WO2024094356A1 - Article made of a flexible polymer material, and method for producing such an article - Google Patents

Article made of a flexible polymer material, and method for producing such an article Download PDF

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Publication number
WO2024094356A1
WO2024094356A1 PCT/EP2023/075681 EP2023075681W WO2024094356A1 WO 2024094356 A1 WO2024094356 A1 WO 2024094356A1 EP 2023075681 W EP2023075681 W EP 2023075681W WO 2024094356 A1 WO2024094356 A1 WO 2024094356A1
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WO
WIPO (PCT)
Prior art keywords
article
weight
article according
flexible polymer
inorganic material
Prior art date
Application number
PCT/EP2023/075681
Other languages
French (fr)
Inventor
Nicolas François
Marek DOVCIK
Sophie NAPOLI
Stewes Bourban
Original Assignee
The Swatch Group Research And Development Ltd
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Publication of WO2024094356A1 publication Critical patent/WO2024094356A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/82—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyester amides or polyether amides
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • A44C5/0053—Flexible straps
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention relates to an article, for example a watch component, made of a flexible polymer material loaded with inorganic materials, for example metallic and/or ceramic.
  • the invention also relates to a method of manufacturing such an article made from a flexible polymer material loaded with inorganic particles.
  • inorganic technical yarns can provide specific and very interesting functions to textiles compared to the use of more traditional textile yarns (i.e. yarns based on natural, artificial or synthetic fibers).
  • the use of ceramic yarn makes it possible to improve the thermal conductivity properties of the textile and to facilitate thermal exchanges between the body and the external environment.
  • Another solution consists of manufacturing textile threads based on synthetic fibers loaded with inorganic particles, for example, particles of ceramic, carbon, or various metals. [0008] However, the content of these inorganic particles does not exceed 10% by weight of the textile yarn because beyond that the loaded filament is too fragile to manufacture a yarn by spinning.
  • inorganic particles for example, particles of ceramic, carbon, or various metals.
  • the tensions imposed during weaving are also an obstacle to the use of synthetic threads loaded with inorganic material with a content greater than 10% by weight.
  • the present invention aims to propose a new composition of matter formed by a flexible polymer loaded with significant contents of at least one inorganic material.
  • This material can be shaped by molding and extrusion processes allowing the production of finished or semi-finished parts.
  • the present invention also relates to a new manufacturing process allowing the manufacture of a finished or semi-finished article made from a flexible polymer material loaded with at least one inorganic material according to the invention making it possible to overcome the problems linked to the manufacture of textile yarn, particularly during spinning.
  • the present invention aims to propose a new manufacturing process making it possible to produce an article in a flexible polymer material loaded with at least one inorganic material, the content of inorganic material in the material is greater than 10% by weight, and particularly between 10% and 70% by weight.
  • the invention also relates to an article made of a flexible polymer material loaded with at least one inorganic material according to the invention.
  • the invention finds a particularly interesting application in the field of watchmaking; however, the invention is not limited to such an application.
  • the invention is also applicable to the field of technical clothing and technical equipment.
  • the invention is particularly suitable for producing a watch strap.
  • Figure 1 schematically illustrates the section of a composite textile yarn 10 according to the invention made of flexible polymer material P loaded with at least one inorganic material, here inorganic particles C, obtained by an extrusion process according to 'invention.
  • Figure 2 illustrates two examples of weaving weaves that it is possible to produce by a weaving process according to the invention with a textile yarn A, and a composite textile yarn B loaded with inorganic material, here particles inorganic as illustrated in Figure 1.
  • a weaving process according to the invention with a textile yarn A, and a composite textile yarn B loaded with inorganic material, here particles inorganic as illustrated in Figure 1.
  • the invention relates to a composite material comprising a flexible polymer and a filler formed by at least one inorganic material.
  • the inorganic material can be in the form of particles, fibers, etc.
  • the inorganic filler is in the form of particles.
  • the invention also relates to an article made of such a flexible polymer material loaded with at least one inorganic material.
  • the flexible polymer material loaded at least with one inorganic material comprises two main components which are the inorganic material, for example in the form of metallic and/or ceramic particles, and the flexible polymer forming the binder.
  • the material can be termed as a composite material.
  • the material may include one or more coupling agents if the physicochemical interaction between the inorganic filler and the flexible polymer is not sufficient depending on the type of application.
  • the material may also include one or more pigments.
  • the material may also include one or more antibacterial additives to obtain an anti-odor effect for comfort.
  • the material may also include diluents and/or plasticizers.
  • the material can also contain cellulosic fibers making it possible to improve comfort, by draining moisture at the skin/material interface to the outside.
  • the inorganic material may be metallic and/or ceramic.
  • the inorganic material is a ceramic material used for its thermal conductivity properties.
  • Ceramic material used for its thermal conductivity properties.
  • These may be carbides, nitrides or oxides such as Zr ⁇ 2, CeO2, ZnO, etc.
  • the metallic material it may be a conventional carbon steel, a stainless steel, copper, a copper alloy, titanium, a titanium alloy or even tungsten .
  • it is a nickel-free stainless steel.
  • It may also be several inorganic materials comprising a mixture of metallic and ceramic materials.
  • the flexible polymer can be an elastomer-based polymer, that is to say it is mixed with another type of polymer, for example a thermoplastic such as a polyamide.
  • the flexible polymer can consist solely of an elastomer.
  • the elastomer is for example a thermoplastic elastomer based on block copolymers (TPE).
  • the elastomer is for example a thermoplastic elastomer based on polyether amide blocks (PEBA).
  • the polymer is a biosourced polymer of renewable origin, or at least partially biosourced.
  • the polymer may comprise blocks of polyamide 11.
  • the elastomer is for example a thermoplastic elastomer with a mechanical mixture of a thermoplastic polymer and an elastomer.
  • the elastomer is for example a thermoplastic elastomer with a mechanical mixture of a thermoplastic polymer and a TPO-O or TPO, TPE-V or TPV elastomer.
  • the elastomer is for example a silicone or even a vulcanized rubber, for example an ethylene-propylene-diene monomer rubber (EPDM) or a natural rubber.
  • EPDM ethylene-propylene-diene monomer rubber
  • natural rubber we will favor a deproteinized natural rubber in order to avoid allergies.
  • the elastomer advantageously has a hardness of between 30 shore A and 85 shore A.
  • the elastomer has a hardness of between 65 shore A and 75 shore A.
  • the elastomer has a hardness of 75 shore A.
  • the content by weight of the inorganic filler in the flexible polymer material is greater than 10%.
  • the content by weight of the inorganic filler in the flexible polymer material can go up to 70% or even 80% by weight with this manufacturing method according to the invention. Beyond that with known elastomers, manufacturing problems may be encountered.
  • the content by weight of the inorganic filler in the flexible polymer material is preferably greater than or equal to 15%
  • the content by weight of the inorganic filler in the flexible polymer material is preferably greater than or equal to 20%.
