EP2126191A1 - Ionising radiation grafting method using a reactive surfactant molecule and resulting textile substrate and battery separator - Google Patents

Ionising radiation grafting method using a reactive surfactant molecule and resulting textile substrate and battery separator

Info

Publication number
EP2126191A1
EP2126191A1 EP08761809A EP08761809A EP2126191A1 EP 2126191 A1 EP2126191 A1 EP 2126191A1 EP 08761809 A EP08761809 A EP 08761809A EP 08761809 A EP08761809 A EP 08761809A EP 2126191 A1 EP2126191 A1 EP 2126191A1
Authority
EP
European Patent Office
Prior art keywords
textile substrate
groups
group
grafting
functional
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.)
Withdrawn
Application number
EP08761809A
Other languages
German (de)
French (fr)
Inventor
Nabila Kourda
Philippe Le Thuaut
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 EP2126191A1 publication Critical patent/EP2126191A1/en
Withdrawn legal-status Critical Current

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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
    • D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
    • D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M14/32—Polyesters

Definitions

  • the invention relates to a method of grafting functional chemical groups on a textile substrate, as well as a textile substrate and a battery separator grafted by implementing such a method.
  • the invention is particularly applicable to the grafting of textile substrates so as to give them an ion exchange function.
  • the invention provides a method of grafting a bipolar textile substrate, that is to say comprising a different ion exchange function on each of its faces.
  • the grafted textile substrates according to the invention are particularly useful in the agri-food, pharmaceutical, medical, energy, biological and environmental fields.
  • the use of textile ion exchange substrates according to the invention allows:
  • the implementation of the known methods poses the problem of removing the solvent and ungrafted chemical substances that are contained in the textile substrate, as well as the problem of their subsequent recycling.
  • the aim of the invention is to overcome the problems of the prior art by proposing a process for grafting functional chemical groups onto a textile substrate which is particularly simple and adaptable in its implementation, said method also making it possible to obtain quality bipolar textile substrates.
  • the invention provides a method of grafting functional chemical groups on a textile substrate, said method providing for impregnating said substrate with a solution of a functional molecule comprising the functional chemical group and a reactive group under ionizing radiation, said solution further comprising a surfactant molecule which is capable of improving the wettability of the textile substrate by said solution, said surfactant molecule comprising at least two types of reactive groups under ionizing radiation, said method providing for the application of ionizing radiation to the textile substrate impregnated for, by reaction of the reactive groups, ensuring the grafting of the functional molecules by bridging with the surfactant molecules.
  • the invention proposes a textile substrate of which at least one surface is grafted with functional chemical groups, said grafting being carried out by bridging with a surfactant molecule by means of such a process.
  • the invention provides a battery separator comprising a textile substrate on which are grafted sulfonic groups and phosphoric and / or carboxylic groups, said grafting being carried out by bridging with at least one surfactant molecule by means of a such a method.
  • the invention relates to a method of grafting functional chemical groups on a textile substrate, in particular functional chemical groups capable of exchanging cations or anions with their environment, in particular with a medium in which the textile substrate is disposed.
  • the method provides for impregnating the textile substrate with a solution of a functional molecule comprising the functional chemical group and a reactive group under ionizing radiation.
  • the solution may be at least partially in the form of an emulsion.
  • the impregnation is performed by padding, the impregnated textile substrate being dried prior to the application of ionizing radiation.
  • the reactive 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, carboxyl, carbonyl, acrylate, methacrylate, allyl, amine, amide, imide and urethane groups.
  • the chemical cation exchange group is chosen from the group comprising sulphonic, carboxylic and phosphoric groups, the chemical cation exchange group being chosen from the group comprising amino and ammonium groups.
  • the functional molecule is chosen from the group comprising sulphoalkyl methacrylates (in particular sulphopropyl methacrylate), acrylates or alkyl carboxylic methacrylates (in particular acrylic acid), alkyl phosphoric methacrylates and ethylene glycol methacrylate.
  • sulphoalkyl methacrylates in particular sulphopropyl methacrylate
  • acrylates or alkyl carboxylic methacrylates in particular acrylic acid
  • alkyl phosphoric methacrylates and ethylene glycol methacrylate.
  • the solvent of the solution is water, for example the concentration of functional molecule is between 0.5 and 1 M.
  • the solution can comprise other agents, in particular for improving the solubility of the molecules and / or the stability of said solution.
  • the textile substrate is based on fibers made of synthetic material, in particular polyolefinic material, as is frequently imposed by the applications envisaged for grafted textile substrates.
