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FR2920432A1 - Composition, useful for the production of a wire, comprises starch, at least one lipid, ethylene acrylic acid, at least one polymer and water - Google Patents

Composition, useful for the production of a wire, comprises starch, at least one lipid, ethylene acrylic acid, at least one polymer and water Download PDF

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Publication number
FR2920432A1
FR2920432A1 FR0706086A FR0706086A FR2920432A1 FR 2920432 A1 FR2920432 A1 FR 2920432A1 FR 0706086 A FR0706086 A FR 0706086A FR 0706086 A FR0706086 A FR 0706086A FR 2920432 A1 FR2920432 A1 FR 2920432A1
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France
Prior art keywords
composition according
water
biodegradable
starch
eea
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FR0706086A
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French (fr)
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CONTI CELINE
PONTANIER AURELIA
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CONTI CELINE
PONTANIER AURELIA
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Priority to FR0706086A priority Critical patent/FR2920432A1/en
Publication of FR2920432A1 publication Critical patent/FR2920432A1/en
Pending legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/52Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869Acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

Biodegradable composition (I) for the production of a wire, comprises starch, at least one lipid, ethylene acrylic acid (EAA), at least one polymer and water. An independent claim is included for a biodegradable wire obtained by heating the grains of (I) to obtain viscous mixture, and extrusion of the mixture to form the wire.

Description

La présente invention a pour objet une composition biodégradable pour la réalisation d'un fil. Le fil obtenu à partir de cette composition peut être transformé, pour former un filet par nouage ou tricotage. Les filets peuvent être utilisés pour des applications diverses notamment pour jouer un rôle de filets "antiprojection" pour des bennes à déchets, pour constituer un filet de protection de façade lors de la construction ou de la réfection de bâtiments, pour constituer des protections clans le domaine agricole ou arboricole : protection des semences, des vignes, des fruits... II peut s'agir également de filets de pêche, de filets de protection contre les oiseaux ou les insectes, de filets de contenance diverse par exemple pour contenir des marchandises. Enfin, une telle structure tricotée peut être utilisée pour réaliser des vêtements. Il est connu de réaliser des sacs biodégradables ou des barquettes alimentaires réalisées à base d'une composition contenant plus de 80% d'amidon plastifié. Le reste est constitué de fibres végétales, de polyester biodégradable, d'eau et d'additifs d'adhésion. Avec une structure moléculaire qui s'étend dans toutes les directions, une telle composition convient pour réaliser des membranes ou des mousses, mais sa résistance longitudinale est insuffisante pour réaliser des fils. The present invention relates to a biodegradable composition for producing a wire. The yarn obtained from this composition can be processed to form a net by knotting or knitting. The nets can be used for various applications, in particular to play the role of "anti-spray" nets for waste skips, to constitute a protective net of facade during the construction or the repair of buildings, to constitute protections in the agricultural or arboreal field: protection of seeds, vines, fruits ... It can also be fishing nets, nets for protection against birds or insects, nets of various capacity for example to contain goods . Finally, such a knitted structure can be used to make clothes. It is known to produce biodegradable bags or food trays made from a composition containing more than 80% of plasticized starch. The rest consists of vegetable fibers, biodegradable polyester, water and adhesion additives. With a molecular structure that extends in all directions, such a composition is suitable for making membranes or foams, but its longitudinal strength is insufficient to make son.