  • the content by weight of the inorganic filler in the flexible polymer material is preferably greater than or equal to 30%.
  • the content by weight of the inorganic filler in the flexible polymer material is preferably greater than or equal to 40%.
  • the inorganic material in the form of a powder, forming the filler of the material as well as optionally the coupling agents, pigments, diluents, plasticizers or others, are introduced into the polymer during the manufacturing process of the flexible polymer material in the form of granules.
  • the inorganic material is for example a ceramic powder whose particles have a size between 100 nm and 10 mu pm.
  • the inorganic material is for example a zirconia powder whose particles have a size between 100 nm and 10 mu.
  • the granules of flexible polymer material with an inorganic filler are manufactured by cutting a rod resulting from an extrusion of the various materials mentioned above which are introduced into an extruder hopper.
  • the material includes a coupling agent
  • this can be introduced initially into the hopper of the extruder either separately or with the granules of the polymer before introducing the inorganic material in the form of powder. , (for example a metal and/or ceramic powder) which is subsequently introduced into the extruder.
  • the coupling agent is introduced separately, it can be introduced in powder form.
  • a pre-mixture for good integration of the inorganic material into the mixture, a pre-mixture must be prepared by a high-speed mixing process between the coupling agent and the inorganic material. This pre-mixture can then be fed into a twin-screw extruder in order to be well dispersed in the polymer.
  • the material contains pigments, they can be introduced during extrusion and advantageously in a second step. It is also possible to mix it with the polymer granules just before extrusion.
  • the article can be manufactured by molding, by injection, by extrusion or by 3D printing.
  • the article produced is both a finished part and a semi-finished part.
  • the granules of flexible polymer material with inorganic filler described above are prepared, then introduced into a hopper to be melted, the material is then kneaded then injected into a mold to form the article or a part of the article (by overmolding another part).
  • the injection is carried out in a mold which has a temperature between 60 and 100° C., preferably between 70 and 80° C., while the material during the injection has a temperature between 200° C. and 300°C, and preferably between 250 and 300°C.
  • the article can also be manufactured by 3D printing such as by FDM (Fusion Deposition Molding), either from granules described above or directly from an extruded wire not cut into granules.
  • FDM Fusion Deposition Molding
  • the article can be a constituent element of watches, jewelry, bracelets, etc.
  • the article can also be a constituent element of a spectacle, for example a frame, a branch, a pad.
  • the article according to the invention can also be a constituent element, or form the entirety, of a sporting article, a kitchen article, an article or a musical instrument, an article of leather goods or donrdashery, an automobile or aeronautical component, a component for an electronic article (for example example protective phone case, computer keyboard, computer keyboard keys, headphones, etc.), a writing article, etc.
  • a constituent element for example protective phone case, computer keyboard, computer keyboard keys, headphones, etc.
  • the article is a component or part of a component whose functionality requires a certain function, the choice of the inorganic filler will be made according to the desired function.
  • the article is made from a composite material comprising a flexible elastomeric polymer, or based on a flexible elastomeric polymer and a ceramic filler.
  • the ceramic filler makes it possible to improve the thermal conductivity of the material.
  • this article can for example be a bracelet.
  • the article can also be manufactured by a textile processing process so as to make a technical textile article.
  • the article can be manufactured by weaving, knitting, braiding, embroidery, etc.
  • the process for manufacturing a composite textile yarn consists initially of preparing granules of flexible polymer material with an inorganic filler as described above with a desired inorganic particle content, preferably greater than 10% by weight.
  • a composite textile yarn for the manufacture of a technical textile article having improved thermal conductivity we can choose for example a PEBA elastomeric polymer mixed with a zirconia powder, whose zirconia mass content is 40%, and whose particles have a size between 100 nm and 10 mu.
  • the composite textile yarn subsequently called yarn B, is a monofilament obtained by extrusion in the form of a flexible profile, having for example a circular, oval or even polygonal section depending on the needs and technical or aesthetic effects desired for the textile article made from the composite textile yarn according to the invention.
  • the section of wire B is included in a diameter of between 0.2 mm and 2 mm.
  • the extruder die is adapted to obtain the desired profile with the right section and diameter.
  • the wire B obtained will be too fragile due to its high content of inorganic filler, for example ceramic in the given embodiment.
  • the wire B obtained will be too thick and will cause problems during weaving. It can only be used as a warp thread.
  • the die is configured to obtain a composite textile yarn, yarn B, with a circular section with a diameter of 0.7 mm in order to maximize surface contacts, particularly to the skin.
  • Figure 1 schematically illustrates the section of wire B made of flexible polymer material P loaded with inorganic particles C obtained by the extrusion manufacturing process which has just been described.
  • the composite textile yarn B thus obtained is woven with a second identical textile yarn B to form a warp yarn of type B and a weft yarn of type B.
  • the composite textile yarn B thus obtained is woven with a second textile yarn B' obtained in a manner similar to the yarn B, but whose charge is different, for example inorganic or other.
  • the textile yarn B thus obtained is woven with a more conventional textile yarn, called yarn A, not loaded with inorganic material, for example obtained by spinning with a count of 470 dTex so as to provide flexibility to the woven textile article and to facilitate weaving.
  • the textile yarn A is for example composed of filaments or fibers of synthetic material, for example of thermoplastic polymer.
  • textile yarn A is a yarn composed of polyamide filaments or fibers, preferably aliphatic polyamide of renewable origin, such as for example polyamide 11.
  • the thread B loaded with inorganic material is preferentially used as warp thread and the unfilled thread A is used as weft thread.
  • the constraints imposed during weaving on the textile yarn B loaded with inorganic particles are further minimized.
  • the reverse is also possible.
  • the composite textile yarn according to the invention makes it possible to make a technical textile article by conventional weaving methods well known to those skilled in the art.
  • Figure 2 illustrates two types of weaving weave that can be produced during the weaving process with a textile yarn A and a textile yarn B loaded with inorganic particles.
  • the weave is a twill or satin in order to be able to have floats of threads B on threads A and to be able to maximize the apparent surface of threads B to increase the contact surface with the skin.
  • the inorganic material is a ceramic; however it is possible to vary the nature of the filler in the elastomeric polymer in order to vary the function.
  • the inorganic material can be metallic to provide a metallic or pearly effect to obtain an aesthetic effect.
  • the inorganic material can be a precious metal.
  • Such a process for manufacturing a textile yarn by extrusion also makes it possible to increase the pigment content of a textile yarn, such as for example the phosphorescent pigment content to obtain a more intense luminous effect at night than with commercial textile yarns which do not contain more than 10% by weight of pigment.
  • the elastomeric polymer can also be loaded with an antibacterial additive.
  • the inorganic material here inorganic particles, is always coated in the polymer material which makes it possible to overcome the problems of irritation of the skin because the inorganic material is not directly in contact with the user's skin.
  • the material according to the invention also makes it possible to provide an additional function to the article, such as for example the increase in thermal conductivity with the use of ceramic particles in the material.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

One aspect of the invention relates to an article characterized in that it is made of a material comprising a flexible polymer (P) and a filler made of at least one inorganic material (C).