  • the fibers may be polypropylene, polyethylene, polyester, polyvinyl alcohol or polytetrafluoroethylene (PTFE), or a mixture of these different fibers.
  • the substrate may comprise a nonwoven web, for example having a thickness of between 0.2 and 5 mm and a weight of between 30 and 600 g / m 2 .
  • the textile substrate may be formed of at least one woven or knitted layer.
  • the grafting method according to the invention can also be implemented with textile substrates made of natural fibers, such as cotton or wool, or artificial fibers, such as viscose or cellulose.
  • the method provides, for improving the wettability of the textile substrate by the solution, that said solution further comprises a surfactant molecule.
  • said solution further comprises a surfactant molecule.
  • the nature and quantity of the surfactant molecules in the solution are provided so that the surface tension of the solution is similar to that of the fibers.
  • the textile substrate can be impregnated with a large volume of solution, so as to increase the density of functional chemical groups which are grafted onto the textile substrate.
  • the surfactant molecules used comprise at least two types of reactive groups under ionizing radiation, which types may be identical or different from each other and identical or different from that of the functional molecule.
  • the reaction of the reactive groups ensures the grafting of the functional molecules by bridging with the surfactant molecules.
  • the reactions of the reactive groups make it possible to connect the surfactant molecules to the fibers or to each other, as well as the functional molecules to the surfactant molecules or directly to the fibers. A network is thus created between the fibers, the functional molecules and the surfactant molecules which is particularly resistant to the chemical and mechanical stresses that the grafted textile substrate will have to undergo in the context of its use.
  • the ionizing radiation is electron bombardment whose power and duration can be modulated to activate the reactive groups optimally.
  • the grafting process is particularly flexible in that the nature of the surfactant molecule can be chosen as a function of the textile substrate, in particular as a function of its surface tension, whereas the nature of the functional molecule is chosen as a function of the functional chemical group to be grafted.
  • the surfactant molecule may be difunctional by comprising two types of reactive groups, for example the surfactant molecule may be chosen from the group comprising diacrylates, in particular polyethylene glycol diacrylate glycols (PEG DA).
  • PEG DA polyethylene glycol diacrylate glycols
  • PTFE fibers 1 PEG600 DA is particularly satisfactory and, with the high density polyethylene fibers, the use of PEG200 DA is satisfactory.
  • the surfactant molecule can be trifunctional by comprising three types of reactive groups, for example the surfactant molecule can be chosen from the group comprising triacrylates, especially ethoxylated trimethylolpropane triacrylates.
  • the surfactant molecule can be chosen from the group comprising triacrylates, especially ethoxylated trimethylolpropane triacrylates.
  • ethoxylated trimethylolpropane triacrylate is particularly suitable.
  • the textile substrate After the application of the ionizing radiation, the textile substrate can be washed and then dried or undergo other treatments necessary for its subsequent use. In addition, prior to grafting, the textile substrate may undergo particular treatments, in particular to improve its cohesion and / or its wettability.
  • the solution comprises two functional molecules each comprising a different functional chemical group, the application of the ionizing radiation being arranged to graft each of the functional chemical groups on one side of the textile substrate, respectively.
  • the method is arranged to graft the textile substrate to a determined depth so as to form a surface layer of graft material.
  • the textile substrate comprising two faces which are each grafted with a different functional chemical group.
  • the textile substrate may have an anion exchange face and a cation exchange face.
  • the ionizing radiation is applied to each of the faces, with a penetration thickness of said radiation which is less than the thickness of the textile substrate.
  • the application of the radiation can be carried out in a passage on each side of the textile substrate and the power of the ionizing radiation is modulated to obtain the appropriate penetration thickness.
  • the textile substrate can be grafted on one half of its thickness with anion exchange groups, and on the other half with cation exchange groups.
  • the grafting method makes it possible to produce a battery separator comprising a textile substrate, in particular formed of a nonwoven web of synthetic fibers, on which are grafted sulfonic groups and phosphoric and / or carboxylic groups.
  • the grafting is carried out by bridging with at least one surfactant molecule as described above.
  • the battery is of the nickel metal hydride type which has good energy performance but has the defect of generating ammonium ions during recharge / discharge cycles.
  • the ammonium ions pollute the electrodes and therefore reduce the rate of recharging of the battery.
  • the battery life is decreased.
  • the battery separator according to the invention is remarkable in that it incorporates:
  • the trapping function of the ammonium ions which are produced during the electrochemical operation of the battery.