Le but de l'invention est de fournir une composition biodégradable qui permette de réaliser des fils pouvant être utilisés pour la réalisation de filets ou similaires, qui possèdent une résistance longitudinale suffisante pour satisfaire aux applications envisagées. La composition selon l'invention doit répondre aux exigences en 25 terme de non pollution, notamment : - à la norme NF EN 13432 : caractérisation des emballages valorisables par compostage et biodégradation, - à la norme DE6400-99 : devis normalisé pour les plastiques compostables, de l'ASTM (American Society of Testing and Materials), 30 - et à la directive 94/62/CE : emballage et déchets d'emballage. A cet effet, il convient de remplir les critères suivants : - 50 à 100% en poids des compositions doivent être biodégradables dans un délai de 3 à 6 mois ; - la fraction de résidus non désintégrés (taille supérieure à 2 mm) 35 après 3 mois en présence de déchets organiques, doit être inférieure à 10% de la masse initiale ; - les métaux lourds et le fluor doivent être absents de la composition initiale ; - tous les additifs doivent se décomposer et se transformer en un matériau non polluant pour le sol. The object of the invention is to provide a biodegradable composition which makes it possible to produce threads that can be used for producing threads or the like, which have a longitudinal strength sufficient to satisfy the intended applications. The composition according to the invention must meet the requirements in terms of non-pollution, in particular: - to standard NF EN 13432: characterization of packaging recoverable by composting and biodegradation, - to standard DE6400-99: standard specification for compostable plastics , from the American Society of Testing and Materials (ASTM), 30 - and to Directive 94/62 / EC: Packaging and Packaging Waste. For this purpose, the following criteria should be fulfilled: 50 to 100% by weight of the compositions must be biodegradable within 3 to 6 months; the fraction of non-disintegrated residues (size greater than 2 mm) after 3 months in the presence of organic waste must be less than 10% of the initial mass; heavy metals and fluorine must be absent from the initial composition; - all additives must decompose and turn into a non-polluting material for the soil.

Ce matériau doit être également source d'économie car permettant de réaliser des articles à usage unique, tels que des filets de protection qui sont jetables, ce qui évite tout repliage fastidieux et long après une utilisation. A cet effet, la composition biodégradable selon l'invention comprend de l'amidon, au moins un lipide, de l'acide acrylique-éthylène (EEA), au moins un polymère et de l'eau. Avantageusement cette composition contient de 35 à 50% d'amidon, de 10 à 15% de lipides, de 3 à 4 % d'EEA, de 30 à 45% de polymère, et au plus 1,5% d'eau, en poids. L'amidon est un produit que l'on trouve dans la nature, qui est d'un faible coût de revient, qui est soluble et susceptible de se dégrader dans un délai de trois mois. L'amidon natif se transforme, dans la composition, en amidon plastifié, qui est plus résistant et très facile à traiter industriellement. Les lipides permettent d'assurer une liaison entre les différents ingrédients de la composition et de donner une certaine élasticité à celle-ci. This material must also be a source of savings because to make disposable articles, such as protective nets that are disposable, which avoids tedious and long folding after use. For this purpose, the biodegradable composition according to the invention comprises starch, at least one lipid, acrylic acid-ethylene (EEA), at least one polymer and water. Advantageously, this composition contains from 35 to 50% of starch, from 10 to 15% of lipids, from 3 to 4% of EEA, from 30 to 45% of polymer, and at most 1.5% of water, weight. Starch is a low-cost, naturally occurring product that is soluble and degradable within three months. The native starch is transformed in the composition into plasticized starch, which is more resistant and very easy to process industrially. The lipids make it possible to ensure a bond between the various ingredients of the composition and to give a certain elasticity to it.