Description

ARTICLE RÉALISÉ DANS UN MATÉRIAU POLYMÈRE SOUPLE ET PROCÉDÉ DE FABRICATION D’UN TEL ARTICLE ARTICLE MADE FROM A FLEXIBLE POLYMERIC MATERIAL AND METHOD FOR MANUFACTURING SUCH AN ARTICLE
Domaine technique de l’invention Technical field of the invention
[0001] L’invention concerne un article, par exemple un composant horloger, réalisé dans un matériau polymère souple chargé en matières inorganiques, par exemple métalliques et/ou céramiques. [0001] The invention relates to an article, for example a watch component, made of a flexible polymer material loaded with inorganic materials, for example metallic and/or ceramic.
[0002] L’invention concerne également un procédé de fabrication d’un tel article réalisé dans un matériau polymère souple charge en particules inorganiques. [0002] The invention also relates to a method of manufacturing such an article made from a flexible polymer material loaded with inorganic particles.
Arrière-plan technologique Technology background
[0003] L’utilisation de fils techniques inorganiques peut apporter des fonctions spécifiques et très intéressantes aux textiles par rapport à l’utilisation de fils textiles plus classiques (i.e. des fils à base de fibres naturelles, artificielles ou synthétiques). [0003] The use of inorganic technical yarns can provide specific and very interesting functions to textiles compared to the use of more traditional textile yarns (i.e. yarns based on natural, artificial or synthetic fibers).
[0004] Par exemple, l’utilisation de fil céramique permet d’améliorer les propriétés de conductivité thermique du textile et de faciliter les échanges thermiques entre le corps et l’environnement extérieur. [0004] For example, the use of ceramic yarn makes it possible to improve the thermal conductivity properties of the textile and to facilitate thermal exchanges between the body and the external environment.
[0005] Toutefois, l’utilisation de fils textiles céramiques péjore le confort de portage du textile car ces fils céramiques sont abrasifs et irritent la peau. [0005] However, the use of ceramic textile threads worsens the comfort of wearing the textile because these ceramic threads are abrasive and irritate the skin.
[0006] Pour remédier à cet inconvénient et à cet inconfort provoqué par les fils céramiques, il a été proposé de guiper ces fils céramiques avec une gaine textile choisie pour apporter du confort. Toutefois, les fibres de ces gaines textiles de confort sont isolantes thermiquement, ce qui réduit le bénéfice d’échange thermique apporté par les fils céramiques. [0006] To remedy this drawback and this discomfort caused by the ceramic threads, it has been proposed to cover these ceramic threads with a textile sheath chosen to provide comfort. However, the fibers of these comfort textile sheaths are thermally insulating, which reduces the heat exchange benefit provided by the ceramic yarns.
[0007] Une autre solution consiste à fabriquer des fils textiles à base de fibres synthétiques chargées en particules inorganiques, par exemple, des particules de céramique, de carbone, ou de métaux divers. [0008] Toutefois, la teneur de ces particules inorganiques ne dépasse pas 10% en poids du fil textile car au-delà le filament chargé est trop fragile pour fabriquer un fil par filature. Another solution consists of manufacturing textile threads based on synthetic fibers loaded with inorganic particles, for example, particles of ceramic, carbon, or various metals. [0008] However, the content of these inorganic particles does not exceed 10% by weight of the textile yarn because beyond that the loaded filament is too fragile to manufacture a yarn by spinning.
[0009] En effet, le procédé de filature de fils synthétiques fins (par exemple inférieur à 500 dtex) nécessite de nombreuses opérations mécaniques avec des contraintes importantes imposées aux filaments, ce qui entraine des casses importantes si la teneur en matière inorganique de ces filaments est supérieure à 10% en poids. [0009] Indeed, the process of spinning fine synthetic yarns (for example less than 500 dtex) requires numerous mechanical operations with significant constraints imposed on the filaments, which leads to significant breakage if the inorganic material content of these filaments is greater than 10% by weight.
[0010] De plus, les tensions imposées lors du tissage sont également un obstacle à l’utilisation des fils synthétiques chargés en matière inorganique avec une teneur supérieure à 10% en poids. [0010] Furthermore, the tensions imposed during weaving are also an obstacle to the use of synthetic threads loaded with inorganic material with a content greater than 10% by weight.
[0011] Par conséquent, avec des fils textiles chargés obtenu par filature, la teneur en céramique est trop faible pour apporter significativement une conductivité thermique intéressante au textile. [0011] Consequently, with loaded textile yarns obtained by spinning, the ceramic content is too low to significantly provide interesting thermal conductivity to the textile.
[0012] Par conséquent, il existe un besoin pour améliorer les articles incorporant des matières inorganiques. [0012] Consequently, there is a need to improve articles incorporating inorganic materials.
Résumé de l’invention Summary of the invention
[0013] La présente invention vise à proposer une nouvelle composition de matière formée par un polymère souple chargé avec des teneurs importantes d’au moins une matière inorganique. The present invention aims to propose a new composition of matter formed by a flexible polymer loaded with significant contents of at least one inorganic material.
[0014] Cette matière peut être mise en forme par des procédés de moulage et d’extrusion permettant la réalisation de pièces finies ou semi- finies. [0014] This material can be shaped by molding and extrusion processes allowing the production of finished or semi-finished parts.
[0015] La présente invention concerne également un nouveau procédé de fabrication permettant la fabrication d’un article fini ou semi fini réalisé dans un matériau polymère souple chargé avec au moins une matière inorganique selon l’invention permettant de s’affranchir des problématiques liées à la fabrication de fil textile, notamment lors de la filature. [0016] La présente invention vise à proposer un nouveau procédé de fabrication permettant de réaliser un article dans un matériau polymère souple chargé avec au moins une matière inorganique, dont la teneur en matière inorganique dans le matériau est supérieure à 10% en poids, et particulièrement comprise entre 10% et à 70% en poids. [0015] The present invention also relates to a new manufacturing process allowing the manufacture of a finished or semi-finished article made from a flexible polymer material loaded with at least one inorganic material according to the invention making it possible to overcome the problems linked to the manufacture of textile yarn, particularly during spinning. The present invention aims to propose a new manufacturing process making it possible to produce an article in a flexible polymer material loaded with at least one inorganic material, the content of inorganic material in the material is greater than 10% by weight, and particularly between 10% and 70% by weight.
[0017] L’invention concerne également un article réalisé dans un matériau polymère souple chargé avec au moins une matière inorganique selon l’invention. [0017] The invention also relates to an article made of a flexible polymer material loaded with at least one inorganic material according to the invention.
[0018] L’invention trouve une application particulièrement intéressante dans le domaine de l’horlogerie ; toutefois l’invention n’est pas limitée à une telle application. Par exemple, l’invention est également applicable au domaine de l’habillement technique, de l’équipement technique. [0018] The invention finds a particularly interesting application in the field of watchmaking; however, the invention is not limited to such an application. For example, the invention is also applicable to the field of technical clothing and technical equipment.
