[go: up one dir, main page]

EP2122045A2 - Textile substrate including a thermal regulation composition surrounding transfer islands - Google Patents

Textile substrate including a thermal regulation composition surrounding transfer islands

Info

Publication number
EP2122045A2
EP2122045A2 EP08761746A EP08761746A EP2122045A2 EP 2122045 A2 EP2122045 A2 EP 2122045A2 EP 08761746 A EP08761746 A EP 08761746A EP 08761746 A EP08761746 A EP 08761746A EP 2122045 A2 EP2122045 A2 EP 2122045A2
Authority
EP
European Patent Office
Prior art keywords
textile substrate
microcapsules
formulation
substrate according
islands
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08761746A
Other languages
German (de)
French (fr)
Other versions
EP2122045B1 (en
Inventor
Claudine Colin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lainiere de Picardie SA
Lainiere de Picardie BC SAS
Original Assignee
Lainiere de Picardie SA
Lainiere de Picardie BC SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lainiere de Picardie SA, Lainiere de Picardie BC SAS filed Critical Lainiere de Picardie SA
Publication of EP2122045A2 publication Critical patent/EP2122045A2/en
Application granted granted Critical
Publication of EP2122045B1 publication Critical patent/EP2122045B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2041—Two or more non-extruded coatings or impregnations
    • Y10T442/2123—At least one coating or impregnation contains particulate material