L'acide acrylique-éthylène (EEA) est un polymère biodégradable très visqueux qui possède un caractère très adhésif tout en étant très élastique, résistant aux frictions, et très miscible avec les colorants. L'EEA sert de colle entre l'amidon et les polymères. Les polymères confèrent de bonnes caractéristiques mécaniques à 25 la composition. Selon une possibilité, la composition comprend de la polycaprolactone (PCL). La polycaprolactone (PCL) appartient à la famille des polyesters aliphatiques, et possède une structure moléculaire lui permettant d'avoir des 30 caractéristiques physiques intéressantes, avec souplesse, élasticité et résistance, en passant sous une phase liquide à une température comprise entre 59 et 64°C. En outre, ce composant est intéressant, d'un point de vue de sa biodégradabilité, dans la mesure où son temps de demi-vie est de l'ordre de 35 trois mois. Acrylic-Ethylene Acid (EEA) is a highly viscous biodegradable polymer that has a very adhesive nature while being highly elastic, resistant to friction, and very miscible with dyes. EEA serves as a glue between starch and polymers. The polymers impart good mechanical properties to the composition. According to one possibility, the composition comprises polycaprolactone (PCL). Polycaprolactone (PCL) belongs to the family of aliphatic polyesters, and has a molecular structure allowing it to have interesting physical characteristics, with flexibility, elasticity and resistance, passing under a liquid phase at a temperature between 59 and 64 ° C. In addition, this component is interesting from the point of view of its biodegradability, inasmuch as its half-life time is of the order of three months.

Suivant une autre possibilité, cette composition comprend au moins un oligomère à poids moléculaire faible à moyen (50 000 à 10 000). L'oligomère est choisi parmi le polyéthylène (PE) et le propylène (PP). Alternatively, this composition comprises at least one low to medium molecular weight oligomer (50,000 to 10,000). The oligomer is chosen from polyethylene (PE) and propylene (PP).

Ces polymères sont 100% non toxiques et se désintègrent en des fragments de taille inférieure à 2 mm dans un délai de trois mois, dans la nature. Suivant une autre caractéristique de la composition, celle-ci contient un additif constitué par une huile végétale. Cet additif constitué par une huile végétale sert à coller les ingrédients entre eux et à les renforcer. En outre, cette composition contient un colorant constitué par un sel inorganique naturel, le colorant étant choisi parmi les composants suivants : poudre de charbon et oxyde de titane. Avantageusement et de façon générale, cette composition contient de 35 à 50% d'amidon, de 10 à 15% de lipides, de 3 à 4% d'EEA, de 30 à 45% de polymère, de 1 à 1,5% de colorant, de 1 à 1,5% d'additif et au plus 1,5% d'eau, en poids. II est donné ci après trois exemples de composition selon l'invention. These polymers are 100% non-toxic and disintegrate into fragments less than 2 mm in size within three months in nature. According to another characteristic of the composition, it contains an additive consisting of a vegetable oil. This additive consisting of a vegetable oil is used to stick the ingredients together and strengthen them. In addition, this composition contains a dye constituted by a natural inorganic salt, the dye being chosen from the following components: coal powder and titanium oxide. Advantageously and generally, this composition contains from 35 to 50% of starch, from 10 to 15% of lipids, from 3 to 4% of EEA, from 30 to 45% of polymer, from 1 to 1.5% dye, from 1 to 1.5% of additive and at most 1.5% of water, by weight. Three examples of composition according to the invention are given below.

Suivant un premier exemple, cette composition contient 35% d'amidon, 10% de lipides, 3,5% d'EEA, 33,5% de PE, 13,5% de PP, 1,5% de colorant, 1,5% d'additif et 1,5% d'eau, en poids. Suivant un second exemple, cette composition contient 38% d'amidon, 12% de lipides, 30% de PCL, 3,5% d"EEA, 12% de PE, 13,5% 25 de PP, 1,5% de colorant, 1,5% d'additif et 1,5% d'eau, en poids. Suivant un troisième exemple, cette composition contient 48,5% d'amidon, 12% de lipides, 31,5% de PCL, 3,5% d'EEA, 1,5% de colorant, 1,5% d'additif et 1,5% d'eau, en poids. La composition selon l'invention permet de réaliser des grains qui 30 après chauffage, forment un mélange visqueux permettant l'extrusion de fil. Suivant les applications envisagées, et notamment lorsqu'il s'agit d'applications industrielles consistant en la réalisation de filets, le fil possède un diamètre compris entre 0,15 et 0,30mm. De tels fils peuvent être regroupés pour former des câbles, et tricotés ou liés pour la réalisation de filets.According to a first example, this composition contains 35% of starch, 10% of lipids, 3.5% of EEA, 33.5% of PE, 13.5% of PP, 1.5% of dye, 1, 5% of additive and 1.5% of water, by weight. According to a second example, this composition contains 38% of starch, 12% of lipids, 30% of PCL, 3.5% of EEA, 12% of PE, 13.5% of PP, 1.5% of dye, 1.5% additive and 1.5% water, by weight According to a third example, this composition contains 48.5% starch, 12% lipids, 31.5% PCL, 3% 5% of EEA, 1.5% of dye, 1.5% of additive and 1.5% of water, by weight The composition according to the invention makes it possible to produce grains which, after heating, form A viscous mixture allowing the extrusion of wire Depending on the applications envisaged, and in particular when it comes to industrial applications consisting in the production of threads, the wire has a diameter of between 0.15 and 0.30 mm. such yarns can be grouped together to form cables, and knitted or tied together for making threads.