[0019] L’invention est particulièrement adaptée pour la réalisation d’un bracelet de montre. [0019] The invention is particularly suitable for producing a watch strap.
[0020] Les différents aspects, caractéristiques et avantages de l’invention sont décrits dans les revendications ainsi que dans la description suivante. [0020] The different aspects, characteristics and advantages of the invention are described in the claims as well as in the following description.
Brève description des figures Brief description of the figures
[0021] La figure 1 illustre schématiquement la section d’un fil textile composite 10 selon l’invention réalisé en matériau polymère souple P chargé avec au moins une matière inorganique, ici des particules inorganiques C, obtenu par un procédé d’extrusion selon l’invention. [0021] Figure 1 schematically illustrates the section of a composite textile yarn 10 according to the invention made of flexible polymer material P loaded with at least one inorganic material, here inorganic particles C, obtained by an extrusion process according to 'invention.
[0022] La figure 2 illustre deux exemples d’armures de tissage qu’il est possible de réaliser par un procédé de tissage selon l’invention avec un fil textile A, et un fil textile composite B chargé en matière inorganique, ici des particules inorganiques comme illustré à la figure 1 . Description détaillée de l’invention [0022] Figure 2 illustrates two examples of weaving weaves that it is possible to produce by a weaving process according to the invention with a textile yarn A, and a composite textile yarn B loaded with inorganic material, here particles inorganic as illustrated in Figure 1. Detailed description of the invention
[0023] L’invention concerne un matériau composite comportant un polymère souple et une charge formée par au moins une matière inorganique. The invention relates to a composite material comprising a flexible polymer and a filler formed by at least one inorganic material.
[0024] La matière inorganique peut être sous la forme de particules, de fibres, etc. The inorganic material can be in the form of particles, fibers, etc.
[0025] Dans l’exemple qui sera détaillé par la suite, la charge inorganique est sous la forme de particules. [0025] In the example which will be detailed below, the inorganic filler is in the form of particles.
[0026] L’invention concerne également un article réalisé dans un tel matériau polymère souple chargé avec au moins une matière inorganique. The invention also relates to an article made of such a flexible polymer material loaded with at least one inorganic material.
[0027] Le matériau polymère souple chargé au moins avec une matière inorganique comporte deux composants principaux qui sont la matière inorganique, par exemple sous la forme de particules métalliques et/ou céramiques, et le polymère souple formant le liant. Ainsi, le matériau peut être qualifié de matériau composite. The flexible polymer material loaded at least with one inorganic material comprises two main components which are the inorganic material, for example in the form of metallic and/or ceramic particles, and the flexible polymer forming the binder. Thus, the material can be termed as a composite material.
[0028] Optionnellement, le matériau peut comporter un ou plusieurs agents de couplage si l’interaction physico-chimique entre la charge inorganique et le polymère souple n’est pas suffisante en fonction du type d’application. [0028] Optionally, the material may include one or more coupling agents if the physicochemical interaction between the inorganic filler and the flexible polymer is not sufficient depending on the type of application.
[0029] Optionnellement, le matériau peut également comporter un ou plusieurs pigments. [0029] Optionally, the material may also include one or more pigments.
[0030] Optionnellement, le matériau peut également comporter un ou plusieurs additifs antibactériens pour obtenir un effet anti-odeur pour le confort. [0030] Optionally, the material may also include one or more antibacterial additives to obtain an anti-odor effect for comfort.
[0031] Optionnellement, le matériau peut également comporter des diluants et/ou des plastifiants. [0031] Optionally, the material may also include diluents and/or plasticizers.
[0032] Optionnellement le matériau peut aussi contenir des fibres cellulosiques permettant d’améliorer le confort, en drainant l’humidité à l’interface peau/matière vers l’extérieur. [0033] La matière inorganique peut être métallique et/ou céramique. [0032] Optionally the material can also contain cellulosic fibers making it possible to improve comfort, by draining moisture at the skin/material interface to the outside. The inorganic material may be metallic and/or ceramic.
[0034] Préférentiellement, la matière inorganique est une matière céramique utilisée pour ses propriétés de conductivité thermique. Il peut s’agir de carbures, de nitrures ou d’oxydes tels que du ZrÛ2, CeO2, ZnO, etc. Preferably, the inorganic material is a ceramic material used for its thermal conductivity properties. These may be carbides, nitrides or oxides such as ZrÛ2, CeO2, ZnO, etc.
[0035] Pour la matière métallique, il peut s’agir d’un acier conventionnel au carbone, d’un acier inoxydable, de cuivre, d’un alliage de cuivre, de titane, d’un alliage de titane ou encore de tungstène. Préférentiellement, il s’agit d’un acier inoxydable sans nickel. [0035] For the metallic material, it may be a conventional carbon steel, a stainless steel, copper, a copper alloy, titanium, a titanium alloy or even tungsten . Preferably, it is a nickel-free stainless steel.
[0036] Il peut également s’agir de plusieurs matières inorganiques comportant un mélange de matières métallique et céramique. [0036] It may also be several inorganic materials comprising a mixture of metallic and ceramic materials.
[0037] Le polymère souple peut être un polymère à base d’élastomère, c’est-à-dire qu’il est mélangé avec un autre type de polymère par exemple un thermoplastique comme un polyamide. The flexible polymer can be an elastomer-based polymer, that is to say it is mixed with another type of polymer, for example a thermoplastic such as a polyamide.
[0038] Le polymère souple peut être uniquement constitué par un élastomère. The flexible polymer can consist solely of an elastomer.
[0039] L’élastomère est par exemple un élastomère thermoplastique à base de copolymères à blocs (TPE). The elastomer is for example a thermoplastic elastomer based on block copolymers (TPE).
[0040] L’élastomère est par exemple un élastomère thermoplastique à base de polyéther blocs amides (PEBA). The elastomer is for example a thermoplastic elastomer based on polyether amide blocks (PEBA).
[0041] Par exemple, le polymère est un polymère biosourcé d’origine renouvelable, ou au moins partiellement biosourcé. Par exemple, le polymère peut comporter des blocs de polyamide 11 . [0041] For example, the polymer is a biosourced polymer of renewable origin, or at least partially biosourced. For example, the polymer may comprise blocks of polyamide 11.
[0042] L’élastomère est par exemple un élastomère thermoplastique à mélange mécanique d’un polymère thermoplastique et d’un élastomère. The elastomer is for example a thermoplastic elastomer with a mechanical mixture of a thermoplastic polymer and an elastomer.