Definitions

  • the invention relates to a textile substrate incorporating a thermal regulation composition, as well as to a process for manufacturing such a textile substrate.
  • thermo regulation composition which comprises microcapsules incorporating a composition of a phase change material. Indeed, by absorption - thermal energy recovery during phase changes of the material, the textile substrate can delay the temperature changes so as to provide thermal comfort.
  • microcapsules into a textile substrate, it is in particular known to integrate them in the fibers (see in particular the document EP-0 306 202), to arrange them in a layer of polymeric binder which is coated on the textile substrate (see in particular EP-0 611 330), or to fix them to the fibers individually (see in particular document EP-1 275 769).
  • thermal comfort conferred by the thermal regulation composition.
  • this thermal comfort depends on the speed and distribution of heat transfer in the thermal regulation composition.
  • speed of transfer of moisture through the thermal regulation composition is also a relevant factor relative to the perceived thermal comfort.
  • the invention aims to overcome the problems of the prior art by providing a textile substrate incorporating a thermal regulation composition, wherein the heat transfer and / or moisture are optimized to improve the perceived thermal comfort.
  • the invention provides a textile substrate comprising fibers, said substrate incorporating a thermal regulation composition, said substrate further comprising islands of material which are associated with the fibers to be surrounded by the composition thermal regulation, the material forming the islands being able to promote the transfer of heat and / or moisture in the thermal control composition.
  • the thermal regulation composition comprises microcapsules provided with an envelope in which a phase change material is disposed, the melting temperature of said material being arranged to ensure thermoregulation, the microcapsules being associated with the fibers by bridging.
  • the invention provides a method for manufacturing such a textile substrate, said method comprising the steps of:
  • preparing a formulation of microcapsules containing the phase-change material in an envelope said envelope being based on a material comprising a type of reactive group under ionizing radiation, said formulation further comprising at least one bridging agent having two types reactive groups under ionizing radiation;
  • the invention relates to a textile substrate comprising fibers, said substrate being able to be of any type, in particular knitted, woven or comprising a nonwoven web.
  • the textile substrate comprises a nonwoven web of a weight of less than 50 g / m 2 , especially between 30 and 80 g / m 2 , and a thickness of less than 0.5 mm.
  • the length of the fibers of the sheet may be between 30 and 60 mm.
  • the sheet may be bonded by water jet or by any other means to obtain a resistant and absorbent sheet (needling, chemical bonding with suitable binder, thermal bonding).
  • the textile substrate is based on hydrophilic fibers having a titer of less than 4 dtex, so as to promote the flexibility thus, as will be seen in the following description, that the absorption capacity of an aqueous formulation of microcapsules.
  • the fibers may be based on polyester or polyamide.
  • the textile substrate according to the invention incorporates a thermal regulation composition.
  • the thermal control composition may comprise a phase change material whose melting point is between 15 ° C and 38 ° C, preferably between 22 ° C and 35 ° C, so as to ensure thermoregulation in the vicinity of the human body temperature.
  • such a composition may be based on paraffin, in particular comprising between 16 and 22 carbon atoms depending on the desired melting temperature.
  • paraffin in particular comprising between 16 and 22 carbon atoms depending on the desired melting temperature.
  • non-paraffin-containing flame retardant phase change materials may be used, especially for non-fire applications.
  • the thermal regulation composition comprises microcapsules having a size less than 20 microns, in particular between 1 and 10 microns on average.
  • the microcapsules are provided with an envelope in which the phase change material is disposed.
  • the microcapsules can be integrated in the fibers, arranged in a layer of polymeric binder which is coated on the textile substrate, or fixed to the fibers individually.
  • the thermal regulation composition may comprise two types of microcapsules, the phase-change materials of each of the types of microcapsules differing in their melting temperature.
  • the two types of microcapsules may be those referenced Lurapret TX PMC 28 and Lurapret TX PMC 35 from BASF, which respectively have a melting point at 28 ° C. and 35 ° C.
  • the phase-change material is respectively n-Octadecane and n-Eicosane, the storage or calorization storage capacity being of the order of 170 J / g.
  • the envelope of these microcapsules is based on polymethyl methacrylate (PMMA).
  • the substrate further comprises islands of material which are associated with the fibers to be surrounded, at least partially, by the thermal regulation composition, the material forming the islets being able to promote the transfer of heat and / or moisture in the thermal regulation composition.
  • the islands promote heat exchange and / or moisture in the thermal control composition so as to improve the thermal comfort conferred.
  • the exchanges are carried out essentially by conduction by providing that the islands are in contact, or at least in the immediate vicinity, of the regulation composition.
  • the thermal regulation composition comprises microcapsules
  • the islands promote the transfer of heat between them so as to improve the absorption kinematic, respectively restitution, of caloric energy by the phase change material.
  • the islands are formed based on a hygroscopic polymer material, in particular chosen from the group comprising polyvinylalcohol (PVA), cellulose derivatives, cellulose Carboxy Methyl, Chitosan, derivatives of Chitin.
  • PVA polyvinylalcohol
  • cellulose derivatives cellulose Carboxy Methyl
  • Chitosan derivatives of Chitin.
  • the islets may also contain microcapsules which are embedded in the material, said microcapsules incorporating an active substance.
  • the active substance may also be a phase change material improving thermoregulation, or have other functions, for example hygienic or comfort.
  • the active substance may comprise essential oils, in particular for improving respiration, perfumes, repellents, especially mosquito repellents, conductive or antistatic fillers, bacteriostatic agents such as silver salts, - justifys.
  • Chitosan provides a bacteriostatic function in addition to hygroscopy.
  • the islands are arranged on at least one surface of the textile substrate, in the form of a discrete network of geometric zones, for example in the form of a two-dimensional network of points of rectangular shape or the like.
  • the islands can cover between 5% and 40% of the surface of the textile substrate on which they are arranged.
  • the islands can form or include an inscription or logo visible on one side of the textile substrate, for example by incorporating a pigment into the material forming them.
  • the textile substrate can be used to make a textile article, especially for bedding such as pillows, duvets, or for clothing, including sports or professional.
  • the textile article may comprise, on one side of the textile substrate, an inner textile layer and, on the other side of said substrate, an outer textile layer which is arranged to trap a volume of air, such as a layer of wadding.
  • a volume of air such as a layer of wadding.
  • the textile article may further comprise a breathable layer, for example hydrophilic or hydrophobic porous, which is disposed on the outer textile layer so as to let the body breathe by preventing liquid water from reaching it.
  • a method of manufacturing a textile substrate according to the invention is described below in which the microcapsules are associated with the fibers by bridging between their envelope and the fibers of said substrate.
  • the textile substrate may incorporate more than 10 g / m 2 , in particular more than 40 g / m 2 , of microcapsules so as to allow the absorption and recovery of 5 to more than 150 J / g of caloric energy. .
  • the method provides for preparing a microcapsule formulation containing the phase change material in an envelope, said envelope being based on a material comprising a reactive group type under ionizing radiation.
  • groups may comprise an unsaturated bond which, under the effect of ionizing radiation, forms a reactive free radical.
  • the reactive groups under ionizing radiation are chosen from the group comprising hydroxyl groups, carboxyl groups, carbonyl groups, acrylates, methacrylates, amines, amides, imides, urethanes, styrenes.
  • the envelope may comprise several types of reactive groups under ionizing radiation.
  • the microcapsule formulation further comprises at least one bridging agent having two types of reactive groups under radiation. ionizing, said types being identical or different.
  • at least some reactive groups may be chosen to be thermally reactive.
  • the microcapsule composition may comprise a mixture of coupling agents, in particular chosen from the group comprising glycidyl acrylate or methacrylate (AGLY, MAGLY), polyethylene glycol 200, 400, 600diacrylates (PEG200 DA, PEG400 DA, PEG600 DA), dipropylene glycol diacrylate (DPGDA), potassium sulfopropyl methacrylate (SPMK) and lauryl methacrylate or acrylate.
  • GLY glycidyl acrylate or methacrylate
  • DPGDA dipropylene glycol diacrylate
  • SPMK potassium sulfopropyl methacrylate
  • AGLY or MAGLY is a difunctional bridging agent having an epoxy group and an acrylate or methacrylate group and PEG DA are difunctional internal plasticizers which participate in bridging by lengthening the binding chains between the microcapsules and the fibers .
  • PEG DA difunctional internal plasticizers which participate in bridging by lengthening the binding chains between the microcapsules and the fibers .
  • the mass ratio between the bridging agent (s) and the microcapsules is preferably less than 0.5, in particular between 0.10 and 0.30.
  • the microcapsule formulation may comprise between 30% and 60% by weight, in particular between 40% and 50% by weight, of microcapsules dispersed in a solvent, in particular in water.
  • the microcapsule formulation may further comprise at least one agent improving the stability of the dispersion, for example sulfopropyl methacrylate (SPM) or sulfopropyl acrylate (SPA) which are anionic monomers reactive under ionizing radiation, or an acrylic latex such as that marketed under the name HYCAR 26319 which improves the wetting of the microcapsules by the bridging agents while creating bridges between the microcapsules and the substrate.
  • said agent may be a gel polyacrylate or a polyurethane dispersion.
  • the functionalization process further comprises a step of preparing a material capable of promoting the transfer of heat and / or moisture, and then a step of applying the material to at least one area of the surface of the textile substrate so that to form islands associated with the fibers.
  • the material forming the islets also has a tightness to the formulation of microcapsules so, as will be seen later, to prevent the subsequent impregnation of the islets with the microcapsule formulation.
  • the zones devoid of microcapsules can form zones of preferential folds of said substrate.
  • the material forming the islands is based on polyvinyl alcohol (PVA) at least partially hydrolyzed which is dissolved in water, said solution further comprising a release agent for the formulation of microcapsules.
  • PVA polyvinyl alcohol
  • the release agent may be a glycerol and the viscosity of the material is provided to trap the release agent to prevent migration.
  • the material can be thixotropic and have a viscosity of between 50 and 300 dPa.s so as to allow the application in paste form with migration through the textile substrate to coat the fibers.
  • the material forming the islands may be applied by screen printing, followed by at least partial drying of said material before impregnation of the textile substrate with the microcapsule formulation.
  • the amount of deposited material may be between 5 and 40 g / m 2 .
  • the method then provides for impregnating the textile substrate with the microcapsule formulation.
  • the impregnation can be performed by padding, the conditions of said padding and the characteristics of the textile substrate being adapted to carry at least 80% and preferably at least 150% by weight of microcapsule formulation in said textile substrate.
  • the formulation of microcapsules can be thixotropic and its viscosity between 130 and 150 mPa.s, especially by adding a fluidifier to said formulation, such as isopropanol.
  • a fluidifier such as isopropanol.
  • the textile substrate may undergo, prior to its impregnation, particular treatments, in particular to improve its cohesion and / or its wettability.
  • the calendering pressure during padding is relatively low, in particular of the order of 1 to 2 bar, to allow a significant load with penetration and a homogeneous distribution of the microcapsule formulation in the textile substrate.
  • the amount of formulation impregnated in a textile substrate with a surface mass of 50 g / m 2 may be greater than 50 g / m 2 , in particular between 50 g / m 2 and 150 g / m 2 .
  • the textile substrate may be dried, in particular by means of infrared lamps, before the application of ionizing radiation to the impregnated textile substrate. Drying also makes it possible to thermofix the microcapsule formulation in the textile substrate.
  • the heat-setting may be carried out after the application of the ionizing radiation, for example at a temperature between 100 and 140 0 C, to complete the fixing of the microcapsules by reactions of the thermally reactive bridging agents.
  • the power and duration of the radiation are arranged to activate the reactive groups so as to bridge the microcapsules on said substrate.
  • the ionizing radiation is ion bombardment generated by an electron accelerator, which can be realized in one or two passages, including a passage on each side of the textile substrate.
  • the power of the ionizing radiation combined with the presence of the different reactive groups makes it possible to fix a large quantity of microcapsules in the textile substrate.
  • the reactions between the reactive groups of the envelope and the bridging agents make it possible to connect the envelope of the microcapsules to the fibers, the microcapsules between them and possibly the bridging agents between them, so as to create a network.
  • the textile substrate can be washed and then dried or undergo other treatments necessary for its subsequent use.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)

Abstract

A fiber-containing textile substrate (A), incorporating a thermal regulation composition (I), also has 'islets', associated with the fibers and surrounded by (I), of material (II) for promoting the transfer of heat and/or moisture into (I). An independent claim is included for the production of (A), incorporating (I) and (II), where (I) is in the form of microcapsules (MC's) containing phase-change material (Ia), by: (1) preparing a formulation containing the MC's, comprising (Ia) in a shell of material (III) with groups reacting under ionizing radiation (IZR), and a crosslinker (IV) with two types of groups reacting under IZR; (2) applying (II) to at least one zone on the surface of (A) in the form of islets; (3) impregnating (A) with the MC formulation; and (4) irradiating with IZR to crosslink the MC's on (A) via the reactive groups.

