EP2108070B1 - Method for functionalising a textile substrate by cross-linking bonding under a ionising radiation - Google Patents
Method for functionalising a textile substrate by cross-linking bonding under a ionising radiation Download PDFInfo
- Publication number
- EP2108070B1 EP2108070B1 EP20080761747 EP08761747A EP2108070B1 EP 2108070 B1 EP2108070 B1 EP 2108070B1 EP 20080761747 EP20080761747 EP 20080761747 EP 08761747 A EP08761747 A EP 08761747A EP 2108070 B1 EP2108070 B1 EP 2108070B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- textile substrate
- functionalising
- microcapsules
- textile
- substrate
- 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.)
- Not-in-force
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Classifications
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- 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
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- 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
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- 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
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- 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.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3472—Woven fabric including an additional woven fabric layer
- Y10T442/3602—Three or more distinct layers
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- 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.]
- Y10T442/40—Knit fabric [i.e., knit strand or strip material]
Definitions
- the invention relates to a method of functionalizing a textile substrate by means of an active composition, a functionalized textile substrate by implementing such a method, and a textile article made with such a textile substrate.
- the invention applies in particular to the functionalization of textile substrates so as to give them thermal control properties.
- it is known to fix to the textile substrate 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.
- This method if it solves the problems of the previously discussed method, finds its limits relative to the amount of microcapsules that can be fixed.
- the aim of the invention is to overcome the drawbacks of the prior art by proposing a process for functionalizing a textile substrate in which a large quantity of an active composition can be incorporated, without significantly limiting the flexibility and the breathability of said textile substrate.
- the invention provides a functionalized textile substrate by implementing such a method, said substrate incorporating more than 10 g / m 2 of microcapsules containing the active composition, said microcapsules being associated by bridging between their envelope and the fibers of said substrate.
- the invention proposes a textile article made with such a textile substrate, said article further comprising, on one side of the textile substrate, an inner textile layer and, on the other side of said substrate, a textile layer. exterior which is arranged to trap a volume of air.
- the invention relates to a method of functionalizing a textile substrate by means of an active composition.
- the active substance may be able to provide a thermal regulation function to the textile substrate.
- the active substance may have other functions, for example hygienic or comfort.
- the active substance may comprise essential oils, in particular for improving respiration, perfumes, repellents, especially anti-mosquitoes, conductive or antistatic fillers, bacteriostatic agents such as silver salts, anti-odor.
- the method provides for preparing a microcapsule formulation containing the active composition in an envelope, said microcapsules having a size of less than 20 ⁇ m, in particular between 1 and 10 ⁇ m on average.
- the active substance comprises 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 human body temperature.
- such an active 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 envelope of the microcapsules is based on a material comprising a type of reactive group 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 formulation described comprises 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 active substance is respectively n-Octadecane and n-Eicosane, the storage or caloric storage capacity being of the order of 170 J / g.
- the envelope is based on polymethylmethacrylate (PMMA) which has reactive acrylate groups under ionizing radiation.
- the microcapsule formulation further comprises at least one bridging agent having two types of reactive groups under ionizing radiation, which types may be the same or different.
- the reactive groups under ionizing radiation may be chosen from the group comprising hydroxyl groups, carboxyl groups, carbonyl groups, acrylates, methacrylates, amines, amides, imides, urethanes, styrene.
- at least some reactive groups may be chosen to be thermally reactive.
- the microcapsule composition may comprise a mixture of bridging agents, in particular chosen from the group comprising glycidyl acrylate or methacrylate (AGLY, MAGLY), polyethylene glycol 200, 400, 600 diacrylate (PEG200 DA, PEG400 DA, PEG600 DA), dipropylene glycol diacrylate (DPGA), potassium sulfopropyl methacrylate (SPMK) and lauryl methacrylate or acrylate.
- glycidyl acrylate or methacrylate AGLY, MAGLY
- polyethylene glycol 200, 400, 600 diacrylate PEG200 DA, PEG400 DA, PEG600 DA
- DPGA 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 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.
- the textile substrate may be based on hydrophilic fibers.
- 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 ° C, to complete the fixation 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 electron bombardment generated by an electron accelerator, which can be carried out in one or two passages, in particular in 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.
- the functionalization process further comprises a step of preparing a material having a tightness to the formulation of microcapsules and, prior to the impregnation of the textile substrate with the microcapsule formulation, to apply the waterproof material to at least one area of the surface of the textile substrate so as to prevent subsequent impregnation of said area with the microcapsule formulation.