[0043] L’élastomère est par exemple un élastomère thermoplastique à mélange mécanique d’un polymère thermoplastique et d’un élastomère TPO- O ou TPO, TPE-V ou TPV. [0044] L’élastomère est par exemple un silicone ou encore un caoutchouc vulcanisé, par exemple un caoutchouc éthylène-propylène-diène monomère (EPDM) ou un caoutchouc naturel. Dans le cas d’un caoutchouc naturel on privilégiera un caoutchouc naturel déprotéiné afin d’éviter les allergies. The elastomer is for example a thermoplastic elastomer with a mechanical mixture of a thermoplastic polymer and a TPO-O or TPO, TPE-V or TPV elastomer. The elastomer is for example a silicone or even a vulcanized rubber, for example an ethylene-propylene-diene monomer rubber (EPDM) or a natural rubber. In the case of natural rubber, we will favor a deproteinized natural rubber in order to avoid allergies.
[0045] L’élastomère présente avantageusement une dureté comprise entre 30 shore A et 85 shore A. [0045] The elastomer advantageously has a hardness of between 30 shore A and 85 shore A.
[0046] Préférentiellement, l’élastomère présente une dureté comprise entre 65 shore A et 75 shore A. [0046] Preferably, the elastomer has a hardness of between 65 shore A and 75 shore A.
[0047] Préférentiellement, l’élastomère présente une dureté de 75 shore A. [0047] Preferably, the elastomer has a hardness of 75 shore A.
[0048] La teneur en poids de la charge inorganique dans le matériau polymère souple est supérieure à 10%. The content by weight of the inorganic filler in the flexible polymer material is greater than 10%.
[0049] La teneur en poids de la charge inorganique dans le matériau polymère souple peut aller jusqu’à 70% voire 80% en poids avec ce mode de fabrication selon l’invention. Au-delà avec les élastomères connus, des problématiques de fabrication peuvent être rencontrées. The content by weight of the inorganic filler in the flexible polymer material can go up to 70% or even 80% by weight with this manufacturing method according to the invention. Beyond that with known elastomers, manufacturing problems may be encountered.
[0050] La teneur en poids de la charge inorganique dans le matériau polymère souple est préférentiellement supérieure ou égale à 15% [0050] The content by weight of the inorganic filler in the flexible polymer material is preferably greater than or equal to 15%
[0051] La teneur en poids de la charge inorganique dans le matériau polymère souple est préférentiellement supérieure ou égale à 20%. [0051] The content by weight of the inorganic filler in the flexible polymer material is preferably greater than or equal to 20%.
[0052] La teneur en poids de la charge inorganique dans le matériau polymère souple est préférentiellement supérieure ou égale à 30%. [0052] The content by weight of the inorganic filler in the flexible polymer material is preferably greater than or equal to 30%.
[0053] La teneur en poids de la charge inorganique dans le matériau polymère souple est préférentiellement supérieure ou égale à 40%. [0053] The content by weight of the inorganic filler in the flexible polymer material is preferably greater than or equal to 40%.
[0054] La matière inorganique, sous forme d’une poudre, formant la charge du matériau ainsi qu’optionnellement les agents de couplage, les pigments, les diluants, les plastifiants ou autres, sont introduits au polymère lors du procédé de fabrication du matériau polymère souple sous la forme de granulés. [0054] The inorganic material, in the form of a powder, forming the filler of the material as well as optionally the coupling agents, pigments, diluents, plasticizers or others, are introduced into the polymer during the manufacturing process of the flexible polymer material in the form of granules.
[0055] La matière inorganique est par exemple une poudre céramique dont les particules présentent une taille comprise entre 100 nm et 10 mu pm. The inorganic material is for example a ceramic powder whose particles have a size between 100 nm and 10 mu pm.
[0056] La matière inorganique est par exemple une poudre de zircone dont les particules présentent une taille comprise entre 100 nm et 10 mu. The inorganic material is for example a zirconia powder whose particles have a size between 100 nm and 10 mu.
[0057] Les granulés de matériau polymère souple à charge inorganique sont fabriqués par découpe d’un boudin issu d’une extrusion des différentes matières susmentionnées qui sont introduites dans une trémie d’extrudeuse. [0057] The granules of flexible polymer material with an inorganic filler are manufactured by cutting a rod resulting from an extrusion of the various materials mentioned above which are introduced into an extruder hopper.
[0058] Si le matériau comporte un agent de couplage, celui-ci peut être introduit dans un premier temps dans la trémie de l’extrudeuse soit séparément, soit avec les granulés du polymère avant d’introduire la matière inorganique sous la forme de poudre, (par exemple une poudre métallique et/ou céramique) qui est introduite dans un second temps dans l’extrudeuse. Lorsque l’agent de couplage est introduit séparément, il peut être introduit sous forme de poudre. [0058] If the material includes a coupling agent, this can be introduced initially into the hopper of the extruder either separately or with the granules of the polymer before introducing the inorganic material in the form of powder. , (for example a metal and/or ceramic powder) which is subsequently introduced into the extruder. When the coupling agent is introduced separately, it can be introduced in powder form.
[0059] Préférentiellement, pour une bonne intégration de la matière inorganique dans le mélange, il faut préparer un pré-mélange par procédé de mélange haute vitesse entre l’agent de couplage et la matière inorganique. Ce pré-mélange peut ensuite être gavé dans une extrudeuse bi-visse afin d’être bien disperser dans le polymère. [0059] Preferably, for good integration of the inorganic material into the mixture, a pre-mixture must be prepared by a high-speed mixing process between the coupling agent and the inorganic material. This pre-mixture can then be fed into a twin-screw extruder in order to be well dispersed in the polymer.
[0060] Si le matériau comporte des pigments, ils peuvent être introduits lors de l’extrusion et avantageusement dans un second temps. Il est également envisageable de le mélanger aux granulés du polymère juste avant l’extrusion. Procédés de fabrication d’un article en matériau polymère souple à charge inorganique [0060] If the material contains pigments, they can be introduced during extrusion and advantageously in a second step. It is also possible to mix it with the polymer granules just before extrusion. Methods for manufacturing an article made of flexible polymer material with an inorganic filler
[0061] L’article peut être fabriqué par moulage, par injection, par extrusion ou par impression 3D. [0061] The article can be manufactured by molding, by injection, by extrusion or by 3D printing.
[0062] L’article réalisé est aussi bien une pièce finie qu’une pièce semi- finie. [0062] The article produced is both a finished part and a semi-finished part.
[0063] Pour un moulage par injection, les granulés de matériau polymère souple à charge inorganique décrits précédemment sont préparés, puis introduits dans une trémie pour être fondus, la matière est ensuite malaxée puis injectée dans un moule pour former l’article ou une partie de l’article (par surmoulage d’une autre partie). [0063] For injection molding, the granules of flexible polymer material with inorganic filler described above are prepared, then introduced into a hopper to be melted, the material is then kneaded then injected into a mold to form the article or a part of the article (by overmolding another part).
[0064] Par exemple, l’injection est réalisée dans un moule qui a une température comprise entre 60 et 100°C, de préférence entre 70 et 80°C, tandis que la matière lors de l’injection a une température comprise entre 200 et 300°C, et, de préférence, entre 250 et 300°C. [0064] For example, the injection is carried out in a mold which has a temperature between 60 and 100° C., preferably between 70 and 80° C., while the material during the injection has a temperature between 200° C. and 300°C, and preferably between 250 and 300°C.
