EP0826811B1 - Absorbent nonwoven composite material with a soft surface and a rough surface, and method for its production - Google Patents

Absorbent nonwoven composite material with a soft surface and a rough surface, and method for its production Download PDF

Info

Publication number
EP0826811B1
EP0826811B1 EP19970420136 EP97420136A EP0826811B1 EP 0826811 B1 EP0826811 B1 EP 0826811B1 EP 19970420136 EP19970420136 EP 19970420136 EP 97420136 A EP97420136 A EP 97420136A EP 0826811 B1 EP0826811 B1 EP 0826811B1
Authority
EP
European Patent Office
Prior art keywords
fibres
sheet
fibers
material according
making
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.)
Expired - Lifetime
Application number
EP19970420136
Other languages
German (de)
French (fr)
Other versions
EP0826811A2 (en
EP0826811A3 (en
Inventor
Didier Bigot
Jacques Escoffier
Clément Heintz
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.)
AHLSTROM BRIGNOUD SA
Original Assignee
Ahlstrom Brignoud AA
Ahlstrom Brignoud S A
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 Ahlstrom Brignoud AA, Ahlstrom Brignoud S A filed Critical Ahlstrom Brignoud AA
Publication of EP0826811A2 publication Critical patent/EP0826811A2/en
Publication of EP0826811A3 publication Critical patent/EP0826811A3/en
Application granted granted Critical
Publication of EP0826811B1 publication Critical patent/EP0826811B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • D04H1/498—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres entanglement of layered webs
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/544—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/549—Polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/55—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H13/00—Other non-woven fabrics

Definitions

  • the thickness can be of the order of a few tenths of a millimeter when making a wiping "cloth” to reach a centimeter or even more for articles of the type "sponge", the grammage being able to vary from 30 g / m2 to 200 g / m2, or even more.
  • one of the three techniques for obtaining nonwovens is used, namely the technique so-called “dry process” which consists of making a veil of fibers mechanically or aerodynamically, using conventional textile machines such as openers, carding machines, or the so-called “wet” technique, technique derived from conventional papermaking, which consists in making a suspension of fibers which are received in the form of a sheet, or the so-called “melted” technique of producing a web of continuous filaments synthetics randomly oriented with respect to each other, directly at the outlet of the extrusion dies of said filaments.
  • dry process which consists of making a veil of fibers mechanically or aerodynamically, using conventional textile machines such as openers, carding machines, or the so-called “wet” technique, technique derived from conventional papermaking, which consists in making a suspension of fibers which are received in the form of a sheet, or the so-called “melted” technique of producing a web of continuous filaments synthetics randomly oriented with respect to each other, directly at the outlet of
  • the complex obtained being subjected to a treatment to merge the free ends of the fibers synthetics of the first layer making the latter abrasive by the formation of droplets at the place of the fusion.
  • the respective grammages of the two layers are adapted according to the applications, these grammages being able go from 15 to 200 g / m2 for the second layer and from 10 to 70 g / m2 for the first layer.
  • the invention also relates to a method for producing such a product, said method consisting in make two layers of elementary fibers, the two layers being linked together downstream of the formation zone by a needling treatment by jet of fluid acting at least against the surface of the sheet comprising the fibers hot-melt intended to constitute the "scraping" side of the complex article formed.
  • the nonwoven complex formed is then dried and receiving additional heat treatment allowing partial fusion of the ends chemical fibers from the first layer that remain linked to the basic nonwoven complex.
  • a conventional machine for obtaining of a wet nonwoven for example a machine of the Hydroformer type from the company VOITH, at the outlet of which is arranged a hydraulic binding assembly, also of known type, for example a processing machine by pressurized water jet needles of the "Jet Lace" type from ICBT-PERFOJET, this machine being adjusted so that the jets act preferentially on the face of the multilayer material constituted by the sheet which contains the hot-melt synthetic fibers, which makes it possible to redirect said fibers in the Z direction of the sheet and sort of "file” them inside it.
  • a conventional machine for obtaining of a wet nonwoven for example a machine of the Hydroformer type from the company VOITH, at the outlet of which is arranged a hydraulic binding assembly, also of known type, for example a processing machine by pressurized water jet needles of the "Jet Lace" type from ICBT-PERFOJET, this machine being adjusted so that the jets act preferentially on the face of the multi
  • the second layer by the dry route, the association being carried out at the exit of the formation of this layer by relating to its surface, on the side where the action of the jets of fluid will be exerted interlacing, the first veil made wet or dry.
  • the two overlapping layers are preferably rewetted before subjecting them to the action of the entanglement jets.
  • the nonwoven complex formed is dried and then optionally impregnated with chemical binders.
  • acrylic base possibly copolymerized
  • ethylene-vinyl-acetate polyurethane ... as well as various additives allowing to reinforce properties specific such as hydrophilicity, flexibility.
  • this machine At the outlet of this machine, there is an installation interlacing by fluid jets sold by the company ICBT-PERFOJET under the name JET-LACE, this machine comprising four rows of injectors allowing the complex to be subjected to the action of jets / needles obtained from water under pressure included between 10 bars and 125 bars.
  • the number of jets / needles per meter of width of each row can vary from 800 to 1700 and is advantageously around 1000, the diameter of each injector orifice being generally between 100 and 140 microns, but possibly reaching a value of 300 microns.
  • the two tablecloths are superimposed so that the tablecloth with polypropylene fibers are at the top and, before drying, the complex is subjected to an entangling action by water jets, the four successive series of jets being obtained from of water under increasing pressure ranging from 23 bars for the first, 27 bars for the second, 55 bars for the third and also 55 bars for the fourth.
  • the action of the water jets changes the initial position of the fibers fuses and stiff which, originally, are located perfectly in the plane of the sheet, said fibers being re-oriented along the Z axis of said sheet and their extremity rising under the effect of the knots of entanglement, or even for the longest fibers forming loops between the tangles.
  • the complex is then dried and subjected to treatment inside a tunnel brought to 400 ° C (the temperature of burner in the case where the fused fibers are of the polypropylene type).
  • This heat treatment causes a partial melting of the fibers of polypropylene visible on the surface of the tablecloth making it abrasive by the formation of droplets at the point of fusion.
  • the effective temperature inside the oven is 190 ° C, i.e. higher than the melting point of polypropylene
  • the passage speed of the sheet inside the oven is such that the fibers only melt partially, other synthetic fibers (excluding any fibers binders) entering the composition of the complex being not affected by this heat treatment, thus making it possible to preserve the flexibility of the article.
  • the speed of passage of the sheet at the interior of the furnace is of the order of 90 m / min, the said furnace having a "effective" length of six meters, the nonwoven being previously preheated to a temperature of 140 ° C.
  • a sheet weighing 40 g / m2 is obtained having a flexible and absorbent face and the other side of which has abrasive properties formed by the visible ends of the fibers polypropylene.
  • this sheet can be used either as is to receive additional treatment online with a binder, in this case a polymer emulsion acrylic / vinyl acetate deposited at a rate of 10 g / m2.
  • thermobonding fibers As indicated above.
  • Such products are particularly suitable for carrying out semi-scouring or very absorbent wiping products, but could also be used in other areas, for example in the food industry, for solvent media, bench tops laboratories ...
  • a complex material according to the invention is produced by combining on the one hand a nonwoven obtained by the wet method, and on the other hand, a nonwoven obtained by dry process.
  • the nonwoven obtained by wet process made on the same machine than the previous example, has only one jet, forming in the final product about 50% of the total mass of the fibers.
  • This first layer is added, before treatment by the set of fluid jets on a card web, constituting 50% of the total weight of fibers, card web made of polyester fibers having a title of 1.7 dtex, curly, and a 38 mm cut.
  • This card veil is preferably slightly tangled with water jets beforehand ensure its cohesion and facilitate its handling.
  • the card web is located below the web produced humid, the whole being rewetted before being subjected to the action of entanglement jets made in the same manner as in Example 1.
  • the product is, as in the previous example, subjected to a heat treatment resulting in a partial melting of polypropylene fibers, making the surface where they are present abrasive.
  • a complex product is obtained, the characteristics of which are grouped in the table below.
  • Such a product which has a flexible face formed by the fibers polyester and a rough side is particularly suitable to be used as a variety of wiping materials in a manner similar to those cited in Example 1, and which have a high flexibility innovation.
  • surfactants such as alkyl -sulfonates commonly used in dishwashing liquids, these products being either added alone, or mixed with a binder. It could also be considered to add softeners, degreasers, insecticides, bactericides, flame retardants, solvents.
  • polypropylene is particularly suitable for making the face scratching the article
  • fibers of polyethylene or possibly other fibers such as fibers polyvinyl chloride derivatives whose melting point allows perform heat treatment without deteriorating the characteristics of fibers used in the constitution of the complex.
  • the choice of polypropylene as a material particularly suitable for placing work of the invention is explained by the fact, that at the date of this demand, this is the product with the best ratio price / properties (solvent resistance, stiffness, abrasiveness, skin contact and food).
  • the ply preferably constituting the flexible layer absorbent will consist of fibers selected according to characteristics primarily sought.
  • fibers selected according to characteristics primarily sought.
  • viscose or cotton if you are considering an item with good tear resistance, preferably use fiber polyamide and, if you want to improve the touch, you will use preferably acetate or cellulose fibers (artificial silk).