Abstract

The invention relates to a method for grafting functional chemical groups to a textile substrate, wherein the substrate is impregnated with a solution of a functional molecule, containing the functional chemical group and a group that is reactive to ionising radiation, as well as a surfactant molecule that can improve the wettability of the textile substrate by the solution. The surfactant molecule contains at least two types of groups that are reactive to ionising radiation. Subsequently, ionising radiation is applied to the impregnated textile substrate and the reaction of the reactive groups bridge-grafts the functional molecules to the surfactant molecules. The invention also relates to a textile substrate and a battery separator grafted using the above method.

Description

Procédé de greffage par rayonnement ionisant au moyen d'une molécule tensioactive réactive, substrat textile et séparateur de batterie obtenus par greffage Ionizing radiation grafting method using reactive surfactant molecule, textile substrate and grafted battery separator
L'invention concerne un procédé de greffage de groupements chimiques fonctionnels sur un substrat textile, ainsi qu'un substrat textile et un séparateur de batterie greffés par mise en œuvre d'un tel procédé.The invention relates to a method of grafting functional chemical groups on a textile substrate, as well as a textile substrate and a battery separator grafted by implementing such a method.
L'invention s'applique notamment au greffage des substrats textiles de sorte à leur conférer une fonction échangeuse d'ions. En particulier, l'invention propose un procédé de greffage d'un substrat textile bipolaire, c'est-à-dire comprenant une fonction échangeuse d'ions différente sur chacune de ses faces.The invention is particularly applicable to the grafting of textile substrates so as to give them an ion exchange function. In particular, the invention provides a method of grafting a bipolar textile substrate, that is to say comprising a different ion exchange function on each of its faces.
Les substrats textiles greffés suivant l'invention trouvent notamment leur utilité dans les domaines agro alimentaire, pharmaceutique, médical, énergétique, biologique et environnemental. Par exemple, l'utilisation des substrats textiles échangeurs d'ions selon l'invention permet :The grafted textile substrates according to the invention are particularly useful in the agri-food, pharmaceutical, medical, energy, biological and environmental fields. For example, the use of textile ion exchange substrates according to the invention allows:
- d'augmenter la conductivité des solutions dans le but d'améliorer les procédés de séparation par électrodialyse et les procédés électrochimiques ;to increase the conductivity of the solutions in order to improve the electrodialysis separation processes and the electrochemical processes;
- l'adoucissement de l'eau avec éventuellement une propriété bactériostatique ;- softening of the water with possibly a bacteriostatic property;
- la fabrication de masques ou de vêtements de protection biologique à propriété virucide ;- the manufacture of masks or biological protective clothing with virucidal property;
- l'électrodéionisation pour la production d'eau ultra pure ou pour la déminéralisation de molécules après synthèse ;- Electrodeionization for the production of ultra pure water or for the demineralization of molecules after synthesis;
- la réalisation de séparateurs de batteries ;- the realization of battery separators;
- l'élaboration d'un matériau indicateur de contamination spécifique à une bactérie ou un virus donné à des fins de diagnostic ;- the development of a specific contamination indicator material for a given bacterium or virus for diagnostic purposes;
- le traitement des effluents industriels et de l'eau par procédé d'échange en continu ou en discontinu et par procédé électromembranaire hybride combinant les membranes échangeuses d'ions et les substrats textiles échangeurs d'ions.- the treatment of industrial effluents and water by continuous or discontinuous exchange process and by hybrid electromembrane process combining ion exchange membranes and ion exchange textile substrates.
Selon l'art antérieur, on connaît des procédés industriels de greffage par voie chimique dans lesquels des molécules sont fixées au substrat textile pour être ensuite fonctionnalisées notamment par réactions en milieu acide ou basique.According to the prior art, there are known chemical grafting industrial processes in which molecules are attached to the textile substrate to be subsequently functionalized in particular by reactions in an acidic or basic medium.
En particulier, ces procédés présentent l'inconvénient de devoir être réalisés en solution organique et de nécessiter un chauffage. En outre, ces procédés ne permettent pas de greffer une gamme importante de groupements chimiques fonctionnels, au moins de façon simple et modulable en fonction de la nature du substrat textile.In particular, these processes have the disadvantage of having to be made in organic solution and require heating. In addition, these methods do not make it possible to graft a large range of functional chemical groups, at least in a simple and flexible manner depending on the nature of the textile substrate.
Par ailleurs, après le greffage, la mise en œuvre des procédés connus pose le problème de l'élimination du solvant et des substances chimiques non greffées qui sont contenus dans le substrat textile, ainsi que le problème de leur recyclage ultérieur.Furthermore, after the grafting, the implementation of the known methods poses the problem of removing the solvent and ungrafted chemical substances that are contained in the textile substrate, as well as the problem of their subsequent recycling.
Enfin, la réalisation d'un substrat textile bipolaire avec les procédés de l'art antérieur ne donne pas satisfaction, notamment relativement à la présence de chacune des fonctions échangeuses d'ions sur une seule face.Finally, the production of a bipolar textile substrate with the methods of the prior art does not give satisfaction, particularly with respect to the presence of each of the ion exchange functions on one side.
L'invention a pour but de pallier les problèmes de l'art antérieur en proposant un procédé de greffage de groupements chimiques fonctionnels sur un substrat textile qui soit particulièrement simple et modulable dans sa mise en œuvre, ledit procédé permettant en outre d'obtenir des substrats textiles bipolaires de qualité.The aim of the invention is to overcome the problems of the prior art by proposing a process for grafting functional chemical groups onto a textile substrate which is particularly simple and adaptable in its implementation, said method also making it possible to obtain quality bipolar textile substrates.