[0065] L’article peut également être fabriqué par impression 3D telle que par FDM (Fusion Deposition Molding), soit à partir de granulés décrits précédemment ou soit directement à partir d’un fil extrudé non découpé en granulés. [0065] The article can also be manufactured by 3D printing such as by FDM (Fusion Deposition Molding), either from granules described above or directly from an extruded wire not cut into granules.
[0066] À titre d’exemple, l’article peut être un élément constitutif de montres, bijoux, bracelets, etc. [0066] For example, the article can be a constituent element of watches, jewelry, bracelets, etc.
[0067] L’article peut également être un élément constitutif d’une lunette, par exemple une monture, une branche, un patin. [0067] The article can also be a constituent element of a spectacle, for example a frame, a branch, a pad.
[0068] De manière non limitative et non exhaustive, l’article selon l’invention peut également être un élément constitutif, ou former l’intégralité, d’un article de sport, d’un article de cuisine, d’un article ou d’un instrument de musique, d’un article de maroquinerie ou de mercerie, d’un composant automobile ou aéronautique, d’un composant pour article électronique (par exemple coque de protection de téléphone, clavier d’ordinateur, touches de clavier d’ordinateur, casque audio, ... ), un article d’écriture, etc. [0068] In a non-limiting and non-exhaustive manner, the article according to the invention can also be a constituent element, or form the entirety, of a sporting article, a kitchen article, an article or a musical instrument, an article of leather goods or haberdashery, an automobile or aeronautical component, a component for an electronic article (for example example protective phone case, computer keyboard, computer keyboard keys, headphones, etc.), a writing article, etc.
[0069] Avantageusement, l’article est un composant ou une partie d’un composant dont la fonctionnalité nécessite une certaine fonction, le choix de la charge inorganique sera réalisé en fonction de la fonction désirée. [0069] Advantageously, the article is a component or part of a component whose functionality requires a certain function, the choice of the inorganic filler will be made according to the desired function.
[0070] A titre d’exemple, l’article est réalisé dans un matériau composite comprenant un polymère élastomère souple, ou à base de polymère élastomère souple et d’une charge céramique. La charge céramique permettant d’améliorer la conductivité thermique du matériau. [0070] For example, the article is made from a composite material comprising a flexible elastomeric polymer, or based on a flexible elastomeric polymer and a ceramic filler. The ceramic filler makes it possible to improve the thermal conductivity of the material.
[0071] Dans le domaine particulier de l’horlogerie, cet article peut être par exemple un bracelet. [0071] In the particular field of watchmaking, this article can for example be a bracelet.
Alternative de réalisation Alternative realization
[0072] L’article peut également être fabriqué par un procédé de mise en œuvre textile de manière à confectionner un article textile technique. [0072] The article can also be manufactured by a textile processing process so as to make a technical textile article.
[0073] Ainsi, l’article peut être fabriqué par tissage, tricotage, tressage, par broderie, etc. [0073] Thus, the article can be manufactured by weaving, knitting, braiding, embroidery, etc.
[0074] Pour un tel procédé de mise en œuvre textile, , il est nécessaire de fabriquer au préalable un fil textile composite à partir du matériau polymère souple chargé avec au moins une matière inorganique décrit précédemment. Un tel fil textile doit présenter certaines propriétés pour pouvoir être tissé ensuite. [0074] For such a textile implementation process, it is necessary to first manufacture a composite textile yarn from the flexible polymer material loaded with at least one inorganic material described above. Such a textile yarn must have certain properties in order to be able to be woven afterwards.
[0075] Le procédé de fabrication d’un fil textile composite consiste dans un premier temps à préparer les granulés de matériau polymère souple à charge inorganique comme décrit précédemment avec une teneur en particules inorganiques désirée, préférentiellement supérieure à 10% en poids. [0075] The process for manufacturing a composite textile yarn consists initially of preparing granules of flexible polymer material with an inorganic filler as described above with a desired inorganic particle content, preferably greater than 10% by weight.
[0076] Pour la fabrication d’un fil textile composite pour la confection d’un article textile technique présentant une conductivité thermique améliorée, on peut choisir par exemple un polymère élastomère PEBA mélangé à une poudre de zircone, dont la teneur de masse de zircone est de 40%, et dont les particules présentent une taille comprise entre 100 nm et 10 mu. [0076] For the manufacture of a composite textile yarn for the manufacture of a technical textile article having improved thermal conductivity, we can choose for example a PEBA elastomeric polymer mixed with a zirconia powder, whose zirconia mass content is 40%, and whose particles have a size between 100 nm and 10 mu.
[0077] Le fil textile composite, appelé par la suite fil B, est un monofilament obtenu par extrusion sous forme d’un profilé souple, présentant par exemple une section circulaire, ovale ou encore polygonale en fonction des besoins et des effets techniques ou esthétiques souhaités pour l’article textile confectionné à partir du fil textile composite selon l’invention. [0077] The composite textile yarn, subsequently called yarn B, is a monofilament obtained by extrusion in the form of a flexible profile, having for example a circular, oval or even polygonal section depending on the needs and technical or aesthetic effects desired for the textile article made from the composite textile yarn according to the invention.
[0078] Préférentiellement, la section du fil B est incluse dans un diamètre compris entre 0,2 mm et 2 mm. A cet effet, la filière de l’extrudeuse est adaptée pour obtenir le profilé désiré avec la bonne section et le bon diamètre. [0078] Preferably, the section of wire B is included in a diameter of between 0.2 mm and 2 mm. For this purpose, the extruder die is adapted to obtain the desired profile with the right section and diameter.
[0079] En dessous d’un diamètre de 0,2 mm, le fil B obtenu sera trop fragile de par sa teneur élevée en charge inorganique, par exemple en céramique dans l’exemple de réalisation donné. [0079] Below a diameter of 0.2 mm, the wire B obtained will be too fragile due to its high content of inorganic filler, for example ceramic in the given embodiment.
[0080] Au-delà d’un diamètre de 2mm, le fil B obtenue sera trop épais et occasionnera des problèmes lors du tissage. Il ne pourra être utilisé qu’en fil de chaine. [0080] Beyond a diameter of 2mm, the wire B obtained will be too thick and will cause problems during weaving. It can only be used as a warp thread.
[0081] Préférentiellement, la filière est configurée pour obtenir un fil textile composite, fil B, avec une section circulaire d’un diamètre de 0,7 mm afin de maximiser les contacts de surface, notamment à la peau. [0081] Preferably, the die is configured to obtain a composite textile yarn, yarn B, with a circular section with a diameter of 0.7 mm in order to maximize surface contacts, particularly to the skin.
[0082] La figure 1 illustre schématiquement la section du fil B en matériau polymère souple P chargé en particules inorganiques C obtenu par le procédé de fabrication par extrusion qui vient d’être décrit. [0082] Figure 1 schematically illustrates the section of wire B made of flexible polymer material P loaded with inorganic particles C obtained by the extrusion manufacturing process which has just been described.