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Laminated Bodies (AREA)

Description

De nos jours, de très nombreux produits à usage domestique, vestimentaire, hygiénique, médical, industriel... à base de matières fibreuses, sont réalisés à partir de structures textiles dites "nontissées".Nowadays, many products for domestic, clothing, hygienic, medical, industrial ... based on fibrous materials, are made from so-called "nonwoven" textile structures.

Parmi ces articles, outre des matériaux d'essuyage se présentant sous la forme de feuilles relativement fines, comparables à du papier, mais ayant de très grandes propriétés d'absorption, il a été proposé de réaliser de véritables substituts d'éponge dont les dimensions (longueur, largeur et surtout épaisseur), peuvent varier dans de grandes limites en fonction de l'usage envisagé. A titre indicatif, l'épaisseur peut être de l'ordre de quelques dixièmes de millimètres lorsque l'on réalise un "torchon" d'essuyage pour atteindre un centimètre voire même plus pour des articles du type "éponge", le grammage pouvant, quant à lui, varier de 30 g/m2 à 200 g/m2, voire même plus.Among these items, in addition to wiping materials in the form of relatively thin sheets, comparable to paper, but having very high absorption properties, it has been proposed to produce real sponge substitutes whose dimensions (length, width and above all thickness) can vary within wide limits depending on the intended use. As an indication, the thickness can be of the order of a few tenths of a millimeter when making a wiping "cloth" to reach a centimeter or even more for articles of the type "sponge", the grammage being able to vary from 30 g / m2 to 200 g / m2, or even more.

Pour réaliser ces articles, on utilise l'une des trois techniques d'obtention de nontissés, à savoir soit la technique dite "par voie sèche" qui consiste à réaliser un voile de fibres par voie mécanique ou aérodynamique, en utilisant des machines textiles conventionnelles telles qu'ouvreuses, cardes..., soit la technique dite "par voie humide", technique dérivée de la fabrication conventionnelle du papier, qui consiste à réaliser une suspension de fibres que l'on réceptionne sous forme d'une feuille, soit la technique dite "par voie fondue" consistant à réaliser une nappe de filaments continus synthétiques orientés au hasard les uns par rapport aux autres, et ce directement à la sortie des filières d'extrusion desdits filaments.To make these items, one of the three techniques for obtaining nonwovens is used, namely the technique so-called "dry process" which consists of making a veil of fibers mechanically or aerodynamically, using conventional textile machines such as openers, carding machines, or the so-called "wet" technique, technique derived from conventional papermaking, which consists in making a suspension of fibers which are received in the form of a sheet, or the so-called "melted" technique of producing a web of continuous filaments synthetics randomly oriented with respect to each other, directly at the outlet of the extrusion dies of said filaments.

Il a été proposé depuis fort longtemps d'utiliser ces technologies pour réaliser des articles multicouches, de manière à avoir des propriétés différentes sur les deux côtés de la feuille formée, par exemple une face imprimable ou imperméable et l'autre face fibreuse, ou une face imperméable et une autre face ayant un grand pouvoir d'absorption.It has been proposed for a long time to use these technologies to produce multilayer articles, so to have different properties on the two sides of the formed sheet, for example a printable or waterproof face and the other fibrous face, or an impermeable face and another face having a great absorption power.

La présente invention a trait à un nouveau type de complexe non tissé absorbant constitué d'au moins deux nappes fibreuses superposées, liées entre elles par interpénétration des fibres dans le sens de l'épaisseur caracterisé en ce que :

  • la première nappe est constituée pour tout ou partie de fibres synthétiques thermofusibles sélectionnées de préférence dans la classe des polyoléfines ; avantageusement, cette nappe est constituée d'un mélange de fibres cellulosiques ou autres et de fibres synthétiques thermofusibles, le pourcentage de ces dernières dans la nappe étant supérieur à 30 % et de préférence supérieur à 50 % ;
  • la seconde nappe est, quant à elle, constituée de fibres naturelles et/ou artificielles et/ou synthétiques ayant une température de fusion plus élevée que ces dernières ;
  • l'association des nappes élémentaires est réalisée en les soumettant à un traitement permettant de ré-orienter les fibres synthétiques de la première nappe pour que, d'une part, elles soient intimement liées dans la structure de la seconde nappe et, d'autre part, présentent des extrémités libres ou bouclettes apparentes sur l'une des faces extérieures du complexe formé.
The present invention relates to a new type of absorbent nonwoven complex consisting of at least two superposed fibrous sheets, linked together by interpenetration of the fibers in the direction of the thickness, characterized in that:
  • the first layer consists of all or part of synthetic hot-melt fibers preferably selected from the class of polyolefins; advantageously, this sheet consists of a mixture of cellulosic or other fibers and of hot-melt synthetic fibers, the percentage of the latter in the sheet being greater than 30% and preferably greater than 50%;
  • the second layer, for its part, consists of natural and / or artificial and / or synthetic fibers having a higher melting temperature than the latter;
  • the association of the elementary plies is carried out by subjecting them to a treatment making it possible to re-orient the synthetic fibers of the first ply so that, on the one hand, they are intimately linked in the structure of the second ply and, on the other hand, have free ends or visible loops on one of the outer faces of the complex formed.