Description

Substrat textile incorporant une composition de régulation thermique entourant des îlots de transfertTextile substrate incorporating a thermi q ue control composition surrounding transfer islets
L'invention concerne un substrat textile incorporant une composition de régulation thermique, ainsi qu'un procédé de fabrication d'un tel substrat textile.The invention relates to a textile substrate incorporating a thermal regulation composition, as well as to a process for manufacturing such a textile substrate.
Pour conférer des propriétés de régulation thermique à un substrat textile, il est connu d'utiliser une composition de régulation thermique qui comprend des microcapsules incorporant une composition d'un matériau à changement de phase. En effet, par absorption - restitution d'énergie thermique lors des changements de phase du matériau, le substrat textile permet de temporiser les changements de température de sorte à procurer un confort thermique.To impart thermal regulation properties to a textile substrate, it is known to use a thermal regulation composition which comprises microcapsules incorporating a composition of a phase change material. Indeed, by absorption - thermal energy recovery during phase changes of the material, the textile substrate can delay the temperature changes so as to provide thermal comfort.
Pour incorporer ces microcapsules à un substrat textile, il est notamment connu de les intégrer dans les fibres (voir notamment le document EP-O 306 202), de les disposer dans une couche de liant polymérique qui est enduite sur le substrat textile (voir notamment le document EP-O 611 330), ou encore des les fixer aux fibres de façon individuelle (voir notamment le document EP-1 275 769).To incorporate these microcapsules into a textile substrate, it is in particular known to integrate them in the fibers (see in particular the document EP-0 306 202), to arrange them in a layer of polymeric binder which is coated on the textile substrate (see in particular EP-0 611 330), or to fix them to the fibers individually (see in particular document EP-1 275 769).
Toutefois, dans toutes ces réalisations, il se pose le problème de l'optimisation du confort thermique conféré par la composition de régulation thermique. En particulier, ce confort thermique dépend de la vitesse et de la répartition des transferts thermiques dans la composition de régulation thermique. Par ailleurs, la vitesse de transfert de l'humidité au travers de la composition de régulation thermique est également un facteur pertinent relativement au confort thermique perçu.However, in all these embodiments, there is the problem of optimizing the thermal comfort conferred by the thermal regulation composition. In particular, this thermal comfort depends on the speed and distribution of heat transfer in the thermal regulation composition. Moreover, the speed of transfer of moisture through the thermal regulation composition is also a relevant factor relative to the perceived thermal comfort.
L'invention a pour but de pallier les problèmes de l'art antérieur en proposant un substrat textile incorporant une composition de régulation thermique, dans lequel les transferts thermiques et/ou d'humidité sont optimisés pour améliorer le confort thermique perçu. A cet effet, et selon un premier aspect, l'invention propose un substrat textile comprenant des fibres, ledit substrat incorporant une composition de régulation thermique, ledit substrat comprenant en outre des îlots de matériau qui sont associés aux fibres pour être entourés par la composition de régulation thermique, le matériau formant les îlots étant apte à favoriser le transfert de chaleur et/ou d'humidité dans la composition de régulation thermique.The invention aims to overcome the problems of the prior art by providing a textile substrate incorporating a thermal regulation composition, wherein the heat transfer and / or moisture are optimized to improve the perceived thermal comfort. For this purpose, and according to a first aspect, the invention provides a textile substrate comprising fibers, said substrate incorporating a thermal regulation composition, said substrate further comprising islands of material which are associated with the fibers to be surrounded by the composition thermal regulation, the material forming the islands being able to promote the transfer of heat and / or moisture in the thermal control composition.
Selon une réalisation particulière la composition de régulation thermique comprend des microcapsules pourvues d'une enveloppe dans laquelle un matériau à changement de phase est disposé, la température de fusion dudit matériau étant agencée pour assurer une thermorégulation, les microcapsules étant associées aux fibres par pontage.According to one particular embodiment, the thermal regulation composition comprises microcapsules provided with an envelope in which a phase change material is disposed, the melting temperature of said material being arranged to ensure thermoregulation, the microcapsules being associated with the fibers by bridging.
Selon un deuxième aspect, l'invention propose un procédé de fabrication d'un tel substrat textile, ledit procédé comprenant les étapes prévoyant de :According to a second aspect, the invention provides a method for manufacturing such a textile substrate, said method comprising the steps of:
- préparer une formulation de microcapsules contenant le matériau à changement de phase dans une enveloppe, ladite enveloppe étant à base d'un matériau comprenant un type de groupement réactif sous rayonnement ionisant, ladite formulation comprenant en outre au moins un agent de pontage présentant deux types de groupements réactifs sous rayonnement ionisant ;preparing a formulation of microcapsules containing the phase-change material in an envelope, said envelope being based on a material comprising a type of reactive group under ionizing radiation, said formulation further comprising at least one bridging agent having two types reactive groups under ionizing radiation;
- préparer un matériau apte à favoriser le transfert de chaleur et/ou d'humidité ; - appliquer le matériau sur au moins une zone de la surface du substrat textile de sorte à former des îlots associés aux fibres ; puis- Prepare a material capable of promoting the transfer of heat and / or moisture; applying the material to at least one area of the surface of the textile substrate so as to form islands associated with the fibers; then
- imprégner le substrat textile avec la formulation de microcapsules ; etimpregnating the textile substrate with the microcapsule formulation; and
- appliquer un rayonnement ionisant sur le substrat textile imprégné de sorte à assurer le pontage des microcapsules sur ledit substrat par réaction des groupements réactifs.applying ionizing radiation to the impregnated textile substrate so as to bridge the microcapsules on said substrate by reacting the reactive groups.
D'autres particularités et avantages de l'invention apparaîtront dans la description qui suit de différents modes de réalisation particuliers. L'invention concerne un substrat textile comprenant des fibres, ledit substrat pouvant être de tout type, notamment tricoté, tissé ou encore comprenant une nappe de non tissé. Dans un exemple de réalisation, le substrat textile comprend une nappe de non tissé d'un poids inférieur à 50 g/m2, notamment compris entre 30 et 80 g/m2, et d'une épaisseur inférieure à 0,5 mm. La longueur des fibres de la nappe peut être comprise entre 30 et 60 mm. La nappe peut être liée par jet d'eau ou par tout autre moyen permettant d'obtenir une nappe résistante et absorbante (aiguilletage, liage chimique avec liant adapté, liage thermique).Other features and advantages of the invention will appear in the following description of various particular embodiments. The invention relates to a textile substrate comprising fibers, said substrate being able to be of any type, in particular knitted, woven or comprising a nonwoven web. In an exemplary embodiment, the textile substrate comprises a nonwoven web of a weight of less than 50 g / m 2 , especially between 30 and 80 g / m 2 , and a thickness of less than 0.5 mm. The length of the fibers of the sheet may be between 30 and 60 mm. The sheet may be bonded by water jet or by any other means to obtain a resistant and absorbent sheet (needling, chemical bonding with suitable binder, thermal bonding).
\\
En particulier, le substrat textile est à base de fibres hydrophiles présentant un titre inférieur à 4 dtex, de sorte à favoriser la souplesse ainsi, comme on le verra dans la suite de la description, que la capacité d'absorption d'un formulation aqueuse de microcapsules.In particular, the textile substrate is based on hydrophilic fibers having a titer of less than 4 dtex, so as to promote the flexibility thus, as will be seen in the following description, that the absorption capacity of an aqueous formulation of microcapsules.