[0083] La réalisation d’un fil textile composite en matériau polymère souple chargé avec au moins une matière inorganique par un procédé d’extrusion tel que décrit permet de s’affranchir des problématiques de casse liées à la filature des filaments, notamment par la réalisation de fils avec des sections plus importantes mais aussi par la diminution des contraintes imposées sur le fil lors de la fabrication. [0083] The production of a composite textile yarn in flexible polymer material loaded with at least one inorganic material by an extrusion process as described makes it possible to overcome the problems of breakage linked to the spinning of the filaments, in particular by the making yarns with larger sections but also by the reduction of the constraints imposed on the wire during manufacturing.
[0084] Ainsi, grâce à cette méthode de fabrication d’un fil textile composite, il est possible d’augmenter significativement la teneur en charge inorganique, et notamment en céramique, sans risque de casse du fil lors de la fabrication ou lors de la confection d’un article textile technique par tissage. [0084] Thus, thanks to this method of manufacturing a composite textile yarn, it is possible to significantly increase the content of inorganic filler, and in particular ceramic, without risk of breakage of the yarn during manufacturing or during processing. making a technical textile article by weaving.
[0085] Selon une première variante de réalisation d’un article textile technique, le fil textile composite B ainsi obtenu est tissé avec un deuxième fil textile B identique pour former un fil de chaîne de type B et un fil de trame de type B. [0085] According to a first alternative embodiment of a technical textile article, the composite textile yarn B thus obtained is woven with a second identical textile yarn B to form a warp yarn of type B and a weft yarn of type B.
[0086] Selon une deuxième variante de réalisation d’un article textile, le fil textile composite B ainsi obtenu est tissé avec un deuxième fil textile B’ obtenu de manière similaire au fil B, mais dont la charge est différente, par exemple inorganique ou autre. [0086] According to a second alternative embodiment of a textile article, the composite textile yarn B thus obtained is woven with a second textile yarn B' obtained in a manner similar to the yarn B, but whose charge is different, for example inorganic or other.
[0087] Selon une troisième variante de réalisation d’un article textile, le fil textile B ainsi obtenu est tissé avec un fil textile plus conventionnel, dit fil A, non chargé en matière inorganique, par exemple obtenu par filature avec un titre de 470 dTex de manière à apporter de la souplesse à l’article textile tissé et à faciliter le tissage. [0087] According to a third alternative embodiment of a textile article, the textile yarn B thus obtained is woven with a more conventional textile yarn, called yarn A, not loaded with inorganic material, for example obtained by spinning with a count of 470 dTex so as to provide flexibility to the woven textile article and to facilitate weaving.
[0088] Le fil textile A est par exemple composé de filaments ou de fibres en matière synthétique, par exemple en polymère thermoplastique. [0088] The textile yarn A is for example composed of filaments or fibers of synthetic material, for example of thermoplastic polymer.
[0089] Par exemple le fil textile A est un fil composé de filaments ou fibres en polyamide, préférentiellement en polyamide aliphatiques d’origine renouvelable, comme par exemple le polyamide 11 . [0089] For example, textile yarn A is a yarn composed of polyamide filaments or fibers, preferably aliphatic polyamide of renewable origin, such as for example polyamide 11.
[0090] Dans cette troisième variante, le fil B chargé en matière inorganique est préférentiellement utilisé comme fil de chaîne et le fil A non chargé est utilisé comme fil de trame. Ainsi, on minimise davantage les contraintes imposées lors du tissage sur le fil textile B chargé en particules inorganiques. Toutefois, l’inverse est également possible. [0091] Quelle que soit la variante de tissage, le fil textile composite selon l’invention permet de confectionner un article textile technique par des méthodes conventionnelles de tissage bien connues de l’homme du métier. [0090] In this third variant, the thread B loaded with inorganic material is preferentially used as warp thread and the unfilled thread A is used as weft thread. Thus, the constraints imposed during weaving on the textile yarn B loaded with inorganic particles are further minimized. However, the reverse is also possible. [0091] Whatever the weaving variant, the composite textile yarn according to the invention makes it possible to make a technical textile article by conventional weaving methods well known to those skilled in the art.
[0092] La figure 2 illustre deux types d’armure de tissage qu’il est possible de réaliser lors du procédé de tissage avec un fil textile A et un fil textile B chargé en particules inorganiques. De préférence, l’armure de tissage est un sergé ou un satin afin de pouvoir avoir des flottés de fils B sur des fils A et de pouvoir maximiser la surface apparente de fils B pour augmenter la surface de contact avec la peau. [0092] Figure 2 illustrates two types of weaving weave that can be produced during the weaving process with a textile yarn A and a textile yarn B loaded with inorganic particles. Preferably, the weave is a twill or satin in order to be able to have floats of threads B on threads A and to be able to maximize the apparent surface of threads B to increase the contact surface with the skin.
[0093] Préférentiellement, la matière inorganique est une céramique ; toutefois il est possible de faire varier la nature de la charge dans le polymère élastomère afin de faire varier la fonction. [0093] Preferably, the inorganic material is a ceramic; however it is possible to vary the nature of the filler in the elastomeric polymer in order to vary the function.
[0094] A titre d’exemple, la matière inorganique peut être métallique pour apporter un effet métallisé ou nacré pour obtenir un effet esthétique. [0094] For example, the inorganic material can be metallic to provide a metallic or pearly effect to obtain an aesthetic effect.
[0095] A titre d’exemple, la matière inorganique peut être un métal précieux. [0095] For example, the inorganic material can be a precious metal.
[0096] Un tel procédé de fabrication d’un fil textile par extrusion permet également de pouvoir augmenter la teneur en pigment d’un fil textile, comme par exemple la teneur en pigment phosphorescent pour obtenir un effet lumineux de nuit plus intense qu’avec les fils textiles du commerce qui ne contiennent pas plus de 10% en poids de pigment. [0096] Such a process for manufacturing a textile yarn by extrusion also makes it possible to increase the pigment content of a textile yarn, such as for example the phosphorescent pigment content to obtain a more intense luminous effect at night than with commercial textile yarns which do not contain more than 10% by weight of pigment.
[0097] Pour obtenir un effet anti-odeur pour le confort, le polymère élastomère peut également être chargé avec un additif antibactérien. [0097] To obtain an anti-odor effect for comfort, the elastomeric polymer can also be loaded with an antibacterial additive.