Les documents EP-A-0333211 et EP-A-0577156, dont le contenu est identique décrivent un procédé de fabrication d'un matériau non tissé résultant de l'entrelacement des fibres synthétiques d'une première couche, avec des fibres d'une seconde couche. Selon ces documents, le complexe obtenu peut être soumis à un traitement de liaison thermique permettant d'augmenter la dureté ou la résistance des matériaux pour liaison des fibres synthétiques entre elles sans pour autant que leur structure soit détériorée.Documents EP-A-0333211 and EP-A-0577156, whose content is identical describe a method of manufacture of a nonwoven material resulting from the intertwining of synthetic fibers from a first layer, with fibers of a second layer. According to these documents, the complex obtained can be subjected to a thermal bonding treatment to increase the hardness or resistance of materials for bonding synthetic fibers between them without their structure being deteriorated.

Le complex obtenu étant soumis à un traitement permettant de fusioner les extrémités libres des fibres synthétiques de la première nappe rendant cette dernière abrasive par la formation de goutelettes a l'endroit de la fusion.The complex obtained being subjected to a treatment to merge the free ends of the fibers synthetics of the first layer making the latter abrasive by the formation of droplets at the place of the fusion.

La manière dont sont associées les nappes élémentaires sera fonction de la nature desdites nappes.The way in which the elementary layers are associated will depend on the nature of said layers.

A titre indicatif mais non limitatif, cette association pourra, par exemple, être réalisée de la manière suivante :

  • par exemple dans le cas où les deux nappes élémentaires sont obtenues selon la technique dite par voie humide ou papetière, leur réalisation sera faite sur une machine permettant d'obtenir et de superposer deux jets correspondant chacun à l'une des nappes ; dans ce cas, la superposition se fera en ligne, avant même séchage, et on procédera au complexage par l'action de jets d'eau sous pression ;
  • dans le cas où les deux nappes élémentaires sont obtenues selon la technique dite par sèche, dite aussi textile, elles seront également superposées et leur liaison sera obtenue par un traitement d'enchevêtrement par jets d'eau ;
  • enfin, dans le cas où l'on réalise un complexe à partir de deux nappes obtenues par des techniques différentes, il sera possible de prélier légèrement l'une ou l'autre des nappes par un enchevêtrement obtenu au moyen de jets d'eau en évitant des liaisons bloquantes de type chimique ou thermique ; les deux nappes sont ensuite superposées et liées par enchevêtrement par jets d'eau.
As an indication but not limiting, this association could, for example, be carried out as follows:
  • for example in the case where the two elementary layers are obtained according to the so-called wet or paper technique, their production will be done on a machine making it possible to obtain and superimpose two jets each corresponding to one of the layers; in this case, the superposition will be done in line, before even drying, and the complexing will be carried out by the action of jets of water under pressure;
  • in the case where the two elementary layers are obtained according to the so-called dry technique, also called textile, they will also be superimposed and their connection will be obtained by a tangle treatment by water jets;
  • finally, in the case where a complex is produced from two layers obtained by different techniques, it will be possible to slightly prelude one or the other of the layers by a tangle obtained by means of water jets in avoiding blocking bonds of chemical or thermal type; the two layers are then superimposed and linked by entanglement by water jets.

Avantageusement et en pratique, conformément à l'invention :

  • les fibres synthétiques entrant dans la composition de la première nappe, sont de préférence des fibres de polypropylène ou de polyéthylène :
    • dont le titre est supérieur 5 dtex, la limite haute étant directement en relation avec la pression du fluide d'enchevêtrement da manière à assurer la solidarité des fibres avec le reste de la nappe ; la limite supérieure des fibres sera fonction des disponibilités commerciales qui, à ce jour, proposent des fibres ayant un titre de 17 dtex;
    • dont la longueur est supérieure à 5 mm, la limite supérieure dépendant essentiellement de la technique de fabrication ; ainsi, un titre plus fin entraíne l'utilisation de fibres plus courtes et, la technique par voie humide nécessite une coupe plus courte que la technique par voie sèche ;
    • dont la surface est la moins ronde possible ; ainsi, on utilisera de préférence des fibres multilobées, fibrillables ou à section aplatie, qui sont beaucoup plus réceptives à l'action des jets du fluide d'enchevêtrement;
  • s'il est préférable d'utiliser des fibres de polyoléfines ayant comme caractéristique d'avoir une densité inférieure à 1, il peut cependant être envisagé d'utiliser d'autres types de fibres, par exemple des fibres constituées d'un copolymère de chlorure de vinyle (85 %) et d'acétate de vinyle (15 %) dont la température de fusion est de l'ordre de 160 °C avec une densité de 1,37 g/cm3 ;
  • comme fibres naturelles et/ou artificielles, on peut utiliser tout type de fibres permettant d'obtenir un caractère absorbant, tel que pâte de bois, coton, linters, viscose ; dans le cas d'une fibre chimique telle que la viscose, elle sera éventuellement de section multilobée ou fibrillable de manière à optimiser l'action des jets de fluide;
  • si l'on introduit des fibres synthétiques de structure dans la seconde nappe, celles-ci auront un point de fusion supérieur à celles entrant dans la composition de la première nappe ; on utilisera par exemple des fibres de polyester ou de polyamide 6.6 (de préférence à des polyamides 6), éventuellement frisées;
  • il est possible d'ajouter éventuellement dans l'une ou l'autre des nappes un certain pourcentage de fibres dites liantes, par exemple fibres bi-componantes, dont tout ou partie de la fibre flue sur les fibres voisines lors d'un traitement thermique permettant de réaliser un "collage" rendant les fibres solidaires ; dans un tel cas, le point de fusion de la partie liante de ces fibres liantes sera inférieur au point de fusion des fibres de structure précédemment citée, mais il peut cependant être inférieur ou supérieur à celui des fibres de la première nappe destinées à apporter l'effet "grattant";
  • après superposition des deux nappes, le complexe résultant reçoit un traitement thermique destiné, d'une part, à révéler la pouvoir liant des fibres liantes qui ont été éventuellement introduites, et d'autre part et surtout, à fusionner les extrémités libres des fibres synthétiques de la première nappe de manière à amplifier l'effet "grattant";
  • avant ou après traitement thermique, il est éventuellement possible de réaliser des traitements additionnels mécaniques, tels que par exemple crêpage ou utilisation d'un appareil de type Micrex destiné à assouplir le produit ou chimiques, tels que :
    • additions d'émulsions polymères de type latex destinées à renforcer mécaniquement le produit,
    • addition d'assouplissants chimiques,
    • additions d'agents hydrophiles,
    • imprégnation de liquides dégraissants (type liquide vaisselle), protecteurs pour la peau, détachants...
Advantageously and in practice, in accordance with the invention:
  • the synthetic fibers used in the composition of the first layer, are preferably polypropylene or polyethylene fibers:
    • whose titer is greater than 5 dtex, the upper limit being directly related to the pressure of the entangling fluid so as to ensure the solidarity of the fibers with the rest of the sheet; the upper limit of the fibers will depend on the commercial availabilities which, to date, offer fibers having a titer of 17 dtex;
    • the length of which is greater than 5 mm, the upper limit essentially depending on the manufacturing technique; thus, a finer title leads to the use of shorter fibers and, the wet technique requires a shorter cut than the dry technique;
    • whose surface is as round as possible; thus, use will preferably be made of multilobed, fibrillable or flattened section fibers, which are much more receptive to the action of the jets of the entangling fluid;
  • if it is preferable to use polyolefin fibers having the characteristic of having a density of less than 1, it may however be envisaged to use other types of fibers, for example fibers made of a chloride copolymer vinyl (85%) and vinyl acetate (15%) whose melting temperature is around 160 ° C with a density of 1.37 g / cm3;
  • as natural and / or artificial fibers, it is possible to use any type of fiber making it possible to obtain an absorbent character, such as wood pulp, cotton, linters, viscose; in the case of a chemical fiber such as viscose, it will possibly be of multi-lobed or fibrillable section so as to optimize the action of the fluid jets;
  • if synthetic fibers of structure are introduced into the second layer, these will have a higher melting point than those used in the composition of the first layer; polyester or polyamide 6.6 fibers (preferably polyamides 6) will be used, for example, crimped;
  • it is possible to optionally add to one or the other of the sheets a certain percentage of so-called binder fibers, for example two-component fibers, all or part of the fiber flowing over neighboring fibers during a heat treatment making it possible to "bond" the fibers together; in such a case, the melting point of the binder part of these binder fibers will be lower than the melting point of the fibers of the above-mentioned structure, but it may however be lower or higher than that of the fibers of the first ply intended to provide the 'scratching effect;
  • after superposition of the two layers, the resulting complex receives a heat treatment intended, on the one hand, to reveal the binding power of the binding fibers which have been optionally introduced, and on the other hand and above all, to merge the free ends of the synthetic fibers of the first layer so as to amplify the "scratching"effect;
  • before or after heat treatment, it is possibly possible to carry out additional mechanical treatments, such as, for example, creping or use of a device of the Micrex type intended to soften the product or chemicals, such as:
    • additions of latex-type polymer emulsions intended to mechanically reinforce the product,
    • addition of chemical softeners,
    • additions of hydrophilic agents,
    • impregnation of degreasing liquids (type dishwashing liquid), skin protectants, stain removers ...