En particulier, les fibres peuvent être à base de polyester ou de polyamide. En variante, on peut prévoir un mélange de fibres polyester ou polyamide et de fibres cellulosiques, notamment en coton ou en viscose, par exemple dans une proportion pondérale de 80% / 20%.In particular, the fibers may be based on polyester or polyamide. Alternatively, there can be a mixture of polyester or polyamide fibers and cellulosic fibers, in particular cotton or viscose, for example in a proportion by weight of 80% / 20%.
Le substrat textile selon l'invention incorpore une composition de régulation thermique. La composition de régulation thermique peut comprendre un matériau à changement de phase dont la température de fusion est comprise entre 15°C et 38°C, de préférence entre 22°C et 35°C, de sorte à assurer une thermorégulation au voisinage de la température corporelle humaine.The textile substrate according to the invention incorporates a thermal regulation composition. The thermal control composition may comprise a phase change material whose melting point is between 15 ° C and 38 ° C, preferably between 22 ° C and 35 ° C, so as to ensure thermoregulation in the vicinity of the human body temperature.
De façon connue, une telle composition peut être à base de paraffine, notamment comprenant entre 16 et 22 atomes de carbone en fonction de la température de fusion souhaitée. Ainsi, lorsque la température ambiante augmente, la liquéfaction de la composition permet une absorption d'énergie calorique à température quasi constante et, lorsque la température ambiante diminue, la solidification de ladite composition permet de restituer ladite énergie calorique. En variante, on peut utiliser des matériaux à changement de phase ignifuges ne contenant pas de paraffines, notamment pour des applications non feu.In known manner, such a composition may be based on paraffin, in particular comprising between 16 and 22 carbon atoms depending on the desired melting temperature. Thus, when the ambient temperature increases, the liquefaction of the composition allows an absorption of caloric energy at almost constant temperature and, when the ambient temperature decreases, the solidification of said composition makes it possible to restore said energy Caloric. Alternatively, non-paraffin-containing flame retardant phase change materials may be used, especially for non-fire applications.
Selon une réalisation, la composition de régulation thermique comprend des microcapsules présentant une taille inférieure à 20 μm, notamment comprise entre 1 et 10 μm en moyenne. Les microcapsules sont pourvues d'une enveloppe dans laquelle le matériau à changement de phase est disposé. De façon connue, les microcapsules peuvent être intégrées dans les fibres, disposées dans une couche de liant polymérique qui est enduite sur le substrat textile, ou encore fixées aux fibres de façon individuelle.According to one embodiment, the thermal regulation composition comprises microcapsules having a size less than 20 microns, in particular between 1 and 10 microns on average. The microcapsules are provided with an envelope in which the phase change material is disposed. In known manner, the microcapsules can be integrated in the fibers, arranged in a layer of polymeric binder which is coated on the textile substrate, or fixed to the fibers individually.
La composition de régulation thermique peut comprendre deux types de microcapsules, les matériaux à changement de phase de chacun des types de microcapsules différant par leur température de fusion. En particulier, les deux types de microcapsules peuvent être celles référencées Lurapret TX PMC 28 et Lurapret TX PMC 35 de la société BASF, qui présentent respectivement une température de fusion à 28°C et 35°C. Pour ce faire, le matériau à changement de phase est respectivement du n-Octadécane et du n-Eicosane, la capacité de stockage ou de restitution de calories étant de l'ordre de 170 J/g. Par ailleurs, l'enveloppe de ces microcapsules est à base de polyméthylméthacrylate (PMMA).The thermal regulation composition may comprise two types of microcapsules, the phase-change materials of each of the types of microcapsules differing in their melting temperature. In particular, the two types of microcapsules may be those referenced Lurapret TX PMC 28 and Lurapret TX PMC 35 from BASF, which respectively have a melting point at 28 ° C. and 35 ° C. For this purpose, the phase-change material is respectively n-Octadecane and n-Eicosane, the storage or calorization storage capacity being of the order of 170 J / g. Moreover, the envelope of these microcapsules is based on polymethyl methacrylate (PMMA).
Le substrat comprend en outre des îlots de matériau qui sont associés aux fibres pour être entourés, au moins partiellement, par la composition de régulation thermique, le matériau formant les îlots étant apte à favoriser le transfert de chaleur et/ou d'humidité dans la composition de régulation thermique. Ainsi, les îlots favorisent les échanges thermiques et/ou d'humidité dans la composition de régulation thermique de sorte à améliorer le confort thermique conféré. En particulier, les échanges sont réalisés essentiellement par 'conduction en prévoyant que les îlots soient au contact, ou au moins au voisinage immédiat, de la composition de régulation. Dans le cas où la composition de régulation thermique comprend des microcapsules, les îlots favorisent le transfert de chaleur entre celles-ci de sorte à améliorer la cinématique d'absorption, respectivement de restitution, d'énergie calorique par le matériau à changement de phase.The substrate further comprises islands of material which are associated with the fibers to be surrounded, at least partially, by the thermal regulation composition, the material forming the islets being able to promote the transfer of heat and / or moisture in the thermal regulation composition. Thus, the islands promote heat exchange and / or moisture in the thermal control composition so as to improve the thermal comfort conferred. In particular, the exchanges are carried out essentially by conduction by providing that the islands are in contact, or at least in the immediate vicinity, of the regulation composition. In the case where the thermal regulation composition comprises microcapsules, the islands promote the transfer of heat between them so as to improve the absorption kinematic, respectively restitution, of caloric energy by the phase change material.
Selon une réalisation, les îlots sont formés à base d'un matériau polymère hygroscopique, notamment choisi dans le groupe comprenant le Polyvinylalcool (PVA), les dérivés cellulosiques, le Carboxy Méthyl de cellulose, le Chitosan, les dérivés de Chitine.According to one embodiment, the islands are formed based on a hygroscopic polymer material, in particular chosen from the group comprising polyvinylalcohol (PVA), cellulose derivatives, cellulose Carboxy Methyl, Chitosan, derivatives of Chitin.
Par ailleurs, les îlots peuvent contenir également des microcapsules qui sont enrobées dans le matériau, lesdites microcapsules intégrant une substance active. La substance active peut également être un matériau à changement de phase améliorant la thermorégulation, ou présenter d'autres fonctions, par exemple hygiénique ou de confort. Dans des exemples de réalisation, la substance active peut comprendre des huiles essentielles, notamment pour améliorer la respiration, des parfums, des répulsifs, notamment des antimoustiques, des charges conductrices ou antistatiques, des agents bactériostatiques tels que des sels d'argents, des anti-odeurs. En outre, le Chitosan apporte une fonction bactériostatique en outre de l'hygroscopie.In addition, the islets may also contain microcapsules which are embedded in the material, said microcapsules incorporating an active substance. The active substance may also be a phase change material improving thermoregulation, or have other functions, for example hygienic or comfort. In exemplary embodiments, the active substance may comprise essential oils, in particular for improving respiration, perfumes, repellents, especially mosquito repellents, conductive or antistatic fillers, bacteriostatic agents such as silver salts, -odeurs. In addition, Chitosan provides a bacteriostatic function in addition to hygroscopy.
Selon une réalisation, les îlots sont disposés sur au moins une surface du substrat textile, sous la forme d'un réseau discret de zones géométriques, par exemple sous la forme d'un réseau bidimensionnel de points de forme rectangulaire ou autre. De façon avantageuse, les îlots peuvent recouvrir entre 5% et 40% de la surface du substrat textile sur laquelle ils sont disposés.According to one embodiment, the islands are arranged on at least one surface of the textile substrate, in the form of a discrete network of geometric zones, for example in the form of a two-dimensional network of points of rectangular shape or the like. Advantageously, the islands can cover between 5% and 40% of the surface of the textile substrate on which they are arranged.
Par ailleurs, les îlots peuvent former ou comprendre une inscription ou un logo visible sur une face du substrat textile, par exemple en incorporant un pigment dans le matériau les formant. Le substrat textile peut être utilisé pour confectionner un article textile, notamment destiné à la literie tel que des oreillers, des couettes, ou pour des vêtements, notamment de sport ou professionnels.In addition, the islands can form or include an inscription or logo visible on one side of the textile substrate, for example by incorporating a pigment into the material forming them. The textile substrate can be used to make a textile article, especially for bedding such as pillows, duvets, or for clothing, including sports or professional.
En particulier, l'article textile peut comprendre, d'un coté du substrat textile, une couche textile intérieure et, de l'autre coté dudit substrat, une couche textile extérieure qui est agencée pour emprisonner un volume d'air, tel qu'une couche en ouate. Ainsi, en disposant la couche intérieure en regard du corps, la fonction de régulation thermique est optimisée. Par ailleurs, l'article textile peut comprendre en outre une couche imper-respirante, par exemple hydrophile ou hydrophobe poreuse, qui est disposée sur la couche textile extérieure de sorte à laisser respirer le corps en empêchant l'eau liquide de l'atteindre.In particular, the textile article may comprise, on one side of the textile substrate, an inner textile layer and, on the other side of said substrate, an outer textile layer which is arranged to trap a volume of air, such as a layer of wadding. Thus, by arranging the inner layer facing the body, the thermal regulation function is optimized. Furthermore, the textile article may further comprise a breathable layer, for example hydrophilic or hydrophobic porous, which is disposed on the outer textile layer so as to let the body breathe by preventing liquid water from reaching it.
On décrit ci-dessous un procédé de fabrication d'un substrat textile selon l'invention dans lequel les microcapsules sont associées aux fibres par pontage entre leur enveloppe et les fibres dudit substrat. En outre, le substrat textile peut incorporer plus de 10 g/m2, notamment plus de 40 g/m2, de microcapsules de sorte à permettre l'absorption et la restitution de 5 à plus de 150 J/g d'énergie calorique.A method of manufacturing a textile substrate according to the invention is described below in which the microcapsules are associated with the fibers by bridging between their envelope and the fibers of said substrate. In addition, the textile substrate may incorporate more than 10 g / m 2 , in particular more than 40 g / m 2 , of microcapsules so as to allow the absorption and recovery of 5 to more than 150 J / g of caloric energy. .
Le procédé prévoit de préparer une formulation de microcapsules contenant le matériau à changement de phase dans une enveloppe, ladite enveloppe étant à base d'un matériau comprenant un type de groupement réactif sous rayonnement ionisant. En particulier, de tels groupements peuvent comprendre une liaison insaturée qui, sous l'effet du rayonnement ionisant, forme un radical libre réactif. Dans des exemples de réalisation, les groupements réactifs sous rayonnement ionisant sont choisis dans le groupe comprenant les groupements hydroxyles, carboxyles, carbonyles, acrylates, méthacrylates, aminés, amides, imides, uréthanes, styrènes. En variante, l'enveloppe peut comprendre plusieurs types de groupements réactifs sous rayonnement ionisant.The method provides for preparing a microcapsule formulation containing the phase change material in an envelope, said envelope being based on a material comprising a reactive group type under ionizing radiation. In particular, such groups may comprise an unsaturated bond which, under the effect of ionizing radiation, forms a reactive free radical. In exemplary embodiments, the reactive groups under ionizing radiation are chosen from the group comprising hydroxyl groups, carboxyl groups, carbonyl groups, acrylates, methacrylates, amines, amides, imides, urethanes, styrenes. In a variant, the envelope may comprise several types of reactive groups under ionizing radiation.
La formulation de microcapsules comprend en outre au moins un agent de pontage présentant deux types de groupements réactifs sous rayonnement ionisant, lesdits types pouvant être identique ou différent. En outre, au moins certains groupements réactifs peuvent être choisis pour être réactifs thermiquement.The microcapsule formulation further comprises at least one bridging agent having two types of reactive groups under radiation. ionizing, said types being identical or different. In addition, at least some reactive groups may be chosen to be thermally reactive.
Plus précisément, la composition de microcapsules peut comprendre un mélange d'agents de pontage, notamment choisis dans le groupe comprenant le glycidyl acrylate ou méthacrylate (AGLY, MAGLY), les polyéthylènes glycol 200, 400, 600diacrylates (PEG200 DA, PEG400 DA, PEG600 DA), le dipropylène glycol diacrylate (DPGDA), le sulfopropyl méthacrylate de potassium (SPMK) et le lauryl méthacrylate ou acrylate.More specifically, the microcapsule composition may comprise a mixture of coupling agents, in particular chosen from the group comprising glycidyl acrylate or methacrylate (AGLY, MAGLY), polyethylene glycol 200, 400, 600diacrylates (PEG200 DA, PEG400 DA, PEG600 DA), dipropylene glycol diacrylate (DPGDA), potassium sulfopropyl methacrylate (SPMK) and lauryl methacrylate or acrylate.
En particulier, l'AGLY ou le MAGLY est un agent de pontage difonctionnel présentant un groupement époxy et un groupement acrylate ou méthacrylate et les PEG DA sont des plastifiants internes difonctionnels qui participent au pontage en allongeant les chaînes de liaison entre les microcapsules et les fibres. L'utilisation combinée de ces deux types d'agents de pontage permet donc d'améliorer la souplesse du dépôt de microcapsules.In particular, AGLY or MAGLY is a difunctional bridging agent having an epoxy group and an acrylate or methacrylate group and PEG DA are difunctional internal plasticizers which participate in bridging by lengthening the binding chains between the microcapsules and the fibers . The combined use of these two types of bridging agents thus makes it possible to improve the flexibility of the microcapsule deposition.
Le rapport massique entre le ou les agents de pontage et les microcapsules est préférentiellement inférieur à 0,5, notamment compris entre 0,10 et 0,30.The mass ratio between the bridging agent (s) and the microcapsules is preferably less than 0.5, in particular between 0.10 and 0.30.
Par ailleurs, la formulation de microcapsules peut comprendre entre 30% et 60% en poids, notamment entre 40% et 50% en poids, de microcapsules dispersées dans un solvant, notamment dans de l'eau. La formulation de microcapsules peut comprendre en outre au moins un agent améliorant la stabilité de la dispersion, par exemple le sulfopropyl méthacrylate (SPM) ou le sulfopropyl acrylate (SPA) qui sont des monomères à caractère anionique réactifs sous rayonnement ionisant, ou un latex acrylique tel que celui commercialisé sous la dénomination HYCAR 26319 qui améliore le mouillage des microcapsules par les agents de pontage tout en créant des pontages entre les microcapsules et le substrat. En variante, ledit agent peut être un polyacrylate en gel ou une dispersion de polyuréthane. Le procédé de fonctionnalisation comprend en outre une étape de préparation d'un matériau apte à favoriser le transfert de chaleur et/ou d'humidité, puis une étape d'application du matériau sur au moins une zone de la surface du substrat textile de sorte à former des îlots associés aux fibres.Furthermore, the microcapsule formulation may comprise between 30% and 60% by weight, in particular between 40% and 50% by weight, of microcapsules dispersed in a solvent, in particular in water. The microcapsule formulation may further comprise at least one agent improving the stability of the dispersion, for example sulfopropyl methacrylate (SPM) or sulfopropyl acrylate (SPA) which are anionic monomers reactive under ionizing radiation, or an acrylic latex such as that marketed under the name HYCAR 26319 which improves the wetting of the microcapsules by the bridging agents while creating bridges between the microcapsules and the substrate. Alternatively, said agent may be a gel polyacrylate or a polyurethane dispersion. The functionalization process further comprises a step of preparing a material capable of promoting the transfer of heat and / or moisture, and then a step of applying the material to at least one area of the surface of the textile substrate so that to form islands associated with the fibers.