[0098] En plus des deux fils de chaine et de trame décrits précédemment, il est possible d’introduire des fils textiles spécifiques avec des charges inorganiques différentes, ou des fils textiles avec d’autres propriétés afin de combiner plusieurs fonctions techniques et/ou esthétiques dans un même article textile technique dans un même article textile. [0099] Quelle que soit l’alternative de réalisation ou le procédé de fabrication de l’article, la matière inorganique, ici des particules inorganiques, est toujours enrobée dans la matière polymère ce qui permet de s’affranchir des problématiques d’irritations de la peau car la matière inorganique n’est pas directement en contact avec la peau de l’utilisateur. [0098] In addition to the two warp and weft threads described above, it is possible to introduce specific textile threads with different inorganic fillers, or textile threads with other properties in order to combine several technical functions and/or aesthetics in the same technical textile article in the same textile article. [0099] Whatever the alternative of production or the manufacturing process of the article, the inorganic material, here inorganic particles, is always coated in the polymer material which makes it possible to overcome the problems of irritation of the skin because the inorganic material is not directly in contact with the user's skin.
[00100] Le matériau selon l’invention permet également d’apporter une fonction supplémentaire à l’article, comme par exemple l’augmentation de la conductivité thermique avec l’utilisation de particules de céramique dans la matière. [00100] The material according to the invention also makes it possible to provide an additional function to the article, such as for example the increase in thermal conductivity with the use of ceramic particles in the material.

Claims

REVENDICATIONS
1. Article caractérisé en ce qu’il est réalisé dans un matériau composite comprenant un polymère souple (P) et une charge formée par au moins une matière inorganique (C). 1. Article characterized in that it is made of a composite material comprising a flexible polymer (P) and a filler formed by at least one inorganic material (C).
2. Article selon la revendication précédente caractérisé en ce que la matière inorganique (C) est sous la forme de particules ou de fibres. 2. Article according to the preceding claim characterized in that the inorganic material (C) is in the form of particles or fibers.
3. Article selon l’une des revendications précédentes caractérisé en ce que le polymère souple (P) est à base d’élastomère. 3. Article according to one of the preceding claims characterized in that the flexible polymer (P) is based on elastomer.
4. Article selon l’une des revendications précédentes caractérisé en ce que le polymère souple (P) est un élastomère. 4. Article according to one of the preceding claims characterized in that the flexible polymer (P) is an elastomer.
5. Article selon l’une des revendications 3 à 4 caractérisé en ce que l’élastomère est élastomère thermoplastique, un matériau silicone, un caoutchouc vulcanisé, ou un caoutchouc naturel. 5. Article according to one of claims 3 to 4 characterized in that the elastomer is a thermoplastic elastomer, a silicone material, a vulcanized rubber, or a natural rubber.
6. Article selon l’une des revendications 3 à 5 caractérisé en ce que l’élastomère présente une dureté comprise entre 30 shore A et 85 shore A, préférentiellement entre 65 shore A et 75 shore A, préférentiellement égale à 75 shore A. 6. Article according to one of claims 3 to 5 characterized in that the elastomer has a hardness of between 30 shore A and 85 shore A, preferably between 65 shore A and 75 shore A, preferably equal to 75 shore A.
7. Article selon l’une des revendications 2 à 6 caractérisé en ce qu’au moins une matière inorganique (C) est formée par des particules métalliques et/ou céramiques, préférentiellement par des particules de zircone. 7. Article according to one of claims 2 to 6 characterized in that at least one inorganic material (C) is formed by metallic and/or ceramic particles, preferably by zirconia particles.
8. Article selon l’une des revendications précédentes caractérisé en ce que le matériau composite comprend une teneur en matière inorganique supérieure à 10% en poids, préférentiellement supérieure à 15% en poids, préférentiellement supérieure à 20% en poids, préférentiellement supérieure à 30% en poids, et préférentiellement supérieure à 40% en poids. Article selon l’une des revendications précédentes caractérisé en ce que le matériau composite comprend optionnellement un ou plusieurs agents de couplage, un ou plusieurs pigments, un ou plusieurs additifs antibactériens, un ou plusieurs diluants et/ou des plastifiants, des fibres cellulosiques. Procédé de fabrication d’un article selon l’une des revendications précédentes caractérisé en ce que le procédé de fabrication est un procédé de moulage, d’injection, d’extrusion, d’impression 3D, ou un procédé de mise en œuvre textile. Procédé de fabrication d’un article selon la revendication précédente caractérisé en ce qu’il comporte au préalable une étape de fourniture des matières de base du matériau composite comprenant un polymère souple (P) et une charge formée par au moins une matière inorganique (C). Procédé de fabrication d’un article selon la revendication précédente caractérisé en ce que l’étape de fourniture est une étape de préparation de granulés de matériau composite comprenant au moins un polymère souple (P) et une charge formée par au moins une matière inorganique (C), la teneur en matière inorganique (C) étant supérieure à 10% en poids, préférentiellement supérieure à 15% en poids, préférentiellement supérieure à 20% en poids, préférentiellement supérieure à 30% en poids, préférentiellement supérieure à 40% en poids. 8. Article according to one of the preceding claims characterized in that the composite material comprises an inorganic material content greater than 10% by weight, preferably greater than 15% by weight, preferably greater than 20% by weight, preferably greater than 30% by weight, and preferably greater than 40% by weight. Article according to one of the preceding claims, characterized in that the composite material optionally comprises one or more coupling agents, one or more pigments, one or more antibacterial additives, one or more diluents and/or plasticizers, cellulose fibers. Method of manufacturing an article according to one of the preceding claims, characterized in that the manufacturing process is a molding, injection, extrusion, 3D printing process, or a textile implementation process. Method of manufacturing an article according to the preceding claim characterized in that it first comprises a step of supplying the basic materials of the composite material comprising a flexible polymer (P) and a filler formed by at least one inorganic material (C ). Method of manufacturing an article according to the preceding claim characterized in that the supply step is a step of preparing granules of composite material comprising at least one flexible polymer (P) and a filler formed by at least one inorganic material ( C), the content of inorganic material (C) being greater than 10% by weight, preferably greater than 15% by weight, preferably greater than 20% by weight, preferably greater than 30% by weight, preferably greater than 40% by weight .
PCT/EP2023/075681 2022-11-01 2023-09-18 Article made of a flexible polymer material, and method for producing such an article WO2024094356A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007209441A (en) * 2006-02-08 2007-08-23 Eg Junkan Kenkyusho:Kk Radon hot spring bathing mat
WO2011089352A1 (en) * 2010-01-19 2011-07-28 Arkema France Thermoplastic powder composition and three-dimensional objects manufactured by sintering such a composition
EP3978246A1 (en) * 2020-10-02 2022-04-06 Universite De Bretagne Sud Use of a composition including a high rate of inorganic material(s) and a thermoplastic elastomer in an additive manufacturing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007209441A (en) * 2006-02-08 2007-08-23 Eg Junkan Kenkyusho:Kk Radon hot spring bathing mat
WO2011089352A1 (en) * 2010-01-19 2011-07-28 Arkema France Thermoplastic powder composition and three-dimensional objects manufactured by sintering such a composition
EP3978246A1 (en) * 2020-10-02 2022-04-06 Universite De Bretagne Sud Use of a composition including a high rate of inorganic material(s) and a thermoplastic elastomer in an additive manufacturing method

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