Les grammages respectifs des deux couches sont adaptés en fonction des applications, ces grammages pouvant aller de 15 à 200 g/m2 pour la seconde nappe et de 10 à 70 g/m2 pour la première nappe.The respective grammages of the two layers are adapted according to the applications, these grammages being able go from 15 to 200 g / m2 for the second layer and from 10 to 70 g / m2 for the first layer.

L'invention concerne également un procédé permettant la réalisation d'un tel produit, ledit procédé consistant à réaliser deux couches de fibres élémentaires, les deux couches étant liées entre elles en aval de la zone de formation par un traitement d'aiguilletage par jet de fluide agissant au moins contre la surface de la nappe comportant les fibres thermofusibles destinées à constituer la face "grattante" de l'article complexe formé.The invention also relates to a method for producing such a product, said method consisting in make two layers of elementary fibers, the two layers being linked together downstream of the formation zone by a needling treatment by jet of fluid acting at least against the surface of the sheet comprising the fibers hot-melt intended to constitute the "scraping" side of the complex article formed.

Le complexe non tissé formé étant ensuite séché et recevant un traitement thermique complémentaire permettant la fusion partielle des extrémités des fibres chimiques de la première couche qui restent liées au complexe non tissé de base.The nonwoven complex formed is then dried and receiving additional heat treatment allowing partial fusion of the ends chemical fibers from the first layer that remain linked to the basic nonwoven complex.

Pour la mise en oeuvre d'un tel procédé, on peut utiliser par exemple une machine conventionnelle pour l'obtention d'un non tissé par voie humide, par exemple une machine du type Hydroformer de la Société VOITH, à la sortie de laquelle est disposé un ensemble de liage hydraulique, également de type connu, par exemple une machine de traitement par jets-aiguilles d'eau sous pression du type "Jet Lace" de la Société ICBT-PERFOJET, cette machine étant réglée pour que les jets agissent préférentiellement sur la face du matériau multicouches constituée par la nappe qui comporte les fibres synthétiques thermofusibles, ce qui permet de réorienter lesdites fibres dans le sens Z de la feuille et en quelque sorte de les "ficher" à l'intérieur de cette dernière.For the implementation of such a process, one can use for example a conventional machine for obtaining of a wet nonwoven, for example a machine of the Hydroformer type from the company VOITH, at the outlet of which is arranged a hydraulic binding assembly, also of known type, for example a processing machine by pressurized water jet needles of the "Jet Lace" type from ICBT-PERFOJET, this machine being adjusted so that the jets act preferentially on the face of the multilayer material constituted by the sheet which contains the hot-melt synthetic fibers, which makes it possible to redirect said fibers in the Z direction of the sheet and sort of "file" them inside it.

Lorsque les deux couches élémentaires sont réalisées par voie humide, leur association est obtenue sur la toile d'égouttage avant traitement par jets de fluide.When the two elementary layers are made wet, their association is obtained on the canvas drainage before treatment with fluid jets.

Il peut également être envisagé de réaliser la seconde couche par voie sèche, l'association étant réalisée à la sortie de la formation de cette couche en rapportant à sa surface, du côté où va s'exercer l'action des jets de fluide d'entrelaçage, le premier voile réalisé par voie humide ou par voie sèche. Dans un tel cas, les deux couches superposées sont de préférence réhumidifiées avant de les soumettre à l'action des jets d'enchevêtrement.It is also possible to envisage making the second layer by the dry route, the association being carried out at the exit of the formation of this layer by relating to its surface, on the side where the action of the jets of fluid will be exerted interlacing, the first veil made wet or dry. In such a case, the two overlapping layers are preferably rewetted before subjecting them to the action of the entanglement jets.

Après réalisation, le complexe non tissé formé est séché puis éventuellement imprégné de liants chimiques de base acrylique (éventuellement copolymérisé), éthylène-vinyle-acétate, polyuréthane.... ainsi que divers adjuvants permettant de renforcer des propriétés spécifiques telles que l'hydrophilie, la souplesse.After production, the nonwoven complex formed is dried and then optionally impregnated with chemical binders. acrylic base (possibly copolymerized), ethylene-vinyl-acetate, polyurethane ... as well as various additives allowing to reinforce properties specific such as hydrophilicity, flexibility.

Après séchage, on réalise, de préférence sur la même machine, un traitement thermique permettant de provoquer la fusion partielle des extrémités des fibres chimiques de la couche supérieure qui restent liées au complexe nontissé de base, les extrémités fondues augmentant et magnifiant l'effet de rugosité. After drying, preferably, on the same machine, a heat treatment to cause partial melting of ends of chemical fibers in the upper layer which remain bonded to the basic nonwoven complex, the molten ends increasing and magnifying the effect of roughness.