A cet effet, et selon un premier aspect, l'invention propose un procédé de greffage de groupements chimiques fonctionnels sur un substrat textile, ledit procédé prévoyant d'imprégner ledit substrat avec une solution d'une molécule fonctionnelle comprenant le groupement chimique fonctionnel et un groupement réactif sous rayonnement ionisant, ladite solution comprenant en outre une molécule tensioactive qui est apte à améliorer la mouillabilité du substrat textile par ladite solution, ladite molécule tensioactive comprenant au moins deux types de groupements réactifs sous rayonnement ionisant, ledit procédé prévoyant d'appliquer un rayonnement ionisant sur le substrat textile imprégné pour, par réaction des groupements réactifs, assurer le greffage des molécules fonctionnelles par pontage avec les molécules tensioactives.For this purpose, and according to a first aspect, the invention provides a method of grafting functional chemical groups on a textile substrate, said method providing for impregnating said substrate with a solution of a functional molecule comprising the functional chemical group and a reactive group under ionizing radiation, said solution further comprising a surfactant molecule which is capable of improving the wettability of the textile substrate by said solution, said surfactant molecule comprising at least two types of reactive groups under ionizing radiation, said method providing for the application of ionizing radiation to the textile substrate impregnated for, by reaction of the reactive groups, ensuring the grafting of the functional molecules by bridging with the surfactant molecules.
Selon un deuxième aspect, l'invention propose un substrat textile dont au moins une surface est greffée avec des groupements chimiques fonctionnels, ledit greffage étant réalisé par pontage avec une molécule tensioactive au moyen d'un tel procédé.According to a second aspect, the invention proposes a textile substrate of which at least one surface is grafted with functional chemical groups, said grafting being carried out by bridging with a surfactant molecule by means of such a process.
Selon un troisième aspect, l'invention propose un séparateur de batterie comprenant un substrat textile sur lequel sont greffées des groupements sulfoniques et des groupements phosphoriques et/ou carboxyliques, ledit greffage étant réalisé par pontage avec au moins une molécule tensioactive au moyen d'un tel procédé.According to a third aspect, the invention provides a battery separator comprising a textile substrate on which are grafted sulfonic groups and phosphoric and / or carboxylic groups, said grafting being carried out by bridging with at least one surfactant molecule by means of a such a method.
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 greffage de groupements chimiques fonctionnels sur un substrat textile, en particulier de groupements chimiques fonctionnels aptes à échanger des cations ou des anions avec leur environnement, notamment avec un milieu dans lequel le substrat textile est disposé.The invention relates to a method of grafting functional chemical groups on a textile substrate, in particular functional chemical groups capable of exchanging cations or anions with their environment, in particular with a medium in which the textile substrate is disposed.
Le procédé prévoit d'imprégner le substrat textile avec une solution d'une molécule fonctionnelle comprenant le groupement chimique fonctionnel et un groupement réactif sous rayonnement ionisant. En fonction de la solubilité de la molécule fonctionnelle, la solution peut se présenter au moins partiellement sous la forme d'une émulsion. Selon une réalisation, l'imprégnation est réalisée par foulardage, le substrat textile imprégné étant séché préalablement à l'application du rayonnement ionisant.The method provides for impregnating the textile substrate with a solution of a functional molecule comprising the functional chemical group and a reactive group under ionizing radiation. Depending on the solubility of the functional molecule, the solution may be at least partially in the form of an emulsion. According to one embodiment, the impregnation is performed by padding, the impregnated textile substrate being dried prior to the application of ionizing radiation.
En particulier, les groupements réactifs 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, allyles, aminés, amides, imides, uréthanes.In particular, the reactive 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, carboxyl, carbonyl, acrylate, methacrylate, allyl, amine, amide, imide and urethane groups.
Selon une réalisation, le groupement chimique échangeur de cations est choisi dans le groupe comprenant les groupements sulfoniques, carboxyliques et phosphoriques, le groupement chimique échangeur de cations étant choisi dans le groupe comprenant les groupements aminés et ammoniums.According to one embodiment, the chemical cation exchange group is chosen from the group comprising sulphonic, carboxylic and phosphoric groups, the chemical cation exchange group being chosen from the group comprising amino and ammonium groups.
A titre d'exemple, la molécule fonctionnelle est choisie dans le groupe comprenant les sulfoalkyl méthacrylates (notamment le sulfopropyl méthacrylate), les acrylates ou les méthacrylates alkyl carboxyliques (notamment l'acide acrylique), les méthacrylates alkyl phosphoriques, l'éthylène glycol méthacrylate phosphate, les dialkylaminoalkyl méthacrylates (notamment le diméthylaminoéthyl méthacrylate), les méthacrylatealkyl trialkyl ammonium (notamment l'acryloxyéthyltriméthyl ammonium).By way of example, the functional molecule is chosen from the group comprising sulphoalkyl methacrylates (in particular sulphopropyl methacrylate), acrylates or alkyl carboxylic methacrylates (in particular acrylic acid), alkyl phosphoric methacrylates and ethylene glycol methacrylate. phosphate, dialkylaminoalkyl methacrylates (especially dimethylaminoethyl methacrylate), methacrylatalkyl trialkyl ammonium (especially acryloxyethyltrimethylammonium).
De façon avantageuse relativement à la mise en œuvre et à l'écologie, le solvant de la solution est de l'eau, par exemple la concentration en molécule fonctionnelle est comprise entre 0,5 et 1 M. En outre, la solution peut comprendre d'autres agents, notamment destinés à améliorer la solubilité des molécules et/ou la stabilité de ladite solution.Advantageously relative to the implementation and the ecology, the solvent of the solution is water, for example the concentration of functional molecule is between 0.5 and 1 M. In addition, the solution can comprise other agents, in particular for improving the solubility of the molecules and / or the stability of said solution.