Selon la réalisation décrite, le matériau formant les îlots présente en outre une étanchéité à la formulation de microcapsules de sorte, comme on le verra dans la suite, à empêcher l'imprégnation ultérieure des îlots avec la formulation de microcapsules. Ainsi, on peut améliorer la souplesse du substrat textile, en ce que les zones dépourvues de microcapsules peuvent former zones de pliures préférentielles dudit substrat.According to the embodiment described, the material forming the islets also has a tightness to the formulation of microcapsules so, as will be seen later, to prevent the subsequent impregnation of the islets with the microcapsule formulation. Thus, it is possible to improve the flexibility of the textile substrate, in that the zones devoid of microcapsules can form zones of preferential folds of said substrate.
Pour ce faire, le matériau formant les îlots est à base de polyvinylalcool (PVA) au moins partiellement hydrolyse qui est dissout dans l'eau, ladite solution comprenant en outre un agent anti-adhérant pour la formulation de microcapsules. Par exemple, l'agent anti-adhérant peut être un glycérol et la viscosité du matériau est prévue pour piéger l'agent anti-adhérant afin d'éviter sa migration. En particulier, le matériau peut être thixotropique et présenter une viscosité comprise entre 50 et 300 dPa.s de sorte à permettre l'application sous forme de pâte avec migration au travers du substrat textile pour enrober les fibres.To do this, the material forming the islands is based on polyvinyl alcohol (PVA) at least partially hydrolyzed which is dissolved in water, said solution further comprising a release agent for the formulation of microcapsules. For example, the release agent may be a glycerol and the viscosity of the material is provided to trap the release agent to prevent migration. In particular, the material can be thixotropic and have a viscosity of between 50 and 300 dPa.s so as to allow the application in paste form with migration through the textile substrate to coat the fibers.
Le matériau formant les îlots peut être appliqué par sérigraphie, suivie d'un séchage au moins partiel dudit matériau avant imprégnation du substrat textile avec la formulation de microcapsules. La quantité de matériau déposée peut être comprise entre 5 et 40 g/m2.The material forming the islands may be applied by screen printing, followed by at least partial drying of said material before impregnation of the textile substrate with the microcapsule formulation. The amount of deposited material may be between 5 and 40 g / m 2 .
Le procédé prévoit ensuite d'imprégner le substrat textile avec la formulation de microcapsules. L'imprégnation peut être réalisée par foulardage, les conditions dudit foulardage ainsi que les caractéristiques du substrat textile étant adaptées pour emporter au moins 80% et de préférence au moins 150% en poids de formulation de microcapsules dans ledit substrat textile. Ainsi, en combinant une formulation très chargée en microcapsules et un taux d'emport important, il est possible, grâce aux différents groupements réactifs, de fixer une grande quantité de microcapsules dans le substrat textile.The method then provides for impregnating the textile substrate with the microcapsule formulation. The impregnation can be performed by padding, the conditions of said padding and the characteristics of the textile substrate being adapted to carry at least 80% and preferably at least 150% by weight of microcapsule formulation in said textile substrate. Thus, by combining a highly loaded formulation in microcapsules and a high carry rate, it It is possible, thanks to the different reactive groups, to fix a large quantity of microcapsules in the textile substrate.
En particulier, la formulation de microcapsules peut être thixotropique et sa viscosité comprise entre 130 et 150 mPa.s, notamment en ajoutant un fluidifiant à ladite formulation, tel que de l'isopropanol. En outre, avec un substrat textile à base de fibres hydrophiles, il est possible d'obtenir un bon mouillage et une montée satisfaisante de la formulation dans le substrat textile lors de l'imprégnation. En outre, le substrat textile peut subir, préalablement à son imprégnation, des traitements particuliers, notamment pour améliorer sa cohésion et/ou sa mouillabilité.In particular, the formulation of microcapsules can be thixotropic and its viscosity between 130 and 150 mPa.s, especially by adding a fluidifier to said formulation, such as isopropanol. In addition, with a textile substrate based on hydrophilic fibers, it is possible to obtain a good wetting and a satisfactory rise of the formulation in the textile substrate during the impregnation. In addition, the textile substrate may undergo, prior to its impregnation, particular treatments, in particular to improve its cohesion and / or its wettability.
Par ailleurs, la pression de calandrage lors du foulardage est relativement faible, notamment de l'ordre de 1 à 2 bars, pour permettre un emport important avec une pénétration et une répartition homogène de la formulation de microcapsules dans le substrat textile. Dans un exemple de réalisation, la quantité de formulation imprégnée dans un substrat textile de masse surfacique de 50 g/m2 peut être supérieure à 50 g/m2, notamment comprise entre 50 g/m2 et 150 g/m2.Furthermore, the calendering pressure during padding is relatively low, in particular of the order of 1 to 2 bar, to allow a significant load with penetration and a homogeneous distribution of the microcapsule formulation in the textile substrate. In an exemplary embodiment, the amount of formulation impregnated in a textile substrate with a surface mass of 50 g / m 2 may be greater than 50 g / m 2 , in particular between 50 g / m 2 and 150 g / m 2 .
Après imprégnation, le substrat textile peut être séché, notamment au moyen de lampes infrarouges, avant l'application d'un rayonnement ionisant sur le substrat textile imprégné. Le séchage permet en outre d'assurer une thermofixation de la formulation de microcapsules dans le substrat textile. En variante, la thermofixation peut être réalisée postérieurement à l'application du rayonnement ionisant, par exemple à une température comprise entre 100 et 1400C, pour parachever la fixation des microcapsules par réactions des agents de pontage réactifs thermiquement.After impregnation, the textile substrate may be dried, in particular by means of infrared lamps, before the application of ionizing radiation to the impregnated textile substrate. Drying also makes it possible to thermofix the microcapsule formulation in the textile substrate. Alternatively, the heat-setting may be carried out after the application of the ionizing radiation, for example at a temperature between 100 and 140 0 C, to complete the fixing of the microcapsules by reactions of the thermally reactive bridging agents.
La puissance et la durée du rayonnement sont agencées pour activer les groupements réactifs de sorte à assurer le pontage des microcapsules sur ledit substrat. Selon une réalisation, le rayonnement ionisant est un bombardement ionique généré par un accélérateur d'électrons, qui peut être réalisé en un ou deux passages, notamment en un passage de chaque coté du substrat textile. Par ailleurs, la puissance du rayonnement ionisant combiné avec la présence des différents groupements réactifs permet de fixer une grande quantité de microcapsules dans le substrat textile.The power and duration of the radiation are arranged to activate the reactive groups so as to bridge the microcapsules on said substrate. In one embodiment, the ionizing radiation is ion bombardment generated by an electron accelerator, which can be realized in one or two passages, including a passage on each side of the textile substrate. Moreover, the power of the ionizing radiation combined with the presence of the different reactive groups makes it possible to fix a large quantity of microcapsules in the textile substrate.
En outre, les réactions entre les groupements réactifs de l'enveloppe et des agents de pontage permettent de relier l'enveloppe des microcapsules aux fibres, les microcapsules entre elles ainsi qu'éventuellement les agents de pontage entre eux, de sorte à créer un réseau tridimensionnel solide résistant au frottement ainsi qu'au lavage ou au nettoyage à sec.In addition, the reactions between the reactive groups of the envelope and the bridging agents make it possible to connect the envelope of the microcapsules to the fibers, the microcapsules between them and possibly the bridging agents between them, so as to create a network. three-dimensional solid resistant to rubbing and washing or dry cleaning.
Enfin, le substrat textile peut être lavé puis séché ou subir d'autres traitements nécessaires à son utilisation ultérieure. Finally, the textile substrate can be washed and then dried or undergo other treatments necessary for its subsequent use.

Claims

REVENDICATIONS
1. Substrat textile comprenant des fibres, ledit substrat incorporant une composition de régulation thermique, ledit substrat étant caractérisé en ce qu'il comprend en outre des îlots de matériau qui sont associés aux fibres pour être en entourés par la composition de régulation thermique, le matériau formant les îlots étant apte à favoriser le transfert de chaleur et/ou d'humidité dans la composition de régulation thermique.A textile substrate comprising fibers, said substrate incorporating a thermal regulation composition, said substrate being characterized in that it further comprises islands of material which are associated with the fibers to be surrounded by the thermal regulation composition, the Islet-forming material being capable of promoting the transfer of heat and / or moisture into the thermal control composition.
2. Substrat textile selon la revendication 1 , caractérisé en ce que les îlots sont formés à base d'un matériau polymère hygroscopique.2. Textile substrate according to claim 1, characterized in that the islands are formed based on a hygroscopic polymer material.
3. Substrat textile selon la revendication 2, caractérisé en ce que le matériau polymère hygroscopique est choisi dans le groupe comprenant le Polyvinylalcool (PVA), les dérivés cellulosiques, le Carboxy Méthyl de cellulose, le Chitosan, les dérivés de Chitine.3. Textile substrate according to claim 2, characterized in that the hygroscopic polymer material is selected from the group comprising polyvinyl alcohol (PVA), cellulose derivatives, cellulose Carboxy Methyl, Chitosan, Chitin derivatives.
4. Substrat textile selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les îlots contiennent des microcapsules qui sont enrobées dans le matériau, lesdites microcapsules intégrant une substance active.4. Textile substrate according to any one of claims 1 to 3, characterized in that the islets contain microcapsules which are embedded in the material, said microcapsules incorporating an active substance.
5. Substrat textile selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les îlots sont disposés sur au moins une surface du substrat textile, sous la forme d'un réseau discret de zones géométriques.5. Textile substrate according to any one of claims 1 to 4, characterized in that the islands are arranged on at least one surface of the textile substrate, in the form of a discrete network of geometric zones.
6. Substrat textile selon la revendication 5, caractérisé en ce que les îlots recouvrent entre 5% et 40% de la surface du substrat textile sur laquelle ils sont disposés.6. Textile substrate according to claim 5, characterized in that the islands cover between 5% and 40% of the surface of the textile substrate on which they are arranged.
7. Substrat textile selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les fibres sont hydrophiles. 7. Textile substrate according to any one of claims 1 to 6, characterized in that the fibers are hydrophilic.
8. Substrat textile selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il comprend une nappe de non-tissé8. Textile substrate according to any one of claims 1 to 7, characterized in that it comprises a nonwoven web
9. Substrat textile selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la composition de régulation thermique comprend des microcapsules pourvues d'une enveloppe dans laquelle un matériau à changement de phase est disposé, la température de fusion dudit matériau étant agencée pour assurer une thermorégulation.9. Textile substrate according to any one of claims 1 to 8, characterized in that the thermal regulation composition comprises microcapsules provided with an envelope in which a phase change material is disposed, the melting temperature of said material being arranged to provide thermoregulation.
10. Substrat textile selon la revendication 9, caractérisé en ce que la composition de régulation thermique comprend deux types de microcapsules, les matériaux à changement de phase de chacun des types de microcapsules différant par leur température de fusion.10. Textile substrate according to claim 9, characterized in that the thermal regulation composition comprises two types of microcapsules, the phase change materials of each type of microcapsules differ in their melting temperature.
11. Substrat textile selon la revendication 9 ou 10, caractérisé en ce qu'il incorpore plus de 10 g/m2 de microcapsules.11. Textile substrate according to claim 9 or 10, characterized in that it incorporates more than 10 g / m 2 of microcapsules.
12. Substrat textile selon l'une quelconque des revendications 9 à 11, caractérisé en ce que les microcapsules sont associées aux fibres par pontage.12. Textile substrate according to any one of claims 9 to 11, characterized in that the microcapsules are associated with the fibers by bridging.
13. Procédé de fabrication d'un substrat textile selon la revendication 12, ledit procédé comprenant les étapes prévoyant de :13. A method of manufacturing a textile substrate according to claim 12, said method comprising the steps of:
- préparer une formulation de microcapsules contenant le matériau à changement de phase dans une enveloppe, ladite enveloppe étant à base d'un matériau comprenant un type de groupement réactif sous rayonnement ionisant, ladite formulation comprenant en outre au moins un agent de pontage présentant deux types de groupements réactifs sous rayonnement ionisant ;preparing a formulation of microcapsules containing the phase-change material in an envelope, said envelope being based on a material comprising a type of reactive group under ionizing radiation, said formulation further comprising at least one bridging agent having two types reactive groups under ionizing radiation;
- préparer un matériau apte à favoriser le transfert de chaleur et/ou d'humidité ;- Prepare a material capable of promoting the transfer of heat and / or moisture;
- appliquer le matériau sur au moins une zone de la surface du substrat textile de sorte à former des îlots associés aux fibres ; puisapplying the material to at least one area of the surface of the textile substrate so as to form islands associated with the fibers; then
- imprégner le substrat textile avec la formulation de microcapsules ; et - appliquer un rayonnement ionisant sur le substrat textile imprégné de sorte à assurer le pontage des microcapsules sur ledit substrat par réaction des groupements réactifs.impregnating the textile substrate with the microcapsule formulation; and applying ionizing radiation to the impregnated textile substrate so as to bridge the microcapsules on said substrate by reacting the reactive groups.
14. Procédé selon la revendication 13, dans lequel le matériau formant les îlots présente en outre une étanchéité à la formulation de microcapsules de sorte à empêcher l'imprégnation ultérieure des îlots avec la formulation de microcapsules.The method of claim 13, wherein the island-forming material further exhibits sealing to the microcapsule formulation so as to prevent subsequent impregnation of the islets with the microcapsule formulation.
15. Procédé selon la revendication 13 ou 14, dans lequel l'imprégnation est réalisée par foulardage, les conditions dudit foulardage ainsi que les caractéristiques du substrat textile étant adaptées pour emporter au moins 80% et de préférence au moins 150% en poids de formulation de microcapsules dans ledit substrat textile.15. The method of claim 13 or 14, wherein the impregnation is performed by padding, the conditions of said padding and the characteristics of the textile substrate being adapted to carry at least 80% and preferably at least 150% by weight of formulation microcapsules in said textile substrate.
16. Procédé selon la revendication 14 ou 15, dans lequel le matériau des îlots est à base de Polyvinylalcool (PVA) au moins partiellement hydrolyse qui est dissout dans l'eau, ladite solution comprenant en outre un agent anti-adhérant pour la formulation de microcapsules.The process according to claim 14 or 15, wherein the islet material is based on at least partially hydrolyzed polyvinyl alcohol (PVA) which is dissolved in water, said solution further comprising a release agent for the formulation of microcapsules.
17. Procédé de fonctionnalisation selon l'une quelconque des revendications 13 à 16, dans lequel le matériau des îlots est appliqué par sérigraphie, suivie d'un séchage dudit matériau avant imprégnation du substrat textile avec la formulation de microcapsules. 17. Functionalization method according to any one of claims 13 to 16, wherein the material of the islands is applied by screen printing, followed by drying of said material before impregnation of the textile substrate with the microcapsule formulation.
EP20080761746 2007-01-10 2008-01-09 Textile substrate including a thermal regulation composition surrounding transfer islands Not-in-force EP2122045B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0700166A FR2911153B1 (en) 2007-01-10 2007-01-10 TEXTILE SUBSTRATE INCORPORATING A THERMAL REGULATION COMPOSITION SURROUNDING TRANSFER ISLANDS.
PCT/FR2008/000024 WO2008099089A2 (en) 2007-01-10 2008-01-09 Textile substrate including a thermal regulation composition surrounding transfer islands

