérale, par exemple de type kaolin. The cellulosic material A can be colored and comprise a pigmentary layer. The cellulosic material A can comprise a mineral layer, for example of the kaolin type.
[0049] Le matériau B et/ou la solution S comprennent : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b). The material B and/or the solution S comprise: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b).
[0050] La caséine est une protéine issue du lait qui est peu soluble dans l’eau. Elle est principalement obtenue par précipitation en ajoutant au lait un acide (caséine acide) ou de la présure (caséine présure), ou par filtration (caséine miscellaire). La caséine consiste en un mélange de caséine a, caséine b et caséine k ayant des masses molaires comprises entre 19000 et 25000g/mol. Par caséinate, on entend, par exemple, un sel de caséine dont le contre cation est choisi dans le groupe comprenant -de préférence constitué par - calcium, potassium, ammonium, sodium et magnésium. [0050] Casein is a protein derived from milk which is poorly soluble in water. It is mainly obtained by precipitation by adding an acid (acid casein) or rennet (rennet casein) to the milk, or by filtration (miscellar casein). Casein consists of a mixture of a-casein, b-casein and k-casein with molar masses between 19,000 and 25,000 g/mol. By caseinate is meant, for example, a casein salt whose counter cation is chosen from the group comprising—preferably consisting of—calcium, potassium, ammonium, sodium and magnesium.
[0051] Selon un autre mode de réalisation, a) comprend au moins un caséinate, par exemple un caséinate de sodium, ou un mélange de caséinates. According to another embodiment, a) comprises at least one caseinate, for example a sodium caseinate, or a mixture of caseinates.
[0052] Selon un autre mode de réalisation, a) comprend un mélange de caséine et d’au moins un caséinate. Dans ce cas, le rapport en masse entre la caséine et le(s) caséinate(s) peut être compris entre 5/95 et 95/5, 20/80 et 80/20 ou 40/60 et 60/40. According to another embodiment, 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.
[0053] Le matériau B et/ou la solution S peuvent comprendre de la gélatine d). [0054] La gélatine est une protéine qui a un taux élevé de glycine et de proline. Elle est obtenue par hydrolyse partielle du collagène, principalement à partir de collagène contenu dans les peaux et les os d’animaux. Elle peut être de type A (elle provient alors d’un traitement à l’acide du collagène) ou de type B (elle provient alors d’un traitement basique du collagène). Elle peut également être obtenue par traitement enzymatique du collagène. La gélatine utilisée n’a, de préférence, pas été modifiée chimiquement. Selon un mode de réalisation de l’invention, la gélatine utilisée est de la gélatine alimentaire disponible dans le commerce ou de type B, elle peut être sous forme de feuillets, poudre ou granules. Avantageusement, la gélatine utilisée est de type B. The material B and/or the solution S can comprise gelatin d). [0054] Gelatin is a protein which has a high level of glycine and proline. It is obtained by partial hydrolysis of collagen, mainly from collagen contained in the skins and bones of animals. It can be type A (it then comes from an acid treatment of the collagen) or type B (it then comes from a basic treatment of the collagen). It can also be obtained by enzymatic treatment of collagen. The gelatin used has preferably not been chemically modified. According to one embodiment of the invention, the gelatin used is commercially available food gelatin or type B, it can be in the form of sheets, powder or granules. Advantageously, the gelatin used is of type B.
[0055] Le ratio des quantités a) : d), lorsque d) est présent, peut être compris entre 90 :10 et 20 :80, de préférence entre 75 :25 et 25 :75, et préférentiellement entre 60 :40 et 40 :60. Selon un mode de réalisation particulier, le ratio a) :d) est de 50 :50. Selon un mode de réalisation particulier, le ratio a) :d) est compris entre 55 :45 et 45 :55. The ratio of the quantities a): d), when d) is present, can be between 90:10 and 20:80, preferably between 75:25 and 25:75, and preferably between 60:40 and 40 :60. According to a particular embodiment, the ratio a):d) is 50:50. According to a particular embodiment, the ratio a):d) is between 55:45 and 45:55.
[0056] Le plastifiant c) peut être choisi parmi les polyols, les acétates de glycérol, les propionates de glycérol et leurs mélanges. The plasticizer c) can be chosen from polyols, glycerol acetates, glycerol propionates and mixtures thereof.
[0057] À titre d'exemples de polyols, on peut citer le glycérol, l’hexanetriol, les glycols, dont l’éthylène glycol, et les sucres et leurs dérivés. As examples of polyols, mention may be made of glycerol, hexanetriol, glycols, including ethylene glycol, and sugars and their derivatives.
[0058] À titre d'exemples de sucres, on peut citer les disaccharides, tels que le maltose, le lactose, le saccharose et les monosaccharides tels que le fructose. As examples of sugars, mention may be made of disaccharides such as maltose, lactose, sucrose and monosaccharides such as fructose.
[0059] Parmi les dérivés des sucres, on peut citer leurs dérivés hydrogénés tels que le sorbitol, le maltitol, le mannitol, et le xylitol, ou bien encore les produits de transformation de ces dérivés hydrogénés tels que le sorbitane. Among the sugar derivatives, mention may be made of their hydrogenated derivatives such as sorbitol, maltitol, mannitol, and xylitol, or even the transformation products of these hydrogenated derivatives such as sorbitan.
[0060] Selon un mode de réalisation, le plastifiant c) est choisi parmi le glycérol, le sorbitol, le mannitol, l’éthylène glycol et leurs mélanges. Préférentiellement, le plastifiant c) est choisi parmi le glycérol, le sorbitol, et leurs mélanges. Selon un mode de réalisation, le plastifiant c) est du glycérol. According to one embodiment, the plasticizer c) is chosen from glycerol, sorbitol, mannitol, ethylene glycol and mixtures thereof. Preferably, the plasticizer c) is chosen from glycerol, sorbitol, and mixtures thereof. According to one embodiment, the plasticizer c) is glycerol.
[0061] Le plastifiant c) peut contenir de l’eau résiduelle. The plasticizer c) may contain residual water.
[0062] Le plastifiant c) permet de baisser la viscosité du produit en augmentant la mobilité des chaînes moléculaires. The plasticizer c) makes it possible to lower the viscosity of the product by increasing the mobility of the molecular chains.
[0063] Avantageusement, le plastifiant c) est un plastifiant hydrophile. Advantageously, the plasticizer c) is a hydrophilic plasticizer.
[0064] Le matériau B et/ou la solution S peuvent comprendre en outre un agent hydrophobe e). L’agent hydrophobe e) peut être choisi parmi : The material B and/or the solution S may also comprise a hydrophobic agent e). The hydrophobic agent e) can be chosen from:
- les esters de polyacide carboxylique ; - polycarboxylic acid esters;
- les acides carboxyliques en C3-C33, de préférence les acides gras en C4-C28, et, encore plus préférentiellement les acides gras insaturés en C6-C28 ; - C3-C33 carboxylic acids, preferably C4-C28 fatty acids, and even more preferably C6-C28 unsaturated fatty acids;
- et leurs mélanges. - and mixtures thereof.
[0065] Les esters de polyacide carboxylique peuvent être issus d’au moins un polyacide carboxylique et d’au moins un alcool, de préférence un alcool en C1-C18. [0066] Parmi les polyacides carboxyliques préférentiellement retenus dans le cadre de l'invention, on peut citer l’acide citrique, l’acide hydroxycitrique, l’acide tartrique, l’acide malique, l’acide oxalique, l’acide malonique, l’acide succinique, l’acide glutarique, l’acide adipique, l’acide maléique, l’acide fumarique. [0067] Parmi les alcools privilégiés conformément à l'invention, on peut citer les alcools en C2-C6, comme par exemple l’éthanol, le n-propanol, G/so-propanol, le n-butanol et le tert- butanol. The polycarboxylic acid esters can be derived from at least one polycarboxylic acid and from at least one alcohol, preferably a C1-C18 alcohol. Among the polycarboxylic acids preferably retained in the context of the invention, mention may be made of citric acid, hydroxycitric acid, tartaric acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid. Among the preferred alcohols in accordance with the invention, mention may be made of C2-C6 alcohols, such as for example ethanol, n-propanol, G/so-propanol, n-butanol and tert-butanol. .
[0068] Selon un mode de réalisation, l’agent hydrophobe e) est choisi parmi le triéthyl citrate, le tributyl O-acétyl citrate, le tributyl citrate et leurs mélanges. According to one embodiment, the hydrophobic agent e) is chosen from triethyl citrate, tributyl O-acetyl citrate, tributyl citrate and mixtures thereof.
[0069] Selon un mode de réalisation, l’agent hydrophobe e) est un acide carboxylique en C3-C33, de préférence un acide gras en C4-C28, et, encore plus préférentiellement un acide gras insaturé en Ob- C28. According to one embodiment, the hydrophobic agent e) is a C3-C33 carboxylic acid, preferably a C4-C28 fatty acid, and even more preferably an Ob-C28 unsaturated fatty acid.
[0070] Parmi les acides gras en C4-C28 retenus dans le cadre de l'invention, on peut citer l’acide caprylique, l’acide caprique, l’acide laurique, l’acide myristique, l’acide palmitique, l’acide stéarique, et leurs mélanges. [0071] Parmi les acides gras insaturés en C6-C28 particulièrement intéressants, on peut citer l’acide palmitoléique, l’acide oléique, l’acide linoléique, et leurs mélanges. 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 mixtures thereof. Among the particularly interesting C6-C28 unsaturated fatty acids, mention may be made of palmitoleic acid, oleic acid, linoleic acid, and mixtures thereof.
[0072] Le matériau B et/ou la solution S peuvent comprendre en outre au moins un tensioactif f), de préférence choisi parmi les tensioactifs zwitterioniques dont la HLB est comprise entre 2 et 8. The material B and/or the solution S may also comprise at least one surfactant f), preferably chosen from zwitterionic surfactants whose HLB is between 2 and 8.
[0073] Parmi les tensioactifs préférés, on peut citer la lécithine et/ou ses analogues tels que les phosphonates diacétyléniques, et les polysorbates. Les polysorbates sont esters d’acides gras et de polyoxyéthylène sorbitane. Parmi les polysorbates, on peut citer le polysorbate 20, le polysorbate 40, le polysorbate 60, et le polysorbate 80. Among the preferred surfactants, mention may be made of lecithin and/or its analogues such as diacetylene phosphonates and polysorbates. Polysorbates are fatty acid esters of polyoxyethylene sorbitan. Among the polysorbates, mention may be made of polysorbate 20, polysorbate 40, polysorbate 60, and polysorbate 80.
[0074] Selon un mode de réalisation, le ratio des quantités de f) sur e) est supérieur ou égal à 1. Par exemple, ce ratio peut être compris entre 1 ,3 et 3; de préférence entre 1 ,5 est 2,5. [0075] Le matériau B et/ou la solution S peuvent comprendre en outre un polysaccharide g). De préférence g) est choisi parmi le pullulane, l’amidon, les alginates, et leurs mélanges. Le polysaccharide g) peut être un polysaccharide hydrosoluble. According to one embodiment, the ratio of the quantities of f) to e) is greater than or equal to 1. For example, this ratio may be between 1.3 and 3; preferably between 1.5 and 2.5. The material B and/or the solution S may also comprise a polysaccharide g). Preferably g) is chosen from pullulan, starch, alginates, and mixtures thereof. The polysaccharide g) can be a water-soluble polysaccharide.
[0076] Le matériau B et/ou la solution S peuvent comprendre en outre un agent amérisant h), de préférence le benzoate de dénatonium. [0077] L’agent amérisant h) peut être choisi parmi le benzoate de dénatonium, les dérivés du benzoate de dénatonium, le saccharide de dénatonium, le chlorure de dénatonium, le benzoate de saccharose, la quinine, le chlorhydrate de quinine, le sulfate de quinine, la brucine, le sulfate de brucine, le quassia, la quassine, la naringine, la limonine, le phénylthio-carbamide, le quebracho, l'octaacétate de saccharose, la quercétine, la berbérine, et leurs mélanges. [0078] Selon un mode de réalisation, le matériau B et/ou la solution S comprennent également un additif i) choisi parmi les colorants, les coagulants de protéines, les agents antiagglomérant, les agents de glissement et leurs mélanges. Parmi les coagulants, on peut citer l’acide citrique et l’acide acétique. Parmi les agents antiagglomérants, on peut citer la silice colloïdale. Parmi les agents de glissement, on peut citer les polyéthylènes glycols et les composés à chaînes grasses, de préférence en C12-C28, ayant une terminaison amide. [0079] Selon un mode de réalisation, le matériau B et/ou la solution S comprennent un additif j) choisi parmi les agents séquestrants. Par « agent séquestrant », on entend, par exemple, des ligands qui forment des complexes chimiques avec des ions métalliques tels que cuivre, fer, nickel, calcium et magnésium. Parmi les agents séquestrants, on peut citer le citrate diammonique, l’EDTA, les phosphates, l’acide citrique, les pyrophosphates, et leurs mélanges. [0080] Les proportions des différents constituants du matériau B sont exprimés en % en poids par rapport au poids total du matériau B à température ambiante. Selon un mode de réalisation, le matériau B comprend entre 10 et 80 % de caséine et/ou de caséinate a), de préférence entre 20 et 75 %, et, plus préférentiellement encore, entre 25 et 70%. The material B and/or the solution S can additionally comprise a bittering agent h), preferably denatonium benzoate. The bittering agent h) can be chosen from denatonium benzoate, derivatives of denatonium benzoate, denatonium saccharide, denatonium chloride, sucrose benzoate, quinine, quinine hydrochloride, sulphate quinine, brucine, brucine sulfate, quassia, quassine, naringin, limonine, phenylthiocarbamide, quebracho, sucrose octaacetate, quercetin, berberine, and mixtures thereof. According to one embodiment, the material B and/or the solution S also comprise an additive i) chosen from dyes, protein coagulants, anti-caking agents, slip agents and mixtures thereof. Among the coagulants, mention may be made of citric acid and acetic acid. Among the anti-caking agents, mention may be made of colloidal silica. Among the slip agents, mention may be made of polyethylene glycols and compounds with fatty chains, preferably C12-C28, having an amide terminus. According to one embodiment, the material B and/or the solution S comprise an additive j) chosen from sequestering agents. By "sequestering agent" is meant, for example, ligands which form chemical complexes with metal ions such as copper, iron, nickel, calcium and magnesium. Among the sequestering agents, mention may be made of diammonium citrate, EDTA, phosphates, citric acid, pyrophosphates, and mixtures thereof. The proportions of the various constituents of material B are expressed in % by weight relative to the total weight of material B at ambient temperature. According to one embodiment, material B comprises between 10 and 80% casein and/or caseinate a), preferably between 20 and 75%, and, even more preferably, between 25 and 70%.
[0081] Selon un mode de réalisation, le matériau B comprend entre 50 et 80 % de caséine et/ou de caséinate a), de préférence entre 52 et 75 %, et, plus préférentiellement encore, entre 55 et 70%. Selon un mode de réalisation, le matériau B comprend entre 10 et 55 % de caséine et/ou de caséinate a), de préférence entre 20 et 50 %, préférentiellement entre 25 et 40 %, et plus préférentiellement encore entre 30 et 35%. According to one embodiment, material B comprises between 50 and 80% casein and/or caseinate a), preferably between 52 and 75%, and, even more preferably, between 55 and 70%. According to one embodiment, material B comprises between 10 and 55% casein and/or caseinate a), preferably between 20 and 50%, preferably between 25 and 40%, and more preferably still between 30 and 35%.
[0082] Selon un mode de réalisation, le matériau B comprend entre 1 et 55% de gélatine d), de préférence entre 5 et 50 %, préférentiellement entre 10 et 40 %, et plus préférentiellement encore entre 30 et 35%. According to one embodiment, material B comprises between 1 and 55% gelatin d), preferably between 5 and 50%, preferably between 10 and 40%, and more preferably still between 30 and 35%.
[0083] Selon un mode de réalisation particulier, le matériau B comprend entre 30 et 35% de caséine et/ou de caséinate a), et entre 30 et 35% de gélatine d). According to one particular embodiment, material B comprises between 30 and 35% casein and/or caseinate a), and between 30 and 35% gelatin d).
[0084] Le matériau B peut comprendre entre 5 et 15% d’eau b), de préférence entre 7 et 11 %. La quantité d’eau peut être comprise entre 9 et 10%. L’eau agit comme un plastifiant qui doit être distingué du plastifiant c) entrant dans la composition du matériau B. The material B can comprise between 5 and 15% water b), preferably between 7 and 11%. The amount of water can be between 9 and 10%. Water acts as a plasticizer which must be distinguished from plasticizer c) entering into the composition of material B.
[0085] Le matériau B peut comprendre c) entre 10 et 35% d’au moins un plastifiant différent de c), de préférence entre 15 et 30%. The material B can comprise c) between 10 and 35% of at least one plasticizer different from c), preferably between 15 and 30%.
[0086] Le matériau B peut comprendre entre 0,1 et 8% d’un agent hydrophobe e), de préférence entre 1 et 4%. Avantageusement, Le matériau B comprend entre 0,5 et 6%, de préférence entre 1 et 3%, d'un agent hydrophobe e). The material B can comprise between 0.1 and 8% of a hydrophobic agent e), preferably between 1 and 4%. Advantageously, material B comprises between 0.5 and 6%, preferably between 1 and 3%, of a hydrophobic agent e).
[0087] Le matériau B peut comprendre entre 0,5 et 6% d’au moins un tensioactif f), de préférence choisi parmi les tensioactifs zwitterioniques dont la HLB est comprise entre 2 et 8. Avantageusement, le matériau B peut comprendre comprend entre 1 et 5% d’au moins un tensioactif f), de préférence entre 1 ,5 et 4,5 %, et encore plus préférentiellement entre 2 et 4%. [0088] Le matériau B peut comprendre entre 2 et 10 % d’un polysaccharide g), de préférence g) est choisi parmi le pullulane, l’amidon, les alginates, et leurs mélanges. Avantageusement, le matériau B comprend entre 4 et 8% d’un polysaccharide g). The material B can comprise between 0.5 and 6% of at least one surfactant f), preferably chosen from zwitterionic surfactants whose HLB is between 2 and 8. Advantageously, the material B can comprise comprises between 1 and 5% of at least one surfactant f), preferably between 1.5 and 4.5%, and even more preferably between 2 and 4%. The material B can comprise between 2 and 10% of a polysaccharide g), preferably g) is chosen from pullulan, starch, alginates, and mixtures thereof. Advantageously, material B comprises between 4 and 8% of a polysaccharide g).
[0089] Le matériau B peut comprendre entre 0,001 et 0,5 % d’un agent amérisant h), de préférence le benzoate de dénatonium. Avantageusement, le matériau B comprend en outre entre 0,05 et 0,15 % d’un agent amérisant h). Material B can comprise between 0.001 and 0.5% of a bittering agent h), preferably denatonium benzoate. Advantageously, material B also comprises between 0.05 and 0.15% of a bittering agent h).
[0090] Le matériau B peut comprendre entre 0,1% et 5% de i). Le matériau B peut comprendre entre 1 et 5% d’un additif j) choisi parmi les agents séquestrants. [0090] Material B can comprise between 0.1% and 5% of i). Material B can comprise between 1 and 5% of an additive j) chosen from sequestering agents.
[0091] Le matériau B peut être hydrosoluble et/ou biodégradable. Le matériau B peut être biosourcé. Selon un mode de réalisation, le matériau B est un matériau thermoplastique. Le matériau B peut être obtenu par extrusion, comme mentionné dans les exemples. [0091] Material B can be water-soluble and/or biodegradable. Material B can be biobased. According to one embodiment, material B is a thermoplastic material. Material B can be obtained by extrusion, as mentioned in the examples.
[0092] Selon un mode de réalisation, la couche de matériau B est une couche de film de matériau B, de préférence une couche de film de matériau B thermoplastique, biodégradable et hydrosoluble. Typiquement, la couche de film de matériau B a une épaisseur comprise entre 1 et 150 microns, de préférence entre 2 et 50 microns et plus préférentiellement entre 2,5 et 20 microns. According to one embodiment, the layer of material B is a layer of film of material B, preferably a layer of film of thermoplastic, biodegradable and water-soluble material B. Typically, the film layer of material B has a thickness of between 1 and 150 microns, preferably between 2 and 50 microns and more preferably between 2.5 and 20 microns.
[0093] Les proportions des différents constituants de la solution S sont exprimées en % en poids par rapport au poids total de la matière sèche dans la solution S. Selon un mode de réalisation, la solution S comprend entre 0,1 et 90% de matière sèche, de préférence entre 1 et 50 % de matière sèche, préférentiellement entre 5 et 25% de matière sèche, et plus préférentiellement entre 10 et 20% de matière sèche. La solution S peut être obtenue en solubilisant le matériau B dans de l’eau ou en solubilisant les différents composants dans de l’eau. The proportions of the various constituents of the solution S are expressed in % by weight relative to the total weight of the dry matter in the solution S. According to one embodiment, the solution S comprises between 0.1 and 90% of dry matter, preferably between 1 and 50% dry matter, preferably between 5 and 25% dry matter, and more preferably between 10 and 20% dry matter. Solution S can be obtained by dissolving material B in water or by dissolving the various components in water.
[0094] Selon un mode de réalisation, la solution S comprend entre 10 et 80 % de caséine et/ou de caséinate a), de préférence entre 20 et 75 %, et, plus préférentiellement encore, entre 25 et 70%. According to one embodiment, the solution S comprises between 10 and 80% casein and/or caseinate a), preferably between 20 and 75%, and, even more preferably, between 25 and 70%.
[0095] Selon un mode de réalisation, la solution S comprend entre 50 et 80 % de caséine et/ou de caséinate a), de préférence entre 52 et 75 %, et, plus préférentiellement encore, entre 55 et 70%. Selon un mode de réalisation, la solution S comprend entre 10 et 55 % de caséine et/ou de caséinate a), de préférence entre 20 et 50 %, préférentiellement entre 25 et 40 %, et plus préférentiellement encore entre 30 et 35%. According to one embodiment, the solution S comprises between 50 and 80% casein and/or caseinate a), preferably between 52 and 75%, and, even more preferably, between 55 and 70%. According to one embodiment, the solution S comprises between 10 and 55% casein and/or caseinate a), preferably between 20 and 50%, preferably between 25 and 40%, and more preferably still between 30 and 35%.
[0096] Selon un mode de réalisation, la solution S comprend entre 1 et 55% de gélatine d), de préférence entre 5 et 50 %, préférentiellement entre 10 et 40 %, et plus préférentiellement encore entre 30 et 35%. According to one embodiment, the solution S comprises between 1 and 55% of gelatin d), preferably between 5 and 50%, preferably between 10 and 40%, and even more preferably between 30 and 35%.
[0097] Selon un mode de réalisation particulier, la solution S comprend entre 30 et 35% de caséine et/ou de caséinate a), et entre 30 et 35% de gélatine d). According to a particular embodiment, the solution S comprises between 30 and 35% casein and/or caseinate a), and between 30 and 35% gelatin d).
[0098] La solution S peut comprendre c) entre 10 et 35% d’au moins un plastifiant différent de c), de préférence entre 15 et 30%. [0099] La solution S peut comprendre entre 0,1 et 8% d’un agent hydrophobe e), de préférence entre 1 et 4%. Avantageusement, la solution S comprend entre 0,5 et 6%, de préférence entre 1 et 3%, d'un agent hydrophobe e). The solution S can comprise c) between 10 and 35% of at least one plasticizer different from c), preferably between 15 and 30%. The solution S can comprise between 0.1 and 8% of a hydrophobic agent e), preferably between 1 and 4%. Advantageously, the solution S comprises between 0.5 and 6%, preferably between 1 and 3%, of a hydrophobic agent e).
[0100] La solution S peut comprendre entre 0,5 et 6% d’au moins un tensioactif f), de préférence choisi parmi les tensioactifs zwitterioniques dont la HLB est comprise entre 2 et 8. Avantageusement, la solution S peut comprendre comprend entre 1 et 5% d’au moins un tensioactif f), de préférence entre 1 ,5 et 4,5 %, et encore plus préférentiellement entre 2 et 4%. The solution S can comprise between 0.5 and 6% of at least one surfactant f), preferably chosen from zwitterionic surfactants whose HLB is between 2 and 8. Advantageously, the solution S can comprise comprises between 1 and 5% of at least one surfactant f), preferably between 1.5 and 4.5%, and even more preferably between 2 and 4%.
[0101] La solution S peut comprendre entre 2 et 10 % d’un polysaccharide g), de préférence g) est choisi parmi le pullulane, l’amidon, les alginates, et leurs mélanges. Avantageusement, la solution S comprend entre 4 et 8% d’un polysaccharide g). The solution S can comprise between 2 and 10% of a polysaccharide g), preferably g) is chosen from pullulan, starch, alginates, and mixtures thereof. Advantageously, the solution S comprises between 4 and 8% of a polysaccharide g).
[0102] La solution S peut comprendre entre 0,001 et 0,5 % d’un agent amérisant h), de préférence le benzoate de dénatonium. Avantageusement, la solution S comprend en outre entre 0,05 et 0,15 % d’un agent amérisant h). The solution S can comprise between 0.001 and 0.5% of a bittering agent h), preferably denatonium benzoate. Advantageously, the solution S further comprises between 0.05 and 0.15% of a bittering agent h).
[0103] La solution S peut comprendre entre 0,1% et 5% de i). La solution S peut comprendre entre 1 et 5% d’un additif j) choisi parmi les agents séquestrants. The solution S can comprise between 0.1% and 5% of i). The solution S can comprise between 1 and 5% of an additive j) chosen from sequestering agents.
[0104] La solution S peut également contenir un agent conservateur et/ou un biocide. La concentration en agent conservateur et/ou un biocide peut être comprise entre 0,1 et 5%. The solution S can also contain a preservative and/or a biocide. The concentration of preservative and/or a biocide can be between 0.1 and 5%.
Emballage comprenant un matériau multicouche Packaging comprising multi-layer material
[0105] La présente divulgation a également pour objet un emballage comprenant un matériau multicouche. Dans certains cas, l’emballage comprend d’autres couches que le matériau multicouche, dans d’autres cas, l’emballage est constitué du matériau multicouche. The present disclosure also relates to a packaging comprising a multilayer material. In some cases, the packaging includes other layers than the multilayer material, in other cases the packaging consists of the multilayer material.
[0106] La présente divulgation a également pour objet l’utilisation d’un matériau multicouche pour emballer des produits divers (pharmaceutiques, alimentaires, chimiques, cosmétiques,...). The present disclosure also relates to the use of a multilayer material for packaging various products (pharmaceuticals, food, chemicals, cosmetics, etc.).
[0107] La présente divulgation a également pour objet un produit emballé par un emballage comprenant un matériau multicouche. The present disclosure also relates to a product packaged by packaging comprising a multilayer material.
[0108] Le produit peut être sous forme solide, liquide ou sous forme de gel. Le produit emballé peut être n’importe quel objet, par exemple il peut s’agir d’une pièce mécanique, d’un objet de bricolage, d’un objet de jardinage, d’un magazine, d’un journal, ou de vaisselle jetable. The product can be in solid, liquid or gel form. The packaged product can be any object, for example it can be a mechanical part, a do-it-yourself object, a gardening object, a magazine, a newspaper, or disposable dishes.
[0109] Le produit emballé peut par exemple être choisi parmi les produits pharmaceutiques, alimentaires, chimiques, et cosmétiques. The packaged product can for example be chosen from among pharmaceutical, food, chemical and cosmetic products.
[0110] Selon un mode de réalisation, le produit emballé est un produit alimentaire, comme par exemple de la viande, du poisson, des légumes, des fruits, des pâtisseries, des viennoiseries, du chocolat, des confiseries, des additifs alimentaires, des ingrédients, des préparations sèches, des poudres alimentaires, des plats préparés. According to one embodiment, the packaged product is a food product, such as for example meat, fish, vegetables, fruits, pastries, pastries, chocolate, confectionery, food additives, ingredients, dry preparations, food powders, ready meals.
[0111] Selon un mode de réalisation, le produit emballé est un produit cosmétique. Selon un mode de réalisation, le produit emballé est un détergent. [0112] Les détergents peuvent se trouver sous forme de liquide ou de poudre, compacte ou non. Par exemple, il peut s’agir d’une tablette de détergent. Parmi les tablettes de détergent, on peut citer les tablettes de produit pour lave-vaisselle et les tablettes de lessive. Il peut également s’agir de détergent liquide, comme de la lessive liquide. Procédé de fabrication d’un matériau multicouche [0111] According to one embodiment, the packaged product is a cosmetic product. According to one embodiment, the packaged product is a detergent. The detergents can be in the form of liquid or powder, compact or not. For example, it may be a detergent tablet. Detergent tablets include dishwasher detergent tablets and laundry detergent tablets. It can also be liquid detergent, such as liquid laundry detergent. Method of manufacturing a multilayer material
[0113] Le matériau multicouche peut être fabriqué par des procédés de lamination, d’enduction, de contre-collage, de co-extrusion ou d’extrusion couchage bien connus par l’homme du métier. The multilayer material can be manufactured by lamination, coating, lamination, co-extrusion or coating extrusion processes well known to those skilled in the art.
[0114] La présente divulgation a également pour objet un procédé de fabrication d’un matériau multicouche, caractérisé en ce qu’il est effectué - soit par enduction d’une couche de matériau cellulosique A avec une solution S comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b) ; The present disclosure also relates to a method for manufacturing a multilayer material, characterized in that it is carried out - either by coating a layer of cellulosic material A with a solution S comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b);
- soit par assemblage d’une couche de matériau cellulosique A et d’une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b), éventuellement au moyen d’un liant, l’assemblage étant de préférence effectué par complexage ou lamination. - either by assembling a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), possibly by means of a binder, the assembly being preferably carried out by lamination or lamination.
[0115] Selon un mode de réalisation, la fabrication du matériau multicouche est réalisée par enduction. Dans ce cas, la couche de matériau cellulosique A est revêtue avec une solution S. Cela peut être fait en utilisant un matériel de couchage bien connu de l’homme du métier. Après enduction, le matériau cellulosique A revêtu peut être séché, par exemple dans une étuve, afin d’obtenir le matériau multicouche. According to one embodiment, the manufacture of the multilayer material is carried out by coating. In this case, the layer of cellulosic material A is coated with a solution S. This can be done using a coating material well known to those skilled in the art. After coating, the coated cellulosic material A can be dried, for example in an oven, in order to obtain the multilayer material.
[0116] Selon un autre mode de réalisation, la fabrication du matériau multicouche est réalisée par assemblage d’une couche de matériau cellulosique A et d’une couche de matériau B. Dans ce cas, l’assemblage peut être effectué par complexage ou lamination. According to another embodiment, the manufacture of the multilayer material is carried out by assembling a layer of cellulosic material A and a layer of material B. In this case, the assembly can be carried out by lamination or lamination .
[0117] La lamination peut être effectuée à froid ou à chaud. Dans le cas d’une lamination à froid, un liant peut être utilisé. Dans le cas d’une lamination à chaud, cette étape peut être effectuée sans liant. The lamination can be carried out cold or hot. In the case of cold lamination, a binder can be used. In the case of hot lamination, this step can be carried out without a binder.
[0118] La complexation peut être effectuée par une étape de contre-collage, de co-extrusion ou d’extrusion couchage, avec ou sans liant. The complexation can be carried out by a step of lamination, co-extrusion or coating extrusion, with or without a binder.
[0119] Lorsqu’un liant est utilisé, l’assemblage peut par exemple être effectué en enduisant une des faces d’un des matériaux A ou B avec un liant, puis en mettant en contact les deux matériaux de façon que le liant se retrouve entre les deux matériaux. Cet assemblage peut être effectué au moyen d’une calandre. When a binder is used, the assembly can for example be carried out by coating one of the faces of one of the materials A or B with a binder, then by bringing the two materials into contact. so that the binder is found between the two materials. This assembly can be carried out by means of a calender.
EXEMPLES EXAMPLES
[0120] Dans les exemples ci-après, deux types de matériaux cellulosiques (papiers) ont été enduits avec une solution de caséinate de sodium et de glycérol, préparée à partir de granulés thermoplastiques, afin de préparer un matériau multicouche selon l’invention. Sauf mention contraire, dans tout le présent document, les % sont exprimés en % en poids. In the examples below, two types of cellulosic materials (papers) were coated with a solution of sodium caseinate and glycerol, prepared from thermoplastic granules, in order to prepare a multilayer material according to the invention. Unless otherwise stated, throughout this document, the % are expressed in % by weight.
[0121] Les matériaux cellulosiques utilisés sont les suivants : The cellulosic materials used are as follows:
- Papier Algro Sol PCC 90g/m2 en provenance de Sappi, papier Kraft enduit d’un kaolin sur une face, Format 21*35cm, enduction sur la face brillante, - Algro Sol PCC 90g/m 2 paper from Sappi, Kraft paper coated with kaolin on one side, Format 21*35cm, coating on the shiny side,
- Papier Terrana 85g/m2 en provenance de Gascogne Papier, papier kraft naturel frictionné sur 1 face, enduction de la face frictionnée, Format 21*35cm - Terrana 85g/m2 paper from Gascogne Paper, natural kraft paper rubbed on one side, coating of the rubbed side, Format 21*35cm
[0122] Les granulés thermoplastiques utilisés pour l’enduction ont été préparés par extrusion à partir de caséinate de sodium. L’extrudeuse utilisée est une extrudeuse bi-vis corotative BC 21 de marque Clextral®, de diamètre 25 mm, d'entraxe 21 mm et de longueur 900 mm. Cette extrudeuse comporte au moins 4 zones : une première zone d’introduction, une deuxième zone d’introduction, une troisième zone de dégazage, et une quatrième zone de filière. The thermoplastic granules used for the coating were prepared by extrusion from sodium caseinate. The extruder used is a Clextral® BC 21 co-rotating twin-screw extruder, with a diameter of 25 mm, a center distance of 21 mm and a length of 900 mm. This extruder has at least 4 zones: a first introduction zone, a second introduction zone, a third degassing zone, and a fourth die zone.
[0123] La vitesse de rotation des bi-vis est comprise entre 175 et 320 tr/min et les températures des différentes zones sont comprises entre 30 et 120°C. The rotational speed of the twin screws is between 175 and 320 rpm and the temperatures of the different zones are between 30 and 120°C.
La première zone de l'extrudeuse est une zone d'introduction des poudres : caséinate et lécithine. Les liquides sont introduits dans la deuxième zone. L'extrudeuse comporte en outre une zone de dégazage à l'air libre et une dernière zone consistant en une filière jonc cylindrique de diamètre 4 mm. The first zone of the extruder is a powder introduction zone: caseinate and lecithin. The liquids are introduced into the second zone. The extruder further comprises a degassing zone in the open air and a final zone consisting of a cylindrical rod die with a diameter of 4 mm.
Le profil de vis est le suivant : 750 mm de vis à pas direct, 50 mm de vis de mélangeage, 100 mm de vis à pas inverse. The auger profile is as follows: 750 mm direct pitch auger, 50 mm mixing auger, 100 mm reverse pitch auger.
A la sortie de l'extrudeuse, le jonc est séché et introduit dans un granulateur pour donner des granulés de 2 à 3 mm de diamètre. La composition finale des granulés est la suivante : On leaving the extruder, the rod is dried and introduced into a granulator to give granules 2 to 3 mm in diameter. The final composition of the pellets is as follows:
63 % de caséinate de sodium, 63% sodium caseinate,
23,5 % de glycérol, 23.5% glycerol,
10 % d’eau, 10% water,
2,3 % de lécithine de soja, et 1 ,1 % d’acide oléique. 2.3% soy lecithin, and 1.1% oleic acid.
Enduction des papiers Coating of papers
[0124] Dissolution des granulés thermoplastiques dans de l’eau sous agitation, pour obtenir une solution à 11%, 18% ou 19% matière sèche. [0125] L’enduction des papiers avec la solution a été réalisée avec un matériel de couchage de laboratoire, un Elcometer qui permet la translation d’une barre filetée afin d’étaler et de doser une solution à la surface d’un papier. 2 passages d’enduction sur la même face de chacun des papiers ont été réalisés, de manière à obtenir un poids de couche de 9 ou 14g/m2. Les résultats obtenus sont présentés dans le tableau 1. [0124] Dissolution of the thermoplastic granules in water with stirring, to obtain an 11%, 18% or 19% dry matter solution. The coating of the papers with the solution was carried out with laboratory coating equipment, an Elcometer which allows the translation of a threaded bar in order to spread and dose a solution on the surface of a paper. 2 coating passes on the same face of each of the papers were carried out, so as to obtain a layer weight of 9 or 14 g/m 2 . The results obtained are shown in Table 1.
[0126] [Tableau 1] [0126] [Table 1]
Ό127] Les feuilles de papier enduites sont ensuite séchées à l’étuve à 55°C puis sous un sécheur demi-lune à 80°C. Elles sont ensuite placées sous une plaque métallique lourde. Ό127] The coated sheets of paper are then dried in an oven at 55°C and then under a half-moon dryer at 80°C. They are then placed under a heavy metal plate.
Caractérisation des papiers enduits obtenus [0128] Propriétés physiques Characterization of the coated papers obtained [0128] Physical properties
[0129] Grammage et épaisseur [0129] Grammage and thickness
[0130] La caractérisation des papiers supports sans enduction et des papiers enduits a été réalisée dans des conditions normalisées à 23°C- 50% HR (NF EN 20 187, 1993). La mesure du grammage a été réalisée selon la méthode décrite dans la norme NF EN ISO 536, 2012, et la mesure de l’épaisseur selon la méthode décrite dans la norme NF EN ISO 534, 2011. Les résultats obtenus sont en adéquation avec les valeurs attendues et correspondent aux différentes déposes réalisées sur les 2 papiers. The characterization of the support papers without coating and of the coated papers was carried out under standardized conditions at 23° C.-50% RH (NF EN 20 187, 1993). The weight measurement was carried out according to the method described in the NF EN ISO 536, 2012 standard, and the thickness measurement according to the method described in the NF EN ISO 534, 2011 standard. The results obtained are in line with the expected values and correspond to the different deposits made on the 2 papers.
[0131] Test d’adhésion Méthode FINAT [0131] Adhesion test FINAT method
[0132] Une bonne adhésion entre la couche de matériau B comprenant du caséinate de sodium, et la couche de papier A en matériau cellulosique est recherchée. Good adhesion between the layer of material B comprising sodium caseinate, and the layer of paper A made of cellulosic material is desired.
[0133] L’adhésion de la couche enduite sur le papier a été testée selon la méthode Finat 1 : Pour pouvoir réaliser le test dans de bonnes conditions, une amorce doit être faite sur les échantillons, manuellement ou avec du scotch, afin de séparer l’enduction du support et ainsi réaliser le pelage de la couche. Or il n’a pas été possible de créer cette amorce, l’adhésion entre la couche enduite enduction et le support papier étant trop forte. [0133] The adhesion of the coated layer to the paper was tested according to the Finat 1 method: In order to be able to carry out the test under good conditions, a primer must be made on the samples, manually or with tape, in order to separate the coating of the support and thus achieve the peeling of the layer. However, it was not possible to create this primer, the adhesion between the coated layer and the paper support being too strong.
[0134] L’adhésion a ensuite été testée selon la méthode Finat 3 : Dans cette méthode, le support enduit est collé au moyen de scotch sur une plaque. Les éprouvettes ainsi préparées sont réalisées en respectant la méthode Finat 3, à savoir : maintien pendant 20 heures à 23°C sous une pression de 6.86 kPa (70 g/cm2) de l’ensemble plaque/ scotch/papier enduit. Comme dans la méthode Finat 1, aucune délamination entre la couche enduite et le support papier n’a été observé. En effet, la délamination s’est produite au niveau du scotch. The adhesion was then tested according to the Finat 3 method: In this method, the coated support is glued using tape to a plate. The specimens prepared in this way are produced in compliance with the Finat 3 method, namely: maintenance for 20 hours at 23° C. under a pressure of 6.86 kPa (70 g/cm2) of the plate/tape/coated paper assembly. As in the Finat method 1, no delamination between the coated layer and the paper backing was observed. Indeed, the delamination occurred at the level of the tape.
[0135] Ces tests montrent que la couche déposée en surface adhère très bien au support papier, à tel point qu’il n’est pas possible de mesurer la force de pelage. L’adhésion de la couche enduite aux différents supports est très bonne, quel que soit le poids de couche déposés (9 ou 14g/m2). These tests show that the layer deposited on the surface adheres very well to the paper support, to such an extent that it is not possible to measure the peel force. The adhesion of the coated layer to the various supports is very good, whatever the weight of the layer deposited (9 or 14 g/m 2 ).
[0136] Propriétés barrières [0136] Barrier properties
[0137] Barrières aux graisses : Méthode de mesure de l’indice Cobb à l’huile [0137] Grease barriers: Method for measuring the Cobb index with oil
[0138] La mesure de l’indice Cobb est réalisé sur une surface de 25 cm2 et sa durée est fixée ici à 60 sec. De l’huile ISIO 4 colorée avec du rouge Soudan III est utilisée, ce qui permet de visualiser les défauts lorsqu’ils sont présents. Une méthode dérivée de la norme SCAN-P 37 est utilisée. La mesure de l’indice Cobb permet de déterminer la quantité d’huile que peut absorber la surface d’un papier ou d’un carton pendant un temps déterminé, ici 60s. Un indice Cobb le plus bas possible est recherché. The measurement of the Cobb index is carried out on a surface of 25 cm 2 and its duration is fixed here at 60 sec. ISIO 4 oil colored with Sudan red III is used, which makes it possible to visualize the defects when they are present. A method derived from the SCAN-P 37 standard is used. The measurement of the Cobb index makes it possible to determine the quantity of oil that the surface of a paper or cardboard can absorb for a given time, here 60s. The lowest possible Cobb index is sought.
[0139] Les mesures sont effectuées sur 5 échantillons différents. On réalise ensuite une moyenne et l’écart-type. Les mesures sont effectuées à 23°C / 50%HR après un séjour des échantillons dans ces conditions pendant au moins 12 heures. Les résultats sont présentés dans le tableau 2. The measurements are carried out on 5 different samples. We then calculate the mean and the standard deviation. The measurements are carried out at 23° C. / 50% RH after the samples have remained under these conditions for at least 12 hours. The results are shown in Table 2.
[0140] [Tableau 2] [0140] [Table 2]
Ό141] Ces résultats montrent que les matériaux multicouches selon l’invention ont un indice Cobb beaucoup plus bas que les supports papiers non-enduits, ce qui traduit une amélioration des propriétés de barrières aux graisses. Ό141] These results show that the multilayer materials according to the invention have a much lower Cobb index than the uncoated paper supports, which reflects an improvement in the grease barrier properties.
[0142] Barrière à l’oxygène : Caractérisation Mesure OTR à 23°C - 50%HR selon la norme ASTM F 1927 [0142] Oxygen barrier: Characterization OTR measurement at 23°C - 50% RH according to the ASTM F 1927 standard
[0143] La mesure de l’oxygène est faite en utilisant un appareil Presens selon la norme ASTM F1927. La mesure est réalisée à la température et à l’humidité de la salle conditionnée soit 23°C / 50%HR. Les mesures ont été doublées sur 4 échantillons différents. Les résultats sont présentés dans le tableau 3. [0144] [Tableau 3] The oxygen measurement is made using a Presens device according to the ASTM F1927 standard. The measurement is carried out at the temperature and humidity of the conditioned room, i.e. 23°C / 50% RH. The measurements were doubled on 4 different samples. The results are shown in Table 3. [0144] [Table 3]
Ό145] Ces résultats montrent que les matériaux multicouches selon l’invention ont une perméabilité à l’oxygène beaucoup plus basse que les supports papiers non-enduits, ce qui traduit une amélioration des propriétés barrières à l’oxygène. [0146] Recyclabilité des matériaux multicouches selon l’invention Ό145] These results show that the multilayer materials according to the invention have a much lower oxygen permeability than the uncoated paper supports, which reflects an improvement in the oxygen barrier properties. [0146] Recyclability of multilayer materials according to the invention
[0147] La recyclabilité des matériaux multicouches selon l’invention a été déterminée. La recyclabilité d'un emballage est évaluée au sens de la directive 2018/852/UE du 30 mai 2018 (amendant la directive 94/62/CE). The recyclability of the multilayer materials according to the invention has been determined. The recyclability of packaging is assessed within the meaning of Directive 2018/852/EU of May 30, 2018 (amending Directive 94/62/EC).
[0148] La recyclabilité d'un emballage revient à vérifier deux critères pour que ce dernier puisse être valorisable dans l’industrie papetière du recyclage : [0148] The recyclability of a packaging amounts to verifying two criteria so that it can be recovered in the paper recycling industry:
- l’emballage doit avoir une structure à base de papier carton comprenant au moins 50 % en poids de matériau papier-carton, et - the packaging must have a paper-cardboard structure comprising at least 50% by weight of paper-cardboard material, and
- l’emballage doit être conçu avec des matériaux ou combinaison de matériaux qui sont compatibles avec les technologies de recyclage connues, pertinentes et disponibles industriellement. Il ne doit pas affecter négativement les procédés de recyclage. - the packaging must be designed with materials or combinations of materials that are compatible with known, relevant and industrially available recycling technologies. It should not negatively affect recycling processes.
[0149] Tous les matériaux multicouches préparés selon l’invention contiennent au moins 50 % en poids de matériau papier/carton. La première condition est donc remplie All the multilayer materials prepared according to the invention contain at least 50% by weight of paper/cardboard material. The first condition is therefore fulfilled.
[0150] Un test de recyclage a ensuite été effectué avec les matériaux multicouches préparés selon l’invention afin d’évaluer l’impact de la présence de la couche de matériau B comprenant du caséinate de sodium. Les différentes étapes effectuées sont présentées ci-dessous. A recycling test was then carried out with the multilayer materials prepared according to the invention in order to evaluate the impact of the presence of the layer of material B comprising sodium caseinate. The different steps performed are presented below.
[0151] Pulpaqe ou remise en suspension (norme ISO 5263-1*1 [0151] Pulpaqe or resuspension (ISO 5263-1*1 standard
[0152] L'opération de pulpage consiste à individualiser les fibres cellulosiques de manière à rendre pompable la suspension fibreuse en vue de son classage, à l’aide d’un pulpeur de laboratoire. Pour les besoins de l'essai et plus particulièrement de la remise en suspension, nous avons déchiré manuellement l’échantillon de 60g en morceaux d'environ 3 x 3 cm afin de le rendre compatible avec la dimension du pulpeur de laboratoire. La matière première préparée est ensuite remise en suspension dans les conditions suivantes : - Température* : 40 °C The pulping operation consists in individualizing the cellulosic fibers so as to make the fibrous suspension pumpable with a view to classifying it, using a laboratory pulper. For the purposes of the test and more particularly of the resuspension, we manually tore the 60g sample into pieces of about 3 x 3 cm in order to make it compatible with the size of the laboratory pulper. The raw material prepared is then resuspended under the following conditions: - Temperature*: 40°C
- Concentration : 3 % (en poids) - Concentration: 3% (by weight)
- Durée : 15 min - Duration: 15 mins
- Condition : neutre [0153] Ces conditions sont représentatives des conditions appliquées industriellement (* dérogation : température de 40°C pour simuler les températures d’eau dans les procédés de recyclage industriels) - Condition: neutral [0153] These conditions are representative of the conditions applied industrially (* derogation: temperature of 40°C to simulate water temperatures in industrial recycling processes)
[0154] Observation de la suspension fibreuse après désintégration [0154] Observation of the fibrous suspension after disintegration
[0155] Après 15 minutes de désintégration, la matière première désintégrée (appelée pâte ou suspension fibreuse) est observée visuellement afin de vérifier deux points : After 15 minutes of disintegration, the disintegrated raw material (called pulp or fibrous suspension) is observed visually in order to verify two points:
- L’individualisation des fibres indiquant un bon défibrage, et donc un temps de pulpage suffisant. Les 15 minutes peuvent être rallongées si nécessaire - The individualization of the fibers indicating a good defibration, and therefore a sufficient pulping time. The 15 minutes can be extended if necessary
- La couleur des eaux de pulpage pour vérifier un possible dégorgement ou non des emballages (teinte, encre et/ ou vernis). G01561 Classage ou élimination des indésirables non fibreux (norme TAPPI-ANSI T275 sp-18) : - The color of the pulping water to check for possible disgorgement or not of the packaging (colour, ink and/or varnish). G01561 Classification or elimination of non-fibrous undesirables (TAPPI-ANSI T275 sp-18 standard):
[0157] La pâte correspondant à la désintégration de l'échantillon à tester est ensuite recueillie puis classée sur deux appareils de classage de laboratoire Somerville montés en cascade, le premier est équipé d'un tamis à fentes de 15/100 mm et le second d’un tamis de 10/100 mm. La pâte acceptée passe au travers des fentes des classeurs alors que les éléments indésirables (type morceaux de plastique) restent en surface du tamis de classage. Le premier classeur permet de retenir les gros contaminants et le second les éventuels contaminants résiduels. The paste corresponding to the disintegration of the sample to be tested is then collected and then classified on two Somerville laboratory classification devices mounted in cascade, the first is equipped with a 15/100 mm slotted sieve and the second with a 10/100 mm sieve. The accepted paste passes through the slits of the classifiers while the undesirable elements (such as pieces of plastic) remain on the surface of the classifying sieve. The first classifier is used to retain large contaminants and the second any residual contaminants.
[0158] Formette d’aspect [0158] Aspect shaper
[0159] En sortie des étapes de pulpage et de classage 10/100 mm, des feuilles de laboratoire (appelées formettes) sont réalisées selon la méthode Rapid-Kothen (Norme ISO 5269-2 : 2004 Pâtes - Préparation des feuilles de laboratoire) [0159] At the end of the pulping and 10/100 mm classification stages, laboratory sheets (called forms) are produced using the Rapid-Kothen method (ISO 5269-2 standard: 2004 Pulp - Preparation of laboratory sheets)
[0160] Les résultats obtenus sont présentés dans le tableau 4 ci-dessous The results obtained are presented in Table 4 below.
[0161] [Tableau 4] [0161] [Table 4]
Ό162] Ces résultats montrent : Ό162] These results show:
- qu’une bonne individualisation des fibres est obtenue lors du pulpage - that a good individualization of the fibers is obtained during the pulping
- que des taux de rejet corrects sont obtenus lors du classage, ces taux sont acceptables pour la recyclabilité. - que les fermettes en sortie de pulpeur ou de classage ont un aspect visuel tout à fait satisfaisant. - that correct rejection rates are obtained during classification, these rates are acceptable for recyclability. - that the trusses leaving the pulper or classification have a completely satisfactory visual appearance.
[0163] Ces résultats montrent que les matériaux multicouches selon l’invention répondent bien aux différents critères de recyclabilité d’un emballage au sens de la directive 2018/852/UE du 30 mai 2018. [0163] These results show that the multilayer materials according to the invention respond well to the various criteria of recyclability of packaging within the meaning of directive 2018/852/EU of May 30, 2018.
[0164] La présence de la couche de matériau B comprenant du caséinate de sodium et du glycérol, sur une couche A de matériau cellulosique n’affecte pas la recyclabilité de ce matériau cellulosique. The presence of the layer of material B comprising sodium caseinate and glycerol, on a layer A of cellulosic material does not affect the recyclability of this cellulosic material.
[0165] Thermoscellablité des matériaux multicouches selon l’invention [0165] Heat sealability of multilayer materials according to the invention
[0166] Un matériau multicouche a été préparé selon le mode opératoire décrit ci-dessus. Le poids de couche est de 10g/m2. Des essais de thermoscellabilité ont été réalisés sur un appareil Lako Seal Tester SL10 de Lako Sool avec les paramètres suivants : - Pression : 0,2 N/mm2 A multilayer material was prepared according to the procedure described above. The layer weight is 10g/m2. Heat sealability tests were carried out on a Lako Seal Tester SL10 from Lako Sool with the following parameters: - Pressure: 0.2 N/mm 2
Temps de contact : 0,5 s Contact time: 0.5s
- Température : entre 150 et 170°C. - Temperature: between 150 and 170°C.
La dimension des éprouvettes thermoscellées était 20 mm * 25,4 mm. The dimension of the heat-sealed test pieces was 20 mm * 25.4 mm.
[0167] Après le scellage des éprouvettes un conditionnement de 24h à 23°C et 50%HR a été réalisé. Des essais de pelage selon la norme ASTM F88, en T non maintenu ont ensuite été effectués. 3 essais de pelage ont été effectués pour chacune des conditions de scellage sélectionnées. [0167] After sealing the specimens, conditioning for 24 hours at 23° C. and 50% RH was carried out. Peel tests according to the ASTM F88 standard, in a non-maintained T, were then carried out. 3 peel tests were performed for each of the selected sealing conditions.
Largeur des échantillons : 25 mm Sample width: 25 mm
Distance de pelage : = 20mm, soit la distance de scellage Vitesse de pelage : 300 mm/min. [0168] Les résultats obtenus sont présentés dans le tableau 4 ci-dessous. [0169] Tableau 5 Peeling distance: = 20mm, ie the sealing distance Peeling speed: 300 mm/min. The results obtained are shown in Table 4 below. [0169] Table 5
[0170] Ces résultats montrent que le matériau multicouche selon l’invention présente une bonne soudabilité. En effet le fait d’avoir une rupture cohésive, indique que la rupture se produit dans le matériau et non au niveau du scellage. Par ailleurs, les forces de pelage pour les scellages effectués à 150°C, 160°C ou 170°C sont similaires et élevées. Ainsi, les matériaux multicouches selon l’invention ont de bonnes propriétés de thermoscellabilité. These results show that the multilayer material according to the invention has good weldability. Indeed the fact of having a cohesive failure, indicates that the failure occurs in the material and not at the level of the seal. Furthermore, the peel forces for seals made at 150°C, 160°C or 170°C are similar and high. Thus, the multilayer materials according to the invention have good heat-seal properties.

Claims

Revendications Claims
[Revendication 1] Matériau multicouche comprenant : i) Au moins une couche de matériau cellulosique A, et ii) Au moins une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b). [Claim 1] Multilayer material comprising: i) At least one layer of cellulosic material A, and ii) At least one layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b).
[Revendication 2] Matériau multicouche selon la revendication 1, caractérisé en ce que le matériau B comprend en outre de la gélatine d). [Claim 2] Multilayer material according to claim 1, characterized in that material B further comprises gelatin d).
[Revendication 3] Matériau multicouche selon la revendication 1 ou 2, caractérisé en ce que le matériau B comprend également un agent hydrophobe e), de préférence choisi parmi : [Claim 3] Multilayer material according to Claim 1 or 2, characterized in that the material B also comprises a hydrophobic agent e), preferably chosen from:
- les esters de polyacide carboxylique ; - polycarboxylic acid esters;
- les acides carboxyliques en C3-C33, de préférence les acides gras en C4-C28, et, encore plus préférentiellement les acides gras insaturés en C6-C28 ; - C3-C33 carboxylic acids, preferably C4-C28 fatty acids, and even more preferably C6-C28 unsaturated fatty acids;
- et leurs mélanges. - and mixtures thereof.
[Revendication 4] Matériau multicouche selon l’une des revendications précédentes, caractérisé en ce que le matériau B comprend en outre au moins un tensioactif f), de préférence choisi parmi les tensioactifs zwitterioniques dont la HLB est comprise entre 2 et 8. [Claim 4] Multilayer material according to one of the preceding claims, characterized in that the material B also comprises at least one surfactant f), preferably chosen from zwitterionic surfactants whose HLB is between 2 and 8.
[Revendication 5] Matériau multicouche selon l’une des revendications précédentes, caractérisé en ce que le plastifiant c) du matériau B est choisi parmi les polyols, les acétates de glycérol, les propionates de glycérol, et leurs mélanges, de préférence c) est choisi parmi le glycérol, le sorbitol, et leurs mélanges. [Claim 5] Multilayer material according to one of the preceding claims, characterized in that the plasticizer c) of material B is chosen from polyols, glycerol acetates, glycerol propionates, and mixtures thereof, preferably c) is selected from glycerol, sorbitol, and mixtures thereof.
[Revendication 6] Matériau multicouche selon l’une des revendications précédentes, caractérisé en ce que le matériau B comprend entre 10 et 80 % de caséine et/ou de caséinate a), de préférence entre 20 et 75 %, et, plus préférentiellement encore, entre 25 et 70%. [Claim 6] Multilayer material according to one of the preceding claims, characterized in that the material B comprises between 10 and 80% casein and/or caseinate a), preferably between 20 and 75%, and, even more preferably , between 25 and 70%.
[Revendication 7] Matériau multicouche selon l’une des revendications précédentes, caractérisé en ce que le matériau cellulosique A est choisi parmi les papiers et les cartons. [Claim 7] Multilayer material according to one of the preceding claims, characterized in that the cellulosic material A is chosen from paper and cardboard.
[Revendication 8] Matériau multicouche selon l’une des revendications précédentes, caractérisé en ce que la couche de matériau B est une couche de film de matériau B. [Claim 8] Multilayer material according to one of the preceding claims, characterized in that the layer of material B is a film layer of material B.
[Revendication 9] Matériau multicouche obtenu : [Claim 9] Multilayer material obtained:
- soit par enduction d’une couche de matériau cellulosique A avec une solution S comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b) ; - soit par assemblage d’une couche de matériau cellulosique A et d’une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b), éventuellement au moyen d’un liant, l’assemblage étant de préférence effectué par complexage ou lamination. - Either by coating a layer of cellulosic material A with a solution S comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b); - either by assembling a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), optionally by means of a binder, the assembly being preferably carried out by lamination or lamination.
[Revendication 10] Emballage caractérisé en ce qu’il comprend un matériau multicouche selon l’une des revendication 1 à 7. [Claim 10] Packaging characterized in that it comprises a multilayer material according to one of Claims 1 to 7.
[Revendication 11] Produit caractérisé en ce qu’il est emballé par un emballage selon la revendication 10. [Claim 11] Product characterized in that it is packaged by a packaging according to claim 10.
[Revendication 12] Produit selon la revendication 11 , caractérisé en ce qu’il s’agit d’un produit alimentaire. [Claim 12] Product according to claim 11, characterized in that it is a food product.
[Revendication 13] Procédé de fabrication d’un matériau multicouche, caractérisé en ce qu’il est effectué [Claim 13] Process for manufacturing a multilayer material, characterized in that it is carried out
- soit par enduction d’une couche de matériau cellulosique A avec une solution S comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b) ; - soit par assemblage d’une couche de matériau cellulosique A et d’une couche de matériau B comprenant : a. Au moins une caséine et/ou au moins un caséinate ; b. De l’eau, et c. Au moins un plastifiant différent de b), éventuellement au moyen d’un liant, l’assemblage étant de préférence effectué par complexage ou lamination. - either by coating a layer of cellulosic material A with a solution S comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b); - either by assembling a layer of cellulosic material A and a layer of material B comprising: a. At least one casein and/or at least one caseinate; b. Water, and c. At least one plasticizer different from b), optionally by means of a binder, the assembly being preferably carried out by lamination or lamination.
EP22744270.4A 2021-06-23 2022-06-23 Multilayer material useful as packaging, comprising a layer of cellulosic material and a layer of material comprising at least one moins one casein and/or at least one caseinate Pending EP4359315A1 (en)

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FR2106706A FR3124429A1 (en) 2021-06-23 2021-06-23 MULTI-LAYER MATERIAL THAT CAN BE USED AS PACKAGING
PCT/FR2022/051226 WO2022269198A1 (en) 2021-06-23 2022-06-23 Multilayer material useful as packaging, comprising a layer of cellulosic material and a layer of material comprising at least one moins one casein and/or at least one caseinate

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US5089307A (en) * 1989-05-23 1992-02-18 Mitsubishi Rayon Co., Ltd. Edible film and method of making same
FR2810990B1 (en) * 2000-07-03 2002-09-20 Ct De Valorisation Des Glucide COMPOSITION, KITS AND METHOD FOR PROVIDING BARRIER PROPERTIES TO A SUBSTRATE AND THEIR USES
US11345831B2 (en) * 2016-09-01 2022-05-31 Greentech Global Pte. Ltd. Biobased carrier coatings
FR3075215B1 (en) * 2017-12-19 2020-11-20 Lactips BIODEGRADABLE THERMOPLASTIC MATERIAL BASED ON CASEIN AND / OR CASEINATE

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