Dans un mode de réalisation, le substrat textile est à base de fibres en matériau synthétique, notamment polyoléfinique, comme cela est fréquemment imposé par les applications envisagées pour les substrats textiles greffés. A titre d'exemple, les fibres peuvent être en polypropylène, en polyéthylène, en polyester, en polyvinyl alcool ou en polytétrafuoroéthylène (PTFE), ou un mélange de ces différentes fibres.In one embodiment, the textile substrate is based on fibers made of synthetic material, in particular polyolefinic material, as is frequently imposed by the applications envisaged for grafted textile substrates. As for example, the fibers may be polypropylene, polyethylene, polyester, polyvinyl alcohol or polytetrafluoroethylene (PTFE), or a mixture of these different fibers.
Le substrat peut comprendre une nappe de non tissé, par exemple d'une épaisseur comprise entre 0,2 et 5 mm et d'un poids compris entre 30 et 600 g/m2. En variante, le substrat textile peut être formé d'au moins une couche tissée ou tricotée.The substrate may comprise a nonwoven web, for example having a thickness of between 0.2 and 5 mm and a weight of between 30 and 600 g / m 2 . Alternatively, the textile substrate may be formed of at least one woven or knitted layer.
Le procédé de greffage selon l'invention peut également être mis en œuvre avec des substrats textiles en fibres naturelles, telles qu'en coton ou en laine, ou en fibres artificielles, telles qu'en viscose ou en cellulose.The grafting method according to the invention can also be implemented with textile substrates made of natural fibers, such as cotton or wool, or artificial fibers, such as viscose or cellulose.
Le procédé prévoit, pour améliorer la mouillabilité du substrat textile par la solution, que ladite solution comprenne en outre une molécule tensioactive. Ainsi, en améliorant l'affinité entre la solution et les fibres du substrat textile, le procédé permet de greffer des substrats textiles même lorsqu'ils sont à base de fibres synthétiques présentant une hydrophobie importante.The method provides, for improving the wettability of the textile substrate by the solution, that said solution further comprises a surfactant molecule. Thus, by improving the affinity between the solution and the fibers of the textile substrate, the process makes it possible to graft textile substrates even when they are based on synthetic fibers having a high hydrophobicity.
En particulier, la nature et la quantité des molécules tensioactives dans la solution sont prévues pour que la tension de surface de la solution soit analogue à celle des fibres. Ainsi, le substrat textile peut être imprégné avec un grand volume de solution, de sorte à augmenter la densité de groupements chimiques fonctionnels qui sont greffés sur le substrat textile.In particular, the nature and quantity of the surfactant molecules in the solution are provided so that the surface tension of the solution is similar to that of the fibers. Thus, the textile substrate can be impregnated with a large volume of solution, so as to increase the density of functional chemical groups which are grafted onto the textile substrate.
Par ailleurs, pour éviter l'élimination ultérieure de la molécule tensioactive et améliorer le greffage des groupements chimiques fonctionnels, les molécules tensioactives utilisées comprennent au moins deux types de groupements réactifs sous rayonnement ionisant, lesdits types pouvant être identiques ou différents entre eux et identiques ou différents de celui de la molécule fonctionnelle. Ainsi, par application d'un rayonnement ionisant sur le substrat textile imprégné, la réaction des groupements réactifs assure le greffage des molécules fonctionnelles par pontage avec les molécules tensioactives. En effet, les réactions des groupements réactifs permettent de relier les molécules tensioactives aux fibres ou entre elles, ainsi que les molécules fonctionnelles aux molécules tensioactives ou directement aux fibres. Il se crée ainsi un réseau entre les fibres, les molécules fonctionnelles et les molécules tensioactives qui est particulièrement résistant relativement aux contraintes chimiques et mécaniques que le substrat textile greffé aura à subir dans le cadre de son utilisation.Moreover, in order to avoid the subsequent removal of the surfactant molecule and to improve the grafting of the functional chemical groups, the surfactant molecules used comprise at least two types of reactive groups under ionizing radiation, which types may be identical or different from each other and identical or different from that of the functional molecule. Thus, by application of ionizing radiation on the impregnated textile substrate, the reaction of the reactive groups ensures the grafting of the functional molecules by bridging with the surfactant molecules. In fact, the reactions of the reactive groups make it possible to connect the surfactant molecules to the fibers or to each other, as well as the functional molecules to the surfactant molecules or directly to the fibers. A network is thus created between the fibers, the functional molecules and the surfactant molecules which is particularly resistant to the chemical and mechanical stresses that the grafted textile substrate will have to undergo in the context of its use.
Selon une réalisation, le rayonnement ionisant est bombardement électronique dont la puissance et la durée peuvent être modulées pour activer les groupements réactifs de façon optimale.In one embodiment, the ionizing radiation is electron bombardment whose power and duration can be modulated to activate the reactive groups optimally.
Par ailleurs, le procédé de greffage est particulièrement modulable en ce que la nature de la molécule tensioactive peut être choisie en fonction du substrat textile, notamment en fonction de sa tension de surface, alors que la nature de la molécule fonctionnelle est choisie en fonction du groupement chimique fonctionnel qui doit être greffé.Moreover, the grafting process is particularly flexible in that the nature of the surfactant molecule can be chosen as a function of the textile substrate, in particular as a function of its surface tension, whereas the nature of the functional molecule is chosen as a function of the functional chemical group to be grafted.
La molécule tensioactive peut être difonctionnelle en comprenant deux types de groupements réactifs, par exemple la molécule tensioactive peut être choisie dans le groupe comprenant les diacrylates, notamment les polyéthylènes glycols diacrylates (PEG DA). En particulier, avec les fibres en PTFE1 le PEG600 DA est particulièrement satisfaisant et, avec les fibres en polyéthylène haute densité, l'utilisation du PEG200 DA donne satisfaction.The surfactant molecule may be difunctional by comprising two types of reactive groups, for example the surfactant molecule may be chosen from the group comprising diacrylates, in particular polyethylene glycol diacrylate glycols (PEG DA). In particular, with PTFE fibers 1 PEG600 DA is particularly satisfactory and, with the high density polyethylene fibers, the use of PEG200 DA is satisfactory.
En variante, la molécule tensioactive peut être trifonctionnelle en comprenant trois types de groupements réactifs, par exemple la molécule tensioactive peut être choisie dans le groupe comprenant les triacrylates, notamment les triméthylolpropanes triacrylates éthoxylés. En particulier, avec les fibres en polypropylène, le triméthylolpropane triacrylate éthoxylé 20 est particulièrement adapté.Alternatively, the surfactant molecule can be trifunctional by comprising three types of reactive groups, for example the surfactant molecule can be chosen from the group comprising triacrylates, especially ethoxylated trimethylolpropane triacrylates. In particular, with the fibers in polypropylene, ethoxylated trimethylolpropane triacrylate is particularly suitable.
Après l'application du rayonnement ionisant, le substrat textile peut être lavé puis séché ou subir d'autres traitements nécessaires à son utilisation ultérieure. En outre, préalablement au greffage, le substrat textile peut subir des traitements particuliers, notamment pour améliorer sa cohésion et/ou sa mouillabilité.After the application of the ionizing radiation, the textile substrate can be washed and then dried or undergo other treatments necessary for its subsequent use. In addition, prior to grafting, the textile substrate may undergo particular treatments, in particular to improve its cohesion and / or its wettability.
Selon une réalisation, la solution comprend deux molécules fonctionnelles comprenant chacune un groupement chimique fonctionnel différent, l'application du rayonnement ionisant étant agencée pour greffer chacun des groupements chimiques fonctionnels sur respectivement une face du substrat textile. En particulier, le procédé est agencé pour greffer le substrat textile sur une profondeur déterminée de sorte à former une couche superficielle de matériau greffée.According to one embodiment, the solution comprises two functional molecules each comprising a different functional chemical group, the application of the ionizing radiation being arranged to graft each of the functional chemical groups on one side of the textile substrate, respectively. In particular, the method is arranged to graft the textile substrate to a determined depth so as to form a surface layer of graft material.
On obtient ainsi un substrat textile comprenant deux faces qui sont greffées chacune avec un groupement chimique fonctionnel différent. En particulier, le substrat textile peut présenter une face échangeuse d'anions et une face échangeuse de cations.There is thus obtained a textile substrate comprising two faces which are each grafted with a different functional chemical group. In particular, the textile substrate may have an anion exchange face and a cation exchange face.
Pour ce faire, le rayonnement ionisant est appliqué sur chacune des faces, avec une épaisseur de pénétration dudit rayonnement qui est inférieure à l'épaisseur du substrat textile. En particulier, l'application du rayonnement peut être réalisée en un passage de chaque coté du substrat textile et la puissance du rayonnement ionisant est modulée pour obtenir l'épaisseur de pénétration adéquate. Par exemple, le substrat textile peut être greffé sur une moitié de son épaisseur avec des groupements échangeurs d'anions, et sur l'autre moitié avec des groupements échangeurs de cations.To do this, the ionizing radiation is applied to each of the faces, with a penetration thickness of said radiation which is less than the thickness of the textile substrate. In particular, the application of the radiation can be carried out in a passage on each side of the textile substrate and the power of the ionizing radiation is modulated to obtain the appropriate penetration thickness. For example, the textile substrate can be grafted on one half of its thickness with anion exchange groups, and on the other half with cation exchange groups.
Dans une application particulière envisagée, le procédé de greffage permet de réaliser un séparateur de batterie comprenant un substrat textile, notamment formé d'une nappe de non tissé en fibres synthétiques, sur lequel sont greffées des groupements sulfoniques et des groupements phosphoriques et/ou carboxyliques. Ainsi, le greffage est réalisé par pontage avec au moins une molécule tensioactive tel que décrit ci-dessus.In a particular application envisaged, the grafting method makes it possible to produce a battery separator comprising a textile substrate, in particular formed of a nonwoven web of synthetic fibers, on which are grafted sulfonic groups and phosphoric and / or carboxylic groups. Thus, the grafting is carried out by bridging with at least one surfactant molecule as described above.
En particulier, la batterie est du type nickel métal hydrure qui présente de bonnes performances énergétiques mais possède le défaut de générer des ions ammoniums lors des cycles de recharge / décharge. Or, les ions ammoniums polluent les électrodes et diminuent donc le taux de recharge de la batterie. Ainsi, l'autonomie de la batterie se trouve diminuée.In particular, the battery is of the nickel metal hydride type which has good energy performance but has the defect of generating ammonium ions during recharge / discharge cycles. However, the ammonium ions pollute the electrodes and therefore reduce the rate of recharging of the battery. Thus, the battery life is decreased.
Le séparateur de batterie selon l'invention est remarquable en ce qu'il intègre :The battery separator according to the invention is remarkable in that it incorporates:
- par l'intermédiaire des groupements sulfoniques, une fonction d'amélioration de la puissance de la batterie en améliorant la conductivité ;via the sulfonic groups, a function of improving the power of the battery by improving the conductivity;
- par l'intermédiaire des groupements phosphoriques et/ou carboxyliques, la fonction de piégeage des ions ammoniums qui sont produit lors du fonctionnement électrochimique de la batterie. via the phosphoric and / or carboxylic groups, the trapping function of the ammonium ions which are produced during the electrochemical operation of the battery.