L'invention et les avantages qu'elle apporte seront cependant mieux compris grâce aux exemples de réalisation donnés ci-après à titre indicatif mais non limitatif.The invention and the advantages which it brings will however be better understood thanks to the example embodiments given below for information but not limiting.

Ces exemples sont réalisés sur une machine papetière conventionnelle du type Hydroformer VOÏTH, adaptée pour comporter deux arrivées de suspension distinctes et permettant donc de produire une feuille multicouches.These examples are made on a paper machine conventional VOof hydroformer type, adapted to include two separate suspension arrivals and therefore allowing production a multi-layer sheet.

A la sortie de cette machine, est disposée une installation d'entrelaçage par jets de fluide commercialisée par la Société ICBT-PERFOJET sous la dénomination JET-LACE, cette machine comportant quatre rangées d'injecteurs permettant de soumettre le complexe à l'action de jets/aiguilles obtenus à partir d'eau sous pression comprise entre 10 bars et 125 bars. Le nombre de jets/aiguilles par mètre de largeur de chaque rangée peut varier de 800 à 1700 et est avantageusement de l'ordre de 1000, le diamètre de chaque orifice d'injecteur étant en général compris entre 100 et 140 microns, mais pouvant éventuellement atteindre une valeur de 300 microns.At the outlet of this machine, there is an installation interlacing by fluid jets sold by the company ICBT-PERFOJET under the name JET-LACE, this machine comprising four rows of injectors allowing the complex to be subjected to the action of jets / needles obtained from water under pressure included between 10 bars and 125 bars. The number of jets / needles per meter of width of each row can vary from 800 to 1700 and is advantageously around 1000, the diameter of each injector orifice being generally between 100 and 140 microns, but possibly reaching a value of 300 microns.

Exemple 1Example 1

Sur une machine papetière du type précité, on réalise un complexe non tissé conforme à l'invention à partir de deux suspensions fibreuses ayant les compositions suivantes :

  • pour la couche supérieure qui sera ultérieurement soumise à l'action préférentielle des jets d'aiguilletage, et qui constitue globalement 23 % de la masse fibreuse totale du complexe après formation, une suspension d'un mélange comportant :
    • 50 % de fibres de polypropylène (titre 6,7 dtex, coupe 6 mm, section ronde) ; ces fibres sont teintées dans la masse, ce qui permet, dans le produit final, de pouvoir identifier visuellement les différentes couches du produit fini.
    • 50 % de fibres cellulosiques constituées de fibres papetières longues obtenues à partir de pin sylvestre.
  • pour la couche inférieure formant la seconde nappe souple et avantageusement absorbante, et qui constitue globalement 77 % de la masse totale fibreuse dans le complexe final, une suspension comprenant :
    • 67 % de fibres cellulosiques longues obtenues à partir de pin sylvestre,
    • 33 % de fibres de polyester titre 1,7 dtex - coupe 18 mm - section ronde.
On a paper machine of the aforementioned type, a nonwoven complex is produced in accordance with the invention from two fibrous suspensions having the following compositions:
  • for the upper layer which will subsequently be subjected to the preferential action of the needling jets, and which overall constitutes 23% of the total fibrous mass of the complex after formation, a suspension of a mixture comprising:
    • 50% polypropylene fibers (6.7 dtex, 6 mm cut, round section); these fibers are dyed in the mass, which allows, in the final product, to be able to visually identify the different layers of the finished product.
    • 50% of cellulose fibers made up of long paper fibers obtained from Scots pine.
  • for the lower layer forming the second flexible and advantageously absorbent sheet, and which globally constitutes 77% of the total fibrous mass in the final complex, a suspension comprising:
    • 67% of long cellulosic fibers obtained from Scots pine,
    • 33% polyester fibers, title 1.7 dtex - cut 18 mm - round section.

Les deux nappes sont superposées de telle sorte que la nappe comportant les fibres de polypropylène se trouvent à la partie supérieure et, avant séchage, le complexe est soumis à une action d'enchevêtrement par jets d'eau, les quatre séries successives de jets étant obtenues à partir d'eau sous pression croissante allant de 23 bars pour la première, 27 bars pour la seconde, 55 bars pour la troisième et également 55 bars pour la quatrième.The two tablecloths are superimposed so that the tablecloth with polypropylene fibers are at the top and, before drying, the complex is subjected to an entangling action by water jets, the four successive series of jets being obtained from of water under increasing pressure ranging from 23 bars for the first, 27 bars for the second, 55 bars for the third and also 55 bars for the fourth.

L'action des jets d'eau modifie la position initiale des fibres fusibles et raides qui, à l'origine, sont situées parfaitement dans le plan de la feuille, lesdites fibres étant ré-orientées selon l'axe Z de ladite feuille et leur extrémité se relevant sous l'effet des noeuds d'enchevêtrement, voire même pour les fibres les plus longues formant des bouclettes entre les noeuds d'enchevêtrement.The action of the water jets changes the initial position of the fibers fuses and stiff which, originally, are located perfectly in the plane of the sheet, said fibers being re-oriented along the Z axis of said sheet and their extremity rising under the effect of the knots of entanglement, or even for the longest fibers forming loops between the tangles.

Le complexe est ensuite séché et est soumis à un traitement thermique à l'intérieur d'un tunnel porté à 400°C (la température de brûleur dans le cas où les fibres fusionnées sont de type polypropylène). Ce traitement thermique entraíne une fusion partielle des fibres de polypropylène apparentes sur la surface de la nappe rendant cette dernière abrasive par formation de gouttelettes à l'endroit de la fusion. Bien que la température efficace à l'intérieur du four soit de 190°C, c'est-à-dire supérieure au point de fusion du polypropylène, la vitesse de passage de la nappe à l'intérieur du four est telle que les fibres ne fondent que partiellement, les autres fibres synthétiques (hors les éventuelles fibres liantes) entrant dans la composition du complexe n'étant quant à elles pas affectées par ce traitement thermique, permettant donc de conserver la souplesse de l'article. A titre indicatif, la vitesse de passage de la nappe à l'intérieur du four est de l'ordre de 90 m/min, le dit four ayant une longueur "efficace" de six mètres, le nontissé étant préalablement préchauffé à une température de 140°C.The complex is then dried and subjected to treatment inside a tunnel brought to 400 ° C (the temperature of burner in the case where the fused fibers are of the polypropylene type). This heat treatment causes a partial melting of the fibers of polypropylene visible on the surface of the tablecloth making it abrasive by the formation of droplets at the point of fusion. Although the effective temperature inside the oven is 190 ° C, i.e. higher than the melting point of polypropylene, the passage speed of the sheet inside the oven is such that the fibers only melt partially, other synthetic fibers (excluding any fibers binders) entering the composition of the complex being not affected by this heat treatment, thus making it possible to preserve the flexibility of the article. As an indication, the speed of passage of the sheet at the interior of the furnace is of the order of 90 m / min, the said furnace having a "effective" length of six meters, the nonwoven being previously preheated to a temperature of 140 ° C.