35 Comme il ressort de ce qui précède, l'invention apporte une grande amélioration à la technique existante en fournissant une composition permettant la réalisation de fils biodégradables, parfaitement adaptés à la réalisation de structures nouées ou tricotées, tels que des filets. Comme il va de soi, l'invention ne se limite pas aux seules compositions décrites ci-dessus à titre d'exemples, elle en embrasse au 5 contraire toutes les variantes. As is apparent from the foregoing, the invention provides a great improvement to the existing technique by providing a composition for the production of biodegradable yarns, perfectly suited to producing knotted or knitted structures, such as nets. As is obvious, the invention is not limited to the compositions described above as examples, it encompasses all variants.

Claims (14)

REVENDICATIONS 1. Composition biodégradable pour la réalisation d'un fil, caractérisée en ce qu'elle comprend de l'amidon, au moins un lipide, de l'acide 5 acrylique-éthylène (EEA), au moins un polymère et de l'eau. 1. A biodegradable composition for making a yarn, characterized in that it comprises starch, at least one lipid, acrylic acid-ethylene (EEA), at least one polymer and water . 2. Composition biodégradable selon la revendication 1, caractérisée en ce qu'elle contient de 35 à 50% d'amidon, de 10 à 15% de lipides, de 3 à 4 % d'EEA, de 30 à 45% de polymère, et au plus 1,5% d'eau, en 10 poids. 2. Biodegradable composition according to claim 1, characterized in that it contains 35 to 50% starch, 10 to 15% lipids, 3 to 4% EEA, 30 to 45% of polymer, and at most 1.5% water, by weight. 3. Composition biodégradable selon l'une des revendications 1 et 2, caractérisée en ce qu'elle comprend de la polycaprolactone (PCL). 15 3. Biodegradable composition according to one of claims 1 and 2, characterized in that it comprises polycaprolactone (PCL). 15 4. Composition biodégradable selon l'une des revendications 1 à 3, caractérisée en ce qu'elle comprend au moins un oligomère à poids moléculaire faible à moyen (50 000 à 100 000). 4. biodegradable composition according to one of claims 1 to 3, characterized in that it comprises at least one low molecular weight oligomer (50 000 to 100 000). 5. Composition biodégradable selon la revendication 4, 20 caractérisée en ce que l'oligomère est choisi parmi le polyéthylène (PE) et le propylène (PP). 5. Biodegradable composition according to claim 4, characterized in that the oligomer is selected from polyethylene (PE) and propylene (PP). 6. Composition biodégradable selon l'une des revendication 1 à 5, caractérisée en ce qu'elle contient un additif constitué par une huile végétale. 6. Biodegradable composition according to one of claims 1 to 5, characterized in that it contains an additive consisting of a vegetable oil. 7. Composition biodégradable selon l'une des revendications 1 à 6, caractérisée en ce qu'elle contient un colorant constitué par un sel inorganique naturel. 30 7. biodegradable composition according to one of claims 1 to 6, characterized in that it contains a dye consisting of a natural inorganic salt. 30 8. Composition biodégradable selon la revendication 7, caractérisée en ce que le colorant est choisi parmi les composants suivants : poudre de charbon et oxyde de titane. 8. biodegradable composition according to claim 7, characterized in that the dye is selected from the following components: coal powder and titanium oxide. 9. Composition biodégradable selon l'ensemble des revendications 35 1, 2, 6 et 7, caractérisée en ce qu'elle contient de 35 à 50% d'amidon, de 10 à 2515% de lipides, de 3 à 4% d'EEA, de 30 à 45% de polymère, de 1 à 1,5% de colorant, de 1 à 1,5% d'additif et au plus 1,5% d'eau, en poids. 9. Biodegradable composition according to Claims 1, 2, 6 and 7, characterized in that it contains from 35 to 50% of starch, from 10 to 25% of lipids, from 3 to 4% by weight. EEA, 30 to 45% polymer, 1 to 1.5% dye, 1 to 1.5% additive and at most 1.5% water, by weight. 10. Composition selon les revendications 1 à 9, caractérisée en ce 5 qu'elle contient 35% d'amidon, 10% de lipides, 3,5% d'EEA, 33,5% de PE, 13,5% de PP, 1,5% de colorant, 1,5% d'additif et 1,5% d'eau, en poids. 10. Composition according to claims 1 to 9, characterized in that it contains 35% of starch, 10% of lipids, 3.5% of EEA, 33.5% of PE, 13.5% of PP. 1.5% dye, 1.5% additive and 1.5% water, by weight. 11. Composition biodégradable selon les revendications 1 à 9, caractérisée en ce qu'elle contient 38% d'amidon, 12% de lipides, 10 30% de PCL, 3,5% d'EEA, 12% de PE, 1,5% de colorant, 1,5% d'additif et 1,5% d'eau, en poids. 11. Biodegradable composition according to claims 1 to 9, characterized in that it contains 38% of starch, 12% of lipids, 30% of PCL, 3.5% of EEA, 12% of PE, 1, 5% dye, 1.5% additive and 1.5% water, by weight. 12. Composition biodégradable selon les revendications 1 à 9, caractérisée en ce qu'elle contient 48,5% d'amidon, 12% de lipides, 31,5% de 15 PCL, 3,5% d'EEA, 1,5% de colorant, 1,5% d'additif et 1,5% d'eau, en poids. 12. Biodegradable composition according to claims 1 to 9, characterized in that it contains 48.5% of starch, 12% of lipids, 31.5% of PCL, 3.5% of EEA, 1.5 % dye, 1.5% additive and 1.5% water, by weight. 13. Fil biodégradable obtenu à partir de la compositon selon l'une des revendications 1 à 12. 20 13. Biodegradable yarn obtained from the composition according to one of claims 1 to 12. 14. Fil biodégradable selon la revendication 13, caractérisé en ce qu'il est obtenu par chauffage de grains de la composition selon l'une des revendications 1 à 12, obtention d'une matière fluide, et extrusion de cette matière sous forme de fil. 14. biodegradable wire according to claim 13, characterized in that it is obtained by heating grains of the composition according to one of claims 1 to 12, obtaining a fluid material, and extrusion of this material in the form of wire .
FR0706086A 2007-08-30 2007-08-30 Composition, useful for the production of a wire, comprises starch, at least one lipid, ethylene acrylic acid, at least one polymer and water Pending FR2920432A1 (en)

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FR0706086A FR2920432A1 (en) 2007-08-30 2007-08-30 Composition, useful for the production of a wire, comprises starch, at least one lipid, ethylene acrylic acid, at least one polymer and water

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FR0706086A FR2920432A1 (en) 2007-08-30 2007-08-30 Composition, useful for the production of a wire, comprises starch, at least one lipid, ethylene acrylic acid, at least one polymer and water

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