- the application areas of the sealed material can form a two-dimensional network on the surface of the textile substrate, for example in the form of discrete areas of rectangular geometry or other.
- the application areas of the sealed material can form from 5% to 40% of the total surface of the textile substrate.
- the sealing material can be removed from the surface of the textile substrate so as to form areas devoid of microcapsules.
- the elimination of the sealed material in particular carried out by hot washing, makes it possible to remove the possible amount of microcapsule formulation which would not have been fixed during the application of the ionizing radiation.
- one can provide at least one agent improving the dissolution and subsequent removal of the material for example titanium dioxide and / or a surfactant sulfonate.
- the impervious material is based on polyvinyl alcohol (PVA) at least partially hydrolysed which is dissolved in water, said solution further comprising a release agent for the formulation of microcapsules.
- PVA polyvinyl alcohol
- the impervious material may be based on Chitosan or Chitin derivatives.
- the release agent may be a glycerol and the viscosity of the material is provided to trap the release agent to prevent migration.
- the impervious material may 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 impervious material 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 .
- thermoregulating textile substrate absorbs and restores from 5 to more than 150 J / g of caloric energy.
- the textile substrate is based on hydrophilic fibers having a titer of less than 4 dtex, so as to promote the flexibility and the absorption capacity of the microcapsule formulation.
- the fibers may be based on polyester or polyamide.
- the textile substrate may comprise a nonwoven web of a weight of less than 50 g / m 2 , in particular 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 may undergo, prior to its functionalization, particular treatments, in particular to improve its cohesion and / or wettability.
- the textile substrate may also be formed of a knit or fabric.
- the textile substrate when it is functionalized with an active composition comprising a phase-change material, makes it possible to provide thermoregulation.
- an active composition comprising a phase-change material
- thermoregulation two types of microcapsules can be incorporated into the textile substrate to improve the conferred thermoregulation.
- 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.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
L'invention concerne un procédé de fonctionnalisation d'un substrat textile au moyen d'une composition active, un substrat textile fonctionnalisé par mise en oeuvre d'un tel procédé, ainsi qu'un article textile confectionné avec un tel substrat textile.The invention relates to a method of functionalizing a textile substrate by means of an active composition, a functionalized textile substrate by implementing such a method, and a textile article made with such a textile substrate.
L'invention s'applique notamment à la fonctionnalisation des substrats textiles de sorte à leur conférer des propriétés de régulation thermique. Pour ce faire, il est connu de fixer au substrat textile 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.The invention applies in particular to the functionalization of textile substrates so as to give them thermal control properties. To do this, it is known to fix to the textile substrate 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.
Le document
Le document
Pour fixer les microcapsules sur le substrat textile, on connaît, notamment du document
Toutefois, du fait de la présence de la couche de liant, cette solution ne donne pas entièrement satisfaction d'un point de vue de la souplesse du substrat textile. En outre, le poids du substrat textile enduit s'en trouve augmenté de façon préjudiciable. Enfin, la couche de liant étant étanche à l'air, la respirabilité du substrat textile s'en trouve également détériorée. Toutes ces limitations ne permettent pas de confectionner, avec le substrat textile, un article textile convenable, notamment pour être porté à proximité du corps d'une personne.However, because of the presence of the binder layer, this solution does not give full satisfaction from a point of view of the flexibility of the textile substrate. In addition, the weight of the coated textile substrate is increased detrimentally. Finally, since the binder layer is airtight, the breathability of the textile substrate is also deteriorated. All these limitations do not allow to make, with the textile substrate, a suitable textile article, in particular to be worn close to the body of a person.
On connaît par ailleurs du document
Ce procédé, s'il permet de résoudre les problèmes du procédé précédemment exposé, trouve ses limites relativement à la quantité de microcapsules qui peuvent être fixées.This method, if it solves the problems of the previously discussed method, finds its limits relative to the amount of microcapsules that can be fixed.
L'invention a pour but de pallier les inconvénients de l'art antérieur en proposant un procédé de fonctionnalisation d'un substrat textile dans lequel une quantité importante d'une composition active peut être incorporée, et ce sans limiter de façon importante la souplesse et la respirabilité dudit substrat textile.The aim of the invention is to overcome the drawbacks of the prior art by proposing a process for functionalizing a textile substrate in which a large quantity of an active composition can be incorporated, without significantly limiting the flexibility and the breathability of said textile substrate.