Bien entendu, ces valeurs concernant la température et la vitesse ne sont pas limitatives étant donné qu'une vitesse supérieure peut être compensée par une longueur utile du four plus longue, ou une température plus élevée et qu'un autre type de fibres nécessitera une adaptation des températures sélectionnées.Of course, these values for temperature and speed are not limiting since higher speed may be compensated by a longer useful oven length, or a higher temperature and that another type of fiber will require a adaptation of the selected temperatures.

En sortie de machine, on obtient une feuille pesant 40 g/m2 comportant une face souple et absorbante et dont l'autre face présente des propriétés abrasives constituées par les extrémités apparentes des fibres de polypropylène.Leaving the machine, a sheet weighing 40 g / m2 is obtained having a flexible and absorbent face and the other side of which has abrasive properties formed by the visible ends of the fibers polypropylene.

Il convient de noter que le choix des fibres de polyoléfines pour constituer la face apparente grattante de l'article, facilite l'obtention de cette dernière car lors de la mise en suspension pour former la nappe, les dites fibres ayant une densité inférieure à 1 restent en surface lors de la conformation par voie humide.It should be noted that the choice of polyolefin fibers for constitute the scratching visible face of the article, facilitates obtaining the latter because during the suspension to form the sheet, the said fibers having a density less than 1 remain on the surface during the wet conformation.

En fonction des applications souhaitées, cette feuille peut être utilisée soit telle que soit recevoir un traitement complémentaire en ligne avec un liant, dans le cas présent une émulsion de polymère acrylique/acétate de vinyle déposée à raison de 10 g/m2. Depending on the desired applications, this sheet can be used either as is to receive additional treatment online with a binder, in this case a polymer emulsion acrylic / vinyl acetate deposited at a rate of 10 g / m2.

Les caractéristiques et propriétés des nappes obtenues sont regroupées dans le tableau ci-dessous. SANS IMPREGNATION AVEC IMPREGNATION Grammage (g/m2) 40,3 50,7 Epaisseur (microns sous 100 kPa) 268 261 Perméabilité(L/m2/S sous 196 Pa) 1335 1103 Rupture sens long (N/M) 470 1439 Rupture travers (N/M) 170 470 Allongement sens long (%) 2,5 12,3 Allongement travers (%) 5,5 30,0 Rupture humide sens (N/M) 109 952 Rupture humide travers (N/M) 48 286 Déchirure sens long (cN) 118 525 Déchirure travers (cN) 198 1152 Rigidité sens long (cN Handle O meter) 45 80 Rigidité travers (cN Handle O meter) 17 27 Capacité d'absosrption (%) 693 477 The characteristics and properties of the layers obtained are grouped in the table below. WITHOUT IMPREGNATION WITH IMPREGNATION Weight (g / m2) 40.3 50.7 Thickness (microns under 100 kPa) 268 261 Permeability (L / m2 / S under 196 Pa) 1335 1103 Long-term break (N / M) 470 1439 Break through (N / M) 170 470 Elongation long direction (%) 2.5 12.3 Elongation through (%) 5.5 30.0 Wet break sense (N / M) 109 952 Wet break through (N / M) 48 286 Long direction tear (cN) 118 525 Cross tear (cN) 198 1152 Long sense stiffness (cN Handle O meter) 45 80 Cross stiffness (cN Handle O meter) 17 27 Absorption capacity (%) 693 477

Les mesures des caractéristiques des produits sont effectuées dans les conditions suivantes.

  • Grammage : suivant méthode EDANA 40.3-90
  • Epaisseur : suivant méthode AFNOR NF Q 03+016
  • Perméabilité : suivant méthode EDANA 140.1-81
  • Rupture : suivant méthode EDANA 20.2 - 89 modifiée
       distance entre machoirs : 127 mm
       vitesse de traction : 25,4 mm/min
  • Allongement: suivant méthode EDANA 20.2 - 89 modifiée
       distance entre machoirs : 127 mm    vitesse de traction : 25,4 mm/min détection à 75 % de la rupture maximum
  • Rupture humide : suivant même méthode que rupture sèche mais parés séjour des bandes tests 10 min sous 20 mm d'eau distillée à 20°C
  • Déchirure : suivant méthode EDANA 70.3 - 96
  • Rigidité : avec appareillage "HANDLE-0-Meter"
  • Capacité d'absorption : suivant méthode EDANA 10.2 - 96.
    • Measurements of product characteristics are carried out under the following conditions.
  • Weight: according to EDANA 40.3-90 method
  • Thickness: according to AFNOR NF Q 03 + 016 method
  • Permeability: according to EDANA 140.1-81 method
  • Break: according to EDANA 20.2 - 89 method modified
    distance between mills: 127 mm
    pulling speed: 25.4 mm / min
  • Elongation: according to modified EDANA 20.2 - 89 method
    distance between mills: 127 mm pulling speed: 25.4 mm / min detection at 75% of maximum rupture
  • Wet break: following the same method as dry break but trimmed test strips stay 10 min under 20 mm of distilled water at 20 ° C
  • Tear: according to EDANA 70.3 - 96 method
  • Rigidity: with "HANDLE-0-Meter" equipment
  • Absorption capacity: according to EDANA method 10.2 - 96.

    • Il ressort des exemples qui précédent que le produit non imprégné présente une plus grande capacité d'absorption, est beaucoup plus souple, et a en revanche des caractéristiques mécaniques relativement basses qui, le cas échéant, pourraient être compensées par l'introduction d'un certain pourcentage de fibres thermoliantes, comme indiqué précédemment.It appears from the examples above that the non-impregnated product has a greater absorption capacity, is much more flexible, and on the other hand has relatively low mechanical characteristics which, where appropriate, could be offset by the introduction of a certain percentage of thermobonding fibers, as indicated above.

    De tels produits sont particulièrement adaptés pour réaliser des produits d'essuyage semi-décapants ou très absorbants, mais pourraient également être utilisés dans d'autres domaines, par exemple dans le domaine agro-alimentaire, pour les milieux solvants, les paillasses de laboratoires.. .Such products are particularly suitable for carrying out semi-scouring or very absorbent wiping products, but could also be used in other areas, for example in the food industry, for solvent media, bench tops laboratories ...

    Le même produit imprégné au moyen d'un liant polymère est, quant à lui, particulièrement adapté pour réaliser :

    • des essuyages imprégnés de liquide vaisselle pour vaisselle à usage unique (camping..),
    • des essuie-mains imprégnés d'agents dégraissants et adoucissants pour travailleurs manuels (garages..),
    • des essuie-vitres imprégnés d'un liquide adequat pour les véhicules (insectes écrasés, déjections d'oiseaux), le domestique .. ,
    • des essuyages pour bricoleurs (nettoyage de balustrades, dépoussiérage en extérieur..).
    The same product impregnated with a polymeric binder is, in turn, particularly suitable for producing:
    • wipes impregnated with dishwashing liquid for disposable dishes (camping, etc.)
    • hand towels impregnated with degreasing and softening agents for manual workers (garages, etc.),
    • windshield wipers impregnated with a liquid suitable for vehicles (crushed insects, bird droppings), domestic ...,
    • wiping for DIY enthusiasts (cleaning of railings, dusting outdoors ...).