Publications (2)

Publication Number Publication Date
EP2122045A2 true EP2122045A2 (en) 2009-11-25
EP2122045B1 EP2122045B1 (en) 2011-10-19

Family

ID=38328130

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20080761746 Not-in-force EP2122045B1 (en) 2007-01-10 2008-01-09 Textile substrate including a thermal regulation composition surrounding transfer islands

Country Status (14)

Country Link
US (1) US20100099315A1 (en)
EP (1) EP2122045B1 (en)
JP (1) JP2010515835A (en)
KR (1) KR20090100446A (en)
CN (1) CN101627159A (en)
AT (1) ATE529565T1 (en)
AU (1) AU2008214556A1 (en)
CA (1) CA2670008A1 (en)
FR (1) FR2911153B1 (en)
IL (1) IL198816A0 (en)
MA (1) MA31164B1 (en)
TN (1) TN2009000259A1 (en)
WO (1) WO2008099089A2 (en)
ZA (1) ZA200903655B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443878B (en) * 2011-09-23 2014-01-15 大连工业大学 A multi-functional comfortable fiber with phase change temperature adjustment, moisture absorption and perspiration
CN103088647A (en) * 2012-12-12 2013-05-08 吴江麦道纺织有限公司 Processing technology of heat-storage and temperature-regulation cloth
CN104382260B (en) * 2014-12-12 2016-08-24 苏州大学 A kind of temperature regulation and motion Comfortable fabric and molding clothing
CN105133350B (en) * 2015-09-29 2017-09-01 北京宇田相变储能科技有限公司 A kind of hot wet Intelligent adjustment fabric and preparation method thereof
FR3112560B1 (en) * 2020-07-17 2022-11-25 Faurecia Interieur Ind Textile for a vehicle interior trim part, vehicle interior trim part and associated method of manufacture

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5366801A (en) * 1992-05-29 1994-11-22 Triangle Research And Development Corporation Fabric with reversible enhanced thermal properties
WO2001006054A1 (en) * 1999-07-19 2001-01-25 Avantgarb, Llc Nanoparticle-based permanent treatments for textiles
WO2002059414A2 (en) * 2001-01-25 2002-08-01 Outlast Technologies, Inc. Coated articles having enhanced reversible thermal properties and exhibiting improved flexibility, softness, air permeability, or water vapor transport properties
FR2827316B1 (en) * 2001-07-13 2004-07-30 Inter Unec Interaction Univers TEXTILE FIBER SURFACE TREATMENT PROCESS
EP1658395B1 (en) * 2003-08-30 2006-11-08 THÜRINGISCHES INSTITUT FÜR TEXTIL- UND KUNSTSTOFF-FORSCHUNG e.V. Method for producing moulded bodies exhibiting thermoregulation properties
US20060159907A1 (en) * 2004-12-10 2006-07-20 Simona Percec Filled ultramicrocellular structures
PT103265B (en) * 2005-04-22 2007-02-28 Univ Do Minho MICROCAPSULES WITH FUNCTIONAL REACTIVE GROUPS OF CONNECTION TO TEXTILE FIBERS AND APPLICATION AND FIXATION PROCESS

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008099089A2 *

Also Published As

Publication number Publication date
ATE529565T1 (en) 2011-11-15
WO2008099089A2 (en) 2008-08-21
FR2911153B1 (en) 2009-04-10
JP2010515835A (en) 2010-05-13
FR2911153A1 (en) 2008-07-11
WO2008099089A3 (en) 2008-11-06
CA2670008A1 (en) 2008-08-21
US20100099315A1 (en) 2010-04-22
AU2008214556A1 (en) 2008-08-21
EP2122045B1 (en) 2011-10-19
IL198816A0 (en) 2010-02-17
ZA200903655B (en) 2010-04-28
CN101627159A (en) 2010-01-13
KR20090100446A (en) 2009-09-23
MA31164B1 (en) 2010-02-01
TN2009000259A1 (en) 2010-10-18

Similar Documents

Publication Publication Date Title
EP2108070B1 (en) Method for functionalising a textile substrate by cross-linking bonding under a ionising radiation
EP2122045B1 (en) Textile substrate including a thermal regulation composition surrounding transfer islands
FR2784581A1 (en) PATCH, ASSEMBLY OF A PATCH AND A CONTAINER, AND METHOD
EP3575459A1 (en) Coated articles formed of microcapsules with reactive functional groups
KR101180787B1 (en) Manufacturing method of Nanofiber for auto-controlling temperature and humidity
CN1636090A (en) Thermal control nonwoven material
EP0378940B1 (en) Water-swellable composite material substrates useful for its manufacture and its uses
FR2775331A1 (en) FLEXIBLE LINING INSULATING HEAT OR COLD
EP2484322B1 (en) Absorbent article
JP2004300620A (en) Liquid absorber
EP1944408A2 (en) Method for forming a fabric with insect, water- and oilrepellent characteristics
CN118181879A (en) Formaldehyde-removing wall cloth and manufacturing method thereof
CN1183956A (en) Blackhead-removing face pack sheet and its preparing method
EP1889595B1 (en) Cleaning and/or skin care item, and production method thereof
JP3270930B2 (en) Method for modifying one side of woven or knitted fabric or nonwoven fabric and woven or knitted fabric or nonwoven fabric having one surface modified
CA2324933A1 (en) Composite absorbent materials for aqueous liquid
JPS60110440A (en) Non-air-permeable hygroscopic and moisture-dissipating waterproof sheet
KR100805984B1 (en) Sheet-shaped self heating element and its manufacturing method
RU2444583C2 (en) Multicomponent fibre
FR2858225A1 (en) COSMETIC TREATMENT ARTICLE FOR SKIN, MUCOUS MEMBRANES, HAIR OR SCALP AND COSMETIC TREATMENT METHOD.
EP0865410A1 (en) Disposable absorbent articles
JPH10324614A (en) Sheet-like pack material for removing skin dark color and its production
JPH0313359B2 (en)
WO2009004158A2 (en) Method for functionalising a textile substrate with antiseptic and/or virucidal property

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090709

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602008010614

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: D06N0003000000

Ipc: D06M0023120000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: D06M 10/08 20060101ALI20110221BHEP

Ipc: D06M 23/12 20060101AFI20110221BHEP

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008010614

Country of ref document: DE

Effective date: 20111208

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20111019

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20111019

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 529565

Country of ref document: AT

Kind code of ref document: T

Effective date: 20111019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120119

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120219

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120220

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120120

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

BERE Be: lapsed

Owner name: LAINIERE DE PICARDIE

Effective date: 20120131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120119

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20120720

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120119

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008010614

Country of ref document: DE

Effective date: 20120720

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080109

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20150121

Year of fee payment: 8

Ref country code: IT

Payment date: 20150127

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20150122

Year of fee payment: 8

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008010614

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160109