Claims

REVENDICATIONS
1. Procédé de greffage de groupements chimiques fonctionnels sur un substrat textile, ledit procédé prévoyant d'imprégner ledit substrat avec une solution d'une molécule fonctionnelle comprenant le groupement chimique fonctionnel et un groupement réactif sous rayonnement ionisant, ladite solution comprenant en outre une molécule tensioactive qui est apte à améliorer la mouillabilité du substrat textile par ladite solution, ladite molécule tensioactive comprenant au moins deux types de groupements réactifs sous rayonnement ionisant, ledit procédé prévoyant d'appliquer un rayonnement ionisant sur le substrat textile imprégné pour, par réaction des groupements réactifs, assurer le greffage des molécules fonctionnelles par pontage avec les molécules tensioactives.A method of grafting functional chemical groups on a textile substrate, said method providing for impregnating said substrate with a solution of a functional molecule comprising the functional chemical group and a reactive group under ionizing radiation, said solution further comprising a molecule surfactant which is capable of improving the wettability of the textile substrate by said solution, said surfactant molecule comprising at least two types of reactive groups under ionizing radiation, said method providing for the application of ionizing radiation on the textile substrate impregnated for, by reaction of the groups reagents, ensure the grafting of functional molecules by bridging with the surfactant molecules.
2. Procédé de greffage selon la revendication 1, dans lequel le substrat textile est à base de fibres en matériau synthétique.2. grafting method according to claim 1, wherein the textile substrate is based on synthetic fibers.
3. Procédé de greffage selon la revendication 1 ou 2, dans lequel le solvant de la solution est de l'eau.3. grafting method according to claim 1 or 2, wherein the solvent of the solution is water.
4. Procédé de greffage selon l'une quelconque des revendications 1 à 3, dans lequel le groupement chimique fonctionnel est apte à échanger des cations ou des anions.4. grafting method according to any one of claims 1 to 3, wherein the functional chemical group is able to exchange cations or anions.
5. Procédé de greffage selon la revendication 4, dans lequel le groupement chimique échangeur de cations est choisi dans le groupe comprenant les groupements sulfoniques, carboxyliques et phosphoriques, le groupement chimique échangeur de cations étant choisi dans le groupe comprenant les groupements aminés et ammoniums.5. Grafting method according to claim 4, wherein the chemical cation exchange group is selected from the group comprising sulfonic, carboxylic and phosphoric groups, the chemical cation exchange group being selected from the group comprising amino and ammonium groups.
6. Procédé de greffage selon la revendication 5, dans lequel la molécule fonctionnelle est choisie dans le groupe comprenant les sulfoalkyl méthacrylates, les acrylates ou les méthacrylates alkyl carboxyliques, les méthacrylates alkyl phosphoriques, l'éthylène glycol méthacrylate phosphate, les dialkylaminoalkyl méthacrylates, les méthacrylatealkyl trialkyl ammonium.The grafting method according to claim 5, wherein the functional molecule is selected from the group consisting of sulfoalkyl methacrylates, acrylates or alkyl carboxylic methacrylates, alkyl phosphoric methacrylates, ethylene glycol methacrylate phosphate, dialkylaminoalkyl methacrylates, methacrylatalkyl trialkyl ammonium.
7. Procédé de greffage selon l'une quelconque des revendications 1 à 6, dans lequel la solution comprend deux molécules fonctionnelles comprenant chacune un groupement chimique fonctionnel différent, l'application du rayonnement ionisant étant agencée pour greffer chacun des groupements chimiques fonctionnels sur respectivement une face du substrat textile.7. Grafting method according to any one of claims 1 to 6, wherein the solution comprises two functional molecules each comprising a different functional chemical group, the application of ionizing radiation being arranged to graft each of the functional chemical groups on a respective face of the textile substrate.
8. Procédé de greffage selon la revendication 7, dans lequel le rayonnement ionisant est appliqué sur chacune des faces, avec une épaisseur de pénétration dudit rayonnement qui est inférieure à l'épaisseur du substrat textile.8. grafting method according to claim 7, wherein the ionizing radiation is applied to each of the faces, with a penetration thickness of said radiation which is less than the thickness of the textile substrate.
9. Procédé de greffage selon l'une quelconque des revendications 1 à 8, dans lequel les groupements réactifs sous rayonnement ionisant sont choisis dans le groupe comprenant les groupements hydroxyles, carboxyles, carbonyles, acrylates, méthacrylates, allyles, aminés, amides, imides, uréthanes.9. grafting method according to any one of claims 1 to 8, wherein the reactive groups under ionizing radiation are selected from the group consisting of hydroxyl groups, carboxyl, carbonyl, acrylates, methacrylates, allyls, amines, amides, imides, urethanes.
10. Procédé de greffage selon la revendication 9, dans lequel la molécule tensioactive est choisie dans le groupe comprenant les diacrylates, notamment les polyéthylènes glycols diacrylates (PEG DA), et les triacrylates, notamment les triméthylolpropanes triacrylates éthoxylés.10. grafting method according to claim 9, wherein the surfactant molecule is selected from the group comprising diacrylates, including polyethylene glycol diacrylate glycols (PEG DA), and triacrylates, including ethoxylated trimethylolpropanes triacrylates.
11. Procédé de greffage selon l'une quelconque des revendications 1 à 10, dans lequel l'imprégnation est réalisée par foulardage, le substrat textile imprégné étant séché préalablement à l'application du rayonnement ionisant.11. grafting method according to any one of claims 1 to 10, wherein the impregnation is performed by padding, the impregnated textile substrate being dried prior to the application of ionizing radiation.
12. Procédé de greffage selon l'une quelconque des revendications 1 à 11 , dans lequel le rayonnement ionisant est un bombardement électronique.12. Grafting method according to any one of claims 1 to 11, wherein the ionizing radiation is an electron bombardment.
13. Substrat textile dont au moins une surface est greffée avec des groupements chimiques fonctionnels, ledit greffage étant réalisé par pontage avec une molécule tensioactive au moyen d'un procédé selon l'une quelconque des revendications 1 à 12.13. Textile substrate of which at least one surface is grafted with functional chemical groups, said grafting being carried out by bridging with a surfactant molecule by means of a process according to any one of claims 1 to 12.
14. Substrat textile selon la revendication 13, caractérisé en ce qu'il est à base de fibres en matériau synthétique.14. Textile substrate according to claim 13, characterized in that it is based on synthetic fibers.
15. Substrat textile selon la revendication 13 ou 14, caractérisé en ce que le groupement chimique fonctionnel est apte à échanger des cations ou des anions.15. Textile substrate according to claim 13 or 14, characterized in that the functional chemical group is able to exchange cations or anions.
16. Substrat textile selon l'une quelconque des revendications 13 à 15, caractérisé en ce qu'il comprend deux faces qui sont greffées chacune avec un groupement chimique fonctionnel différent.16. Textile substrate according to any one of claims 13 to 15, characterized in that it comprises two faces which are each grafted with a different functional chemical group.
17. Séparateur de batterie comprenant un substrat textile sur lequel sont greffées des groupements sulfoniques et des groupements phosphoriques et/ou carboxyliques, ledit greffage étant réalisé par pontage avec au moins une molécule tensioactive au moyen d'un procédé selon l'une quelconque des revendications 1 à 12. 17. A battery separator comprising a textile substrate on which are grafted sulphonic groups and phosphoric and / or carboxylic groups, said grafting being carried out by bridging with at least one surfactant molecule by means of a process according to any one of the claims. 1 to 12.
EP08761809A 2007-01-29 2008-01-28 Ionising radiation grafting method using a reactive surfactant molecule and resulting textile substrate and battery separator Withdrawn EP2126191A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0700593A FR2911883B1 (en) 2007-01-29 2007-01-29 IONIZING RADIATION GRAFTING PROCESS USING REACTIVE SURFACE MOLECULE, TEXTILE SUBSTRATE AND BATTERY SEPARATOR OBTAINED BY GRAFTING
PCT/FR2008/000098 WO2008110681A1 (en) 2007-01-29 2008-01-28 Ionising radiation grafting method using a reactive surfactant molecule and resulting textile substrate and battery separator

Publications (1)

Publication Number Publication Date
EP2126191A1 true EP2126191A1 (en) 2009-12-02

Family

ID=38445663

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08761809A Withdrawn EP2126191A1 (en) 2007-01-29 2008-01-28 Ionising radiation grafting method using a reactive surfactant molecule and resulting textile substrate and battery separator

Country Status (8)

Country Link
US (1) US20100058542A1 (en)
EP (1) EP2126191A1 (en)
JP (1) JP2010516916A (en)
CN (1) CN101600833A (en)
CA (1) CA2672054A1 (en)
FR (1) FR2911883B1 (en)
RU (1) RU2009124413A (en)
WO (1) WO2008110681A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101735472B (en) * 2009-12-18 2012-04-18 河南科高辐射化工科技有限公司 Porous membrane material continuous radiation grafting method and support equipment therefor
JP2013535683A (en) 2010-07-30 2013-09-12 イー・エム・デイー・ミリポア・コーポレイシヨン Chromatographic media and method
CN102102295A (en) * 2010-11-26 2011-06-22 昆明理工大学 Ion exchange nonwoven fabric with high carboxyl content and preparation method thereof
US20140155589A1 (en) * 2011-07-26 2014-06-05 Kurashiki Boseki Kabushiki Kaisha Inhibitory fiber against virulence factors production and method for producing same
US10441940B2 (en) 2012-08-20 2019-10-15 University Of Maryland, College Park Polymers grafted with organic phosphorous compounds for extracting uranium from solutions
CN103015160B (en) * 2012-12-18 2015-06-03 武汉纺织大学 Method for producing bacteriostatic sole, lining or insole by using bacteriostatic agent
JP6652554B2 (en) 2014-09-02 2020-02-26 イー・エム・デイー・ミリポア・コーポレイシヨン High surface area fiber media with nanofibrillated surface features
JP6665184B2 (en) 2014-12-08 2020-03-13 イー・エム・デイー・ミリポア・コーポレイシヨン Mixed bed ion exchange adsorbent
JP6764718B2 (en) * 2016-07-25 2020-10-07 トヨタ車体株式会社 Molding material mixture and its manufacturing method

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3794465A (en) * 1970-04-16 1974-02-26 Sun Chemical Corp Finishes for textile fabrics
JPH07229062A (en) * 1993-07-07 1995-08-29 Mitsubishi Paper Mills Ltd Moisture absorbing and desorbing sheet
US6211308B1 (en) * 1998-08-20 2001-04-03 Henkel Corporation Method for coating a textile
US6680144B2 (en) * 1999-10-29 2004-01-20 Kvg Technologies, Inc. Battery separator
JP4538164B2 (en) * 2001-03-30 2010-09-08 日本バイリーン株式会社 Ion exchange fiber sheet and method for producing the same
US6638319B2 (en) * 2001-04-04 2003-10-28 Healthtex Apparel Corp. Polymer for printed cotton
JP2003151523A (en) * 2001-06-04 2003-05-23 Komatsu Seiren Co Ltd Battery separator and its manufacturing method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008110681A1 *

Also Published As

Publication number Publication date
RU2009124413A (en) 2011-03-10
FR2911883A1 (en) 2008-08-01
JP2010516916A (en) 2010-05-20
US20100058542A1 (en) 2010-03-11
CA2672054A1 (en) 2008-09-18
FR2911883B1 (en) 2009-05-01
WO2008110681A1 (en) 2008-09-18
CN101600833A (en) 2009-12-09

Similar Documents

Publication Publication Date Title
WO2008110681A1 (en) Ionising radiation grafting method using a reactive surfactant molecule and resulting textile substrate and battery separator
EP1968792B1 (en) Functionalized substrates
CN101821325B (en) Hydrophilic porous substrates
CN103949115A (en) Method for generating denitration catalyst on filter material in situ
CN102057088B (en) Conformal coating of polymer fibers on nonwoven substrates
CN101890315B (en) Carbon nano tube-polymer composite nanofiltration membrane and preparation method thereof
Le Comte et al. Simpler and greener grafting method for improving the stability of anthraquinone-modified carbon electrode in alkaline media
CA2761076A1 (en) Interpenetrating network of anion-exchange polymers, production method thereof and use of same
JP2012503085A5 (en)
WO2003002641A1 (en) Method of modifying polymer material and use thereof
CN102905780B (en) Composite semipermeable membrane
KR101340022B1 (en) Method for coating polydopamine
CN108905651A (en) A kind of preparation method for the functional membrane that oil hydrosol separation and dyestuff removal can be achieved at the same time
CN107829302B (en) A kind of method that ultraviolet light irradiation prepares improved polyalkene non-woven membrane
KR20080066046A (en) Process for production of fuel cell separators and fuel cells
CN1986616A (en) Preparing process of antiseptic graft polymer in micron and nanometer composite structure
CN108816057A (en) A kind of poly-dopamine-ionic liquid composite membrane and preparation method thereof
CN105887464A (en) Finishing method for multifunctional self-cleaning textiles
EP2513205A1 (en) Cation exchange membrane having enhanced selectivity, method for preparing same, and uses thereof
BE546816A (en)
FR2561032A1 (en) CONDUCTIVE RESIN COMPOSITION CONTAINING IODINE
KR20230129159A (en) Composites for electrochemical gas separation
TW201000196A (en) Filtering material and its manufacturing method
KR20190079168A (en) Membrane-electrode assembly prepared from cation exchange membnrane for producing hydrogen water and method for preparing membrane-electrode assembly
JP2004183197A (en) Process for making fiber sheet

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: 20090717

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 20100224

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140423