    Exemple 2Example 2

    On réalise un matériau complexe conforme à l'invention en combinant d'une part un nontissé obtenu par voie humide, et d'autre part, un nontissé obtenu par voie sèche.A complex material according to the invention is produced by combining on the one hand a nonwoven obtained by the wet method, and on the other hand, a nonwoven obtained by dry process.

    Le nontissé obtenu par voie humide, réalisé sur la même machine que l'exemple précédent, ne comporte qu'un seul jet, formant dans le produit final environ 50 % de la masse totale des fibres.The nonwoven obtained by wet process, made on the same machine than the previous example, has only one jet, forming in the final product about 50% of the total mass of the fibers.

    Cette nappe est obtenue à partir d'une suspension fibreuse comportant :

    • 33 % de fibres polypropylène, de titre 6,7 dtex, coupe 6 mm, section ronde ;
    • 67 % de cellulose (pâte de bois) en fibres longues (résineux).
    This sheet is obtained from a fibrous suspension comprising:
    • 33% polypropylene fiber, 6.7 dtex, 6 mm cut, round section;
    • 67% cellulose (wood pulp) in long fibers (resinous).

    Cette première nappe est rapportée, avant traitement par l'ensemble de jets de fluide sur un voile de carde, constituant 50 % du poids total de fibres, voile de carde constitué de fibres polyester ayant un titre de 1,7 dtex, frisées, et une coupe 38 mm. Ce voile de carde est de préférence préalablement légèrement enchevêtré par jets d'eau pour assurer sa cohésion et faciliter sa manipulation.This first layer is added, before treatment by the set of fluid jets on a card web, constituting 50% of the total weight of fibers, card web made of polyester fibers having a title of 1.7 dtex, curly, and a 38 mm cut. This card veil is preferably slightly tangled with water jets beforehand ensure its cohesion and facilitate its handling.

    Le voile de carde est situé en dessous du voile réalisé par voie humide, l'ensemble étant réhumidifié avant d'être soumis à l'action des jets d'enchevêtrement réalisés de la même manière que dans l'exemple 1.The card web is located below the web produced humid, the whole being rewetted before being subjected to the action of entanglement jets made in the same manner as in Example 1.

    Après réalisation du complexe, le produit est, comme dans l'exemple précédent, soumis à un traitement thermique entraínant une fusion partielle des fibres de polypropylène, rendant la surface où elles sont présentes abrasive. After completion of the complex, the product is, as in the previous example, subjected to a heat treatment resulting in a partial melting of polypropylene fibers, making the surface where they are present abrasive.

    On obtient un produit complexe dont les caractéristiques sont regroupées dans le tableau ci-dessous. Grammage 68,4 g/m2 Epaisseur 255 microns sous 100 kPa Perméabilité 1160 L/m2/S sous 196 Pa Rupture sens long 1920 N/M Rupture travers 690 N/M Allongement sens long 29 % Allongement travers 30 % Rupture humide sens long 1600 N/M Rupture humide travers 550 N/M Déchirure sens long 1330 cN Déchirure travers 2810 cN Rigidité sens long 31 cN (Handle-O-Meter) Rigidité travers 5 cN ("   "   " ) Capacité d'absorption 402 % A complex product is obtained, the characteristics of which are grouped in the table below. weight 68.4 g / m2 Thickness 255 microns at 100 kPa Permeability 1160 L / m2 / S at 196 Pa Long break 1920 N / M Break through 690 N / M Long direction elongation 29% Elongation through 30 % Long-term wet break 1600 N / M Wet break through 550 N / M Long tear 1330 cN Tear through 2810 cN Long stiffness 31 cN (Handle-O-Meter) Cross stiffness 5 cN (""") Absorption capacity 402%

    Un tel produit qui comporte une face souple constituée par les fibres de polyester et une face rugueuse, est particulièrement adapté pour être utilisé comme matériaux d'essuyages divers d'une manière similaire à ceux cités dans l'exemple 1, et qui présentent une souplesse fortement amélioriée.Such a product which has a flexible face formed by the fibers polyester and a rough side, is particularly suitable to be used as a variety of wiping materials in a manner similar to those cited in Example 1, and which have a high flexibility amélioriée.

    Bien entendu, l'invention n'est pas limitée aux exemples de réalisation décrits précédemment, mais elle en couvre toutes les variantes réalisées dans le même esprit. Of course, the invention is not limited to the examples of realization described above, but it covers all variants carried out in the same spirit.

    Ainsi, il est possible de traiter le produit pour y incorporer des additifs divers, par exemple des produits tensio-actifs, tels que les alkyl -sulfonates couramment utilisés dans les liquides de vaisselle, ces produits étant soit additionnés seuls, soit en mélange avec un liant. Il pourrait être également envisagé d'ajouter des produits assouplissants, dégraissants, insecticides, bactéricides, ignifugeants, solvants.Thus, it is possible to process the product to incorporate various additives, for example surfactants, such as alkyl -sulfonates commonly used in dishwashing liquids, these products being either added alone, or mixed with a binder. It could also be considered to add softeners, degreasers, insecticides, bactericides, flame retardants, solvents.

    Si le polypropylène est particulièrement adapté pour réaliser la face grattante de l'article, on peut également utiliser des fibres de polyéthylène, voire éventuellement d'autres fibres telles que les fibres dérivées de chlorure de polyvinyle dont le point de fusion permet de réaliser un traitement thermique sans détériorer les caractéristiques des fibres entrant dans la constitution du complexe. Le choix du polypropylène comme matériau particulièrement adapté pour la mise en oeuvre de l'invention, s'explique par le fait, qu'à la date de la présente demande, il s'agit du produit qui présente le meilleur rapport prix/propriétés (résistance aux solvants, rigidité, abrasivité, contact cutané et alimentaire).If polypropylene is particularly suitable for making the face scratching the article, one can also use fibers of polyethylene, or possibly other fibers such as fibers polyvinyl chloride derivatives whose melting point allows perform heat treatment without deteriorating the characteristics of fibers used in the constitution of the complex. The choice of polypropylene as a material particularly suitable for placing work of the invention, is explained by the fact, that at the date of this demand, this is the product with the best ratio price / properties (solvent resistance, stiffness, abrasiveness, skin contact and food).

    Par ailleurs, il pourrait éventuellement envisagé de réaliser des produits de grammage beaucoup plus élevés que ceux indiqués dans la description qui précède.Furthermore, it could possibly consider carrying out grammage products much higher than those indicated in the description above.

    Enfin, la nappe constituant la couche souple de préférence absorbante, sera constituée de fibres sélectionnées en fonction des caractéristiques prioritairement recherchées. A titre indicatif, lorsque l'on souhaite avoir une face souple et fortement absorbante, on utilisera de préférence de la viscose ou du coton, si on envisage un article présentant une bonne résistance à la déchirure, on utilisera de préférence la fibre polyamide et, si l'on souhaite améliorer le toucher, on utilisera de préférence des fibres d'acétate ou de cellulose (soie artificielle).Finally, the ply preferably constituting the flexible layer absorbent, will consist of fibers selected according to characteristics primarily sought. As an indication, when we wish to have a flexible and highly absorbent face, we will use preferably viscose or cotton, if you are considering an item with good tear resistance, preferably use fiber polyamide and, if you want to improve the touch, you will use preferably acetate or cellulose fibers (artificial silk).