A cet effet, et selon un premier aspect, l'invention propose un procédé de fonctionnalisation d'un substrat textile au moyen d'une composition active, ledit procédé comprenant les étapes prévoyant de :
- préparer une formulation de microcapsules contenant la composition active 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 ;
- imprégner le substrat textile avec la formulation de microcapsules ;
- 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.
- preparing a formulation of microcapsules containing the active composition 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 of reactive groups under ionizing radiation;
- impregnating the textile substrate with the microcapsule formulation;
- applying ionizing radiation to the impregnated textile substrate so as to bridge the microcapsules on said substrate by reaction of the reactive groups.
Selon un deuxième aspect, l'invention propose un substrat textile fonctionnalisé par mise en oeuvre d'un tel procédé, ledit substrat incorporant plus de 10 g/m2 de microcapsules contenant la composition active, lesdites microcapsules étant associées par pontage entre leur enveloppe et les fibres dudit substrat.According to a second aspect, the invention provides a functionalized textile substrate by implementing such a method, said substrate incorporating more than 10 g / m 2 of microcapsules containing the active composition, said microcapsules being associated by bridging between their envelope and the fibers of said substrate.
Selon un troisième aspect, l'invention propose un article textile confectionné avec un tel substrat textile, ledit article comprenant en outre, 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.According to a third aspect, the invention proposes a textile article made with such a textile substrate, said article further comprising, on one side of the textile substrate, an inner textile layer and, on the other side of said substrate, a textile layer. exterior which is arranged to trap a volume of air.
D'autres particularités et avantages de l'invention apparaîtront dans la description qui suit de différents modes de réalisation particuliers.Other features and advantages of the invention will appear in the following description of various particular embodiments.
L'invention concerne un procédé de fonctionnalisation d'un substrat textile au moyen d'une composition active. En particulier, la substance active peut être apte à procurer une fonction de régulation thermique au substrat textile. Dans d'autres applications, la substance active peut 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 anti-moustiques, des charges conductrices ou antistatiques, des agents bactériostatiques tels que des sels d'argents, des anti-odeurs.The invention relates to a method of functionalizing a textile substrate by means of an active composition. In particular, the active substance may be able to provide a thermal regulation function to the textile substrate. In other applications, the active substance may 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 anti-mosquitoes, conductive or antistatic fillers, bacteriostatic agents such as silver salts, anti-odor.
Le procédé prévoit de préparer une formulation de microcapsules contenant la composition active dans une enveloppe, lesdites microcapsules présentant une taille inférieure à 20 µm, notamment comprise entre 1 et 10 µm en moyenne.The method provides for preparing a microcapsule formulation containing the active composition in an envelope, said microcapsules having a size of less than 20 μm, in particular between 1 and 10 μm on average.
Dans la formulation décrite ci-dessous, la substance active comprend 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.In the formulation described below, the active substance comprises 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 human body temperature.
De façon connue, une telle composition active 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 active 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 an active 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 active composition allows an absorption of caloric energy at almost constant temperature and, when the temperature ambient decreases, the solidification of said composition makes it possible to restore said caloric energy. Alternatively, non-paraffin-containing flame retardant phase change materials may be used, especially for non-fire applications.
En outre, l'enveloppe des microcapsules est 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, amines, amides, imides, uréthanes, styrènes. En variante, l'enveloppe peut comprendre plusieurs types de groupements réactifs sous rayonnement ionisant.In addition, the envelope of the microcapsules is based on a material comprising a type of reactive group 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 décrite comprend 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, la substance active 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 est à base de polyméthylméthacrylate (PMMA) qui présente des groupements acrylates réactifs sous rayonnement ionisant.The formulation described comprises 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 active substance is respectively n-Octadecane and n-Eicosane, the storage or caloric storage capacity being of the order of 170 J / g. Furthermore, the envelope is based on polymethylmethacrylate (PMMA) which has reactive acrylate 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. De même que pour l'enveloppe, les groupements réactifs sous rayonnement ionisant peuvent être choisis dans le groupe comprenant les groupements hydroxyles, carboxyles, carbonyles, acrylates, méthacrylates, amines, amides, imides, uréthanes, styrènes. 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 ionizing radiation, which types may be the same or different. As for the envelope, the reactive groups under ionizing radiation may be chosen from the group comprising hydroxyl groups, carboxyl groups, carbonyl groups, acrylates, methacrylates, amines, amides, imides, urethanes, styrene. 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, 600 diacrylate (PEG200 DA, PEG400 DA, PEG600 DA), le dipropylène glycol diacrylate (DPGA), le sulfopropyl méthacrylate de potassium (SPMK) et le lauryl méthacrylate ou acrylate.More specifically, the microcapsule composition may comprise a mixture of bridging agents, in particular chosen from the group comprising glycidyl acrylate or methacrylate (AGLY, MAGLY), polyethylene glycol 200, 400, 600 diacrylate (PEG200 DA, PEG400 DA, PEG600 DA), dipropylene glycol diacrylate (DPGA), 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 methacrylate (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.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.
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 textileThe 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 microcapsule formulation and a high loading rate, 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, le substrat textile peut être à base de fibres hydrophiles. Ainsi, il est possible d'obtenir un bon mouillage et une montée satisfaisante de la formulation dans le substrat textile lors de l'imprégnation.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, the textile substrate may be based on hydrophilic fibers. Thus, it is possible to obtain a good wetting and a satisfactory rise of the formulation in the textile substrate during the impregnation.
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 140°C, 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 ° C, to complete the fixation 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 électronique 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. According to one embodiment, the ionizing radiation is electron bombardment generated by an electron accelerator, which can be carried out in one or two passages, in particular in 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.
Selon une réalisation, le procédé de fonctionnalisation comprend en outre une étape de préparation d'un matériau présentant une étanchéité à la formulation de microcapsules et, préalablement à l'imprégnation du substrat textile avec la formulation de microcapsules, d'appliquer le matériau étanche sur au moins une zone de la surface du substrat textile de sorte à empêcher l'imprégnation ultérieure de ladite zone avec la formulation de microcapsules.According to one embodiment, the functionalization process further comprises a step of preparing a material having a tightness to the formulation of microcapsules and, prior to the impregnation of the textile substrate with the microcapsule formulation, to apply the waterproof material to at least one area of the surface of the textile substrate so as to prevent subsequent impregnation of said area with the microcapsule formulation.
Cette réalisation, permet d'améliorer la souplesse du substrat textile fonctionnalisé, en ce que les zones dépourvues de microcapsules peuvent former zones de pliures préférentielles dudit substrat. En outre, certaines zones du substrat textile ne nécessitent pas d'être fonctionnalisées. Dans un exemple de réalisation, les zones d'application du matériau étanche peuvent former un réseau bidimensionnel sur la surface du substrat textile, par exemple sous la forme de zones discrètes de géométrie rectangulaire ou autre. De façon avantageuse, les zones d'application du matériau étanche peuvent former de 5% à 40% de la surface totale du substrat textile.This embodiment makes it possible to improve the flexibility of the functionalized textile substrate, in that the zones devoid of microcapsules can form zones of preferential folds of said substrate. In addition, some areas of the textile substrate do not need to be functionalized. In an exemplary embodiment, the application areas of the sealed material can form a two-dimensional network on the surface of the textile substrate, for example in the form of discrete areas of rectangular geometry or other. In a way Advantageously, the application areas of the sealed material can form from 5% to 40% of the total surface of the textile substrate.
En outre, après l'application du rayonnement ionisant, au moins une partie du matériau étanche peut être retirée de la surface du substrat textile de sorte à former des zones dépourvues de microcapsules. En outre, l'élimination du matériau étanche, notamment réalisée par lavage à chaud, permet de retirer l'éventuelle quantité de formulation de microcapsules qui n'aurait pas été fixée lors de l'application du rayonnement ionisant. Pour ce faire, on peut prévoir au moins un agent améliorant la dissolution et le retrait ultérieur du matériau, par exemple du dioxyde de titane et/ou un sulfonate tensioactif.In addition, after the application of the ionizing radiation, at least a portion of the sealing material can be removed from the surface of the textile substrate so as to form areas devoid of microcapsules. In addition, the elimination of the sealed material, in particular carried out by hot washing, makes it possible to remove the possible amount of microcapsule formulation which would not have been fixed during the application of the ionizing radiation. To do this, one can provide at least one agent improving the dissolution and subsequent removal of the material, for example titanium dioxide and / or a surfactant sulfonate.
Dans le cas où seule une partie du matériau étanche est retirée de la surface, il est en outre possible de bénéficier des propriétés dudit matériau restant, notamment relativement au transfert de calorie ou au transfert d'humidité entre les zones adjacentes qui sont pourvues de microcapsules.In the case where only a part of the sealed material is removed from the surface, it is furthermore possible to benefit from the properties of the said remaining material, in particular relative to the calorie transfer or to the transfer of moisture between the adjacent zones which are provided with microcapsules. .
Selon une réalisation, le matériau étanche est à base de polyvinylalcool (PVA) au moins partiellement hydrolysé qui est dissout dans l'eau, ladite solution comprenant en outre un agent anti-adhérant pour la formulation de microcapsules. En variante, le matériau étanche peut être à base de Chitosan ou de dérivés de Chitine. 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 étanche 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.In one embodiment, the impervious material is based on polyvinyl alcohol (PVA) at least partially hydrolysed which is dissolved in water, said solution further comprising a release agent for the formulation of microcapsules. Alternatively, the impervious material may be based on Chitosan or Chitin derivatives. 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 impervious material may 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 étanche 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 impervious material 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 .
La mise en oeuvre du procédé décrit ci-dessus permet d'obtenir un substrat textile incorporant plus de 10 g/m2, notamment plus de 40 g/m2, de microcapsules contenant la composition active, dans lequel les microcapsules sont associées par pontage entre leur enveloppe et les fibres dudit substrat. Le substrat textile thermorégulant permet d'absorber et de restituer de 5 à plus de 150 J/g d'énergie calorique.The implementation of the method described above makes it possible to obtain a textile substrate incorporating more than 10 g / m 2 , in particular more than 40 g / m 2 , of microcapsules containing the active composition, in which the microcapsules are associated by bridging. between their envelope and the fibers of said substrate. The thermoregulating textile substrate absorbs and restores from 5 to more than 150 J / g of caloric energy.
Dans un exemple de réalisation, le substrat textile est à base de fibres hydrophiles présentant un titre inférieur à 4 dtex, de sorte à favoriser la souplesse et la capacité d'absorption de la formulation de microcapsules.In an exemplary embodiment, the textile substrate is based on hydrophilic fibers having a titer of less than 4 dtex, so as to promote the flexibility and the absorption capacity of the microcapsule formulation.
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 peut comprendre 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).The textile substrate may comprise a nonwoven web of a weight of less than 50 g / m 2 , in particular 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 outre, le substrat textile peut subir, préalablement à sa fonctionnalisation, des traitements particuliers, notamment pour améliorer sa cohésion et/ou sa mouillabilité. Par ailleurs, en fonction de l'application envisagée, le substrat textile peut également être formé d'un tricot ou d'un tissu.In addition, the textile substrate may undergo, prior to its functionalization, particular treatments, in particular to improve its cohesion and / or wettability. Furthermore, depending on the intended application, the textile substrate may also be formed of a knit or fabric.
Le substrat textile, lorsqu'il est fonctionnalisé avec une composition active comprenant un matériau à changement de phase, permet d'assurer une thermorégulation. En particulier, comme mentionné ci-dessus, deux types de microcapsules peuvent être incorporés dans le substrat textile pour améliorer la thermorégulation conférée.The textile substrate, when it is functionalized with an active composition comprising a phase-change material, makes it possible to provide thermoregulation. In particular, as mentioned above, two types of microcapsules can be incorporated into the textile substrate to improve the conferred thermoregulation.
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.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.
Claims (20)
- Method for functionalising a textile substrate by means of an active composition, said method comprising steps for:- preparing a microcapsule formulation containing the active composition in a casing, said casing being based on a material comprising a reactive group type in ionising radiation, said formulation further comprising at least one coupling agent having two reactive group types in ionising radiation;- impregnating the textile substrate with the microcapsule formulation;- applying ionising radiation on the impregnated textile substrate so as to ensure the coupling of the microcapsules on said substrate by reacting the reactive groups.
- Method for functionalising according to claim 1, wherein the microcapsule formulation comprises between 30% and 60% by weight of microcapsules dispersed in at least one solvent.
- Method for functionalising according to claim 2, wherein the microcapsule formulation further comprises at least one agent enhancing the stability of the dispersion.
- Method for functionalising according to any of claims 1 to 3, wherein the microcapsule formulation further comprises a liquefier.
- Method for functionalising according to any of claims 1 to 4, wherein the mass ratio between the coupling agent(s) and the microcapsules is between 0.10 and 0.30.
- Method for functionalising according to any of claims 1 to 5, wherein the reactive groups in ionising radiation are selected in the group comprising the hydroxyl, carboxyl, carbonyl, acrylate, methacrylate, amine, amide, imide, urethane, styrene groups.
- Method for functionalising according to claim 6, wherein the microcapsule composition comprises a mixture of coupling agents selected in the group comprising glycidyl acrylate or methacrylate (AGLY or MAGLY), polyethylene glycol 200, 400, 600 diacrylates (PEG200 DA, PEG400 DA, PEG600 DA), dipropylene glycol diacrylate (DPGDA), sulphopropyl methacrylate potassium (SPMK) and lauryl methacrylate or acrylate.
- Method for functionalising according to claim 6 or 7, wherein the microcapsule casing is based on polymethylmethacrylate (PMMA).
- Method for functionalising according to any of claims 1 to 8, wherein the impregnation is performed by padding, the conditions of said padding and the features of the textile substrate being suitable for carrying at least 80% and preferably at least 150% by weight of microcapsule formulation into said textile substrate.
- Method for functionalising according to any of claims 1 to 9, wherein the textile substrate is dried prior to the application of the ionising radiation.
- Method for functionalising according to any of claims 1 to 10, characterised in that at least some groups are heat-reactive, said method comprising a microcapsule heat-setting step by reacting said groups.
- Method for functionalising according to any of claims 1 to 11, wherein the ionising radiation is an electron bombardment.
- Method for functionalising according to any of claims 1 to 12, comprising steps for:- preparing a material displaying impermeability to the microcapsule formulation; and, prior to the impregnation of the textile substrate with the microcapsule formulation,- applying the impermeable material on at least one area of the surface of the textile substrate so as to prevent the subsequent impregnation of said area with the microcapsule formulation.
- Method for functionalising according to claim 13, wherein, after applying the ionising radiation, at least one portion of the impermeable material is removed from the surface of the textile substrate so as to form areas devoid of microcapsules.
- Method for functionalising according to claim 13 or 14, wherein the impermeable material is based on at least partially hydrolysed polyvinyl alcohol (PVA) which is dissolved in water, said solution further comprising an anti-adherent agent for the microcapsule formulation.
- Method for functionalising according to any of claims 13 to 15, wherein the impermeable material is applied by screen printing, followed by drying of said material prior to impregnation of the textile substrate with the microcapsule formulation.
- Textile substrate functionalised by implementing a method according to any of claims 1 to 16, said substrate incorporating over 10 g/m2 of microcapsules containing the active composition, said microcapsules being associated by coupling between the casing thereof and the fibres of said substrate.
- Textile substrate according to claim 17, wherein the active composition comprising a phase-change material, the melting point whereof is arranged to ensure thermoregulation.
- Textile substrate according to claim 18, wherein two types of microcapsules are incorporated, the phase-change materials of the types of microcapsules differing by the melting point thereof.
- Textile item fashioned with a textile substrate according to any of claims 17 to 19, said item further comprising, on one side of the textile substrate, an inner textile layer and, on the other side of said substrate, an outer textile layer arranged to trap an air volume.
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FR0700164A FR2911152B1 (en) | 2007-01-10 | 2007-01-10 | METHOD FOR FUNCTIONALIZATION OF A TEXTILE SUBSTRATE BY IONIZING RADIATION BRIDGE. |
PCT/FR2008/000025 WO2008099090A2 (en) | 2007-01-10 | 2008-01-09 | Method for functionalising a textile substrate by cross-linking bonding under a ionising radiation |
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CN102337673B (en) * | 2010-07-22 | 2013-07-03 | 中原工学院 | Preparation method of fire resistant phase transition thermal insulation layered fabric for firefighter clothing |
CN103732192B (en) | 2011-08-17 | 2016-03-16 | 3M创新有限公司 | Monomer-grafted fiber and uses thereof |
CN103008330B (en) * | 2012-12-18 | 2015-04-22 | 武汉纺织大学 | Method for producing fragrance decorations by using waste fabrics |
US10431858B2 (en) | 2015-02-04 | 2019-10-01 | Global Web Horizons, Llc | Systems, structures and materials for electrochemical device thermal management |
CN105369380B (en) * | 2015-12-11 | 2017-12-22 | 恒天海龙(潍坊)新材料有限责任公司 | Phase-change temperature-regulating cellulose fiber prepared by solvent method and preparation method thereof |
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US20010044477A1 (en) * | 1998-12-10 | 2001-11-22 | Soane David S. | Expandable polymeric microspheres, their method of production, and uses and products thereof |
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CH692574A5 (en) * | 2001-05-18 | 2002-08-15 | Schoeller Textil Ag | A process for producing temperature-regulating surfaces and products made from this. |
FR2827316B1 (en) | 2001-07-13 | 2004-07-30 | Inter Unec Interaction Univers | TEXTILE FIBER SURFACE TREATMENT PROCESS |
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US20100035492A1 (en) | 2010-02-11 |
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