    Claims (11)

    1. Absorbent non-woven composite material consisting of at least two superposed fibrous sheets bonded together by interpenetration of the fibres in the thickness direction, in which:
      the first sheet consists entirely or partly of thermoplastic synthetic fibres preferably selected from the class of polyolefins;
      the second sheet, for its part, consists of natural and/or artificial and/or synthetic fibres having a higher melting point than the latter fibres;
      the individual sheets are combined by subjecting them to a treatment allowing the synthetic fibres of the first sheet to be reoriented so that, on the one hand, they are intimately bonded into the structure of the second sheet and, on the other hand, have [sic] visible loops or free ends on one of the external faces of the composite formed;
      characterized in that:
      the composite obtained is subjected to a heat treatment to melt the free ends of the synthetic fibres of the first sheet, making the latter abrasive by the formation of droplets at the place of the melting.
    2. Material according to Claim 1, characterized in that the first sheet consists of a mixture of cellulose or other fibres and of thermoplastic synthetic fibres, the percentage of the latter fibres in the sheet being greater than 30% and preferably greater than 50%.
    3. Material according to either of Claims 1 and 2, characterized in that the synthetic fibres used in making up the first sheet are polypropylene or polyethylene fibres.
    4. Material according to Claim 3, characterized in that the fibres have a linear density of greater than 5 dtex for a length of greater than 5 mm.
    5. Material according to one of Claims 1 to 4, characterized in that the natural and/or artificial fibres allowing the absorbent character to be obtained are paper-making fibres, viscose fibres, etc.
    6. Material according to one of Claims 1 to 5, characterized in that the synthetic fibres used in making up the second sheet are polyester or polyamide fibres, optionally crimped, having a melting point above those used in making up the first sheet.
    7. Material according to one of Claims 1 to 6, characterized in that the composite undergoes an additional treatment, such as creping, treatment with wetting agents making it possible to improve its hydrophilicity and the impregnation with a relatively aggressive liquid, such as a washing-up liquid.
    8. Material according to one of Claims 1 to 7, characterized in that the grammage of the second sheet is between 15 and 200 g/m2 and that of the first sheet is between 10 and 70 g/m2.
    9. Process for obtaining a material according to one of Claims 1 to 8, characterized in that two sheets of individual fibres are produced, the two sheets being bonded together downstream of the formation zone by a needle-punching treatment using fluid jets acting at least against the surface of the first sheet, characterized in that the non-woven composite formed is then dried and receives a complementary heat treatment for causing the partial melting of the ends of the chemical fibres of the first layer which remain bonded to the non-woven base composite.
    10. Process according to Claim 9, characterized in that the two individual layers are produced by the wet route, with these being combined on the dewatering belt before treatment using fluid jets.
    11. Process according to Claim 9, characterized in that the second sheet is obtained by the technique called the "dry route", the two individual sheets being combined after the formation of this sheet by the dry route, by attaching, to its surface, on that side where the action of the interlacing fluid jets will be exerted, the first web produced by the wet route, the two superposed sheets being preferably rehumidified before they undergo the action of the entangling jets.
    EP19970420136 1996-08-09 1997-07-29 Absorbent nonwoven composite material with a soft surface and a rough surface, and method for its production Expired - Lifetime EP0826811B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    FR9610235 1996-08-09
    FR9610235A FR2752248B1 (en) 1996-08-09 1996-08-09 ABSORBENT NONWOVEN COMPLEX MATERIAL HAVING A FLEXIBLE FACE AND A ROUGH FACE, AND METHOD FOR OBTAINING SAME

    Publications (3)

    Publication Number Publication Date
    EP0826811A2 EP0826811A2 (en) 1998-03-04
    EP0826811A3 EP0826811A3 (en) 1999-12-15
    EP0826811B1 true EP0826811B1 (en) 2002-10-30

    Family

    ID=9495076

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP19970420136 Expired - Lifetime EP0826811B1 (en) 1996-08-09 1997-07-29 Absorbent nonwoven composite material with a soft surface and a rough surface, and method for its production

    Country Status (4)

    Country Link
    EP (1) EP0826811B1 (en)
    DE (1) DE69716689T2 (en)
    ES (1) ES2183111T3 (en)
    FR (1) FR2752248B1 (en)

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR3128775A1 (en) * 2021-10-29 2023-05-05 Sofitec Air diffusion duct with high acoustic performance, in particular for motor vehicles

    Families Citing this family (16)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    AT405533B (en) * 1996-12-23 1999-09-27 Asota Gmbh DOUBLE-LAYER NEEDLE FILLED
    JP3409988B2 (en) * 1997-03-21 2003-05-26 ユニ・チャーム株式会社 Wipe sheet
    EP0888743A1 (en) * 1997-07-02 1999-01-07 Firma Carl Freudenberg Structured textile material having at least two fleeces and manufacturing process
    FR2795100B1 (en) * 1999-06-16 2001-09-14 Fort James France HYDROPHILIC COTTON PRODUCT WITH A SOFT FACE AND A SCRATCHING FACE
    DE10127514A1 (en) * 2001-06-06 2003-01-30 Hartmann Paul Ag Composite nonwoven material and process for its production
    FR2836161B1 (en) * 2002-02-18 2004-04-30 Jacob Holm France MULTI-LAYERED NON-WOVEN MATERIAL OR VEIL HAVING A ROUGH SIDE AND A SOFT SIDE
    EP1382730A1 (en) * 2002-07-15 2004-01-21 Paul Hartmann AG Cosmetic cotton pad
    AU2002100695B4 (en) * 2002-09-05 2002-12-05 Paolo Alvera A mat
    FR2849869B1 (en) * 2003-01-14 2005-09-09 Ahlstrom Brignoud METHOD FOR MANUFACTURING A COMPOSITE NON-WOVEN FABRIC AND INSTALLATION FOR CARRYING OUT SAID METHOD
    AU2003222932A1 (en) * 2003-02-19 2004-10-11 Jacob Holm Industries France Sas Non-woven fleece having one rough side and one soft absorbent surface
    FR2867067B1 (en) 2004-03-08 2007-09-07 Oreal COSMETIC ARTICLE FOR SINGLE USE
    JP4458903B2 (en) 2004-04-01 2010-04-28 ユニ・チャーム株式会社 Wiper and manufacturing method thereof
    WO2007029335A1 (en) * 2005-09-09 2007-03-15 Sanko Co., Ltd. Cleaning cloth
    US20070098768A1 (en) * 2005-11-01 2007-05-03 Close Kenneth B Two-sided personal-care appliance for health, hygiene, and/or environmental application(s); and method of making said two-sided personal-care appliance
    DE102014107725A1 (en) * 2014-06-02 2015-12-03 TRüTZSCHLER GMBH & CO. KG Process for the preparation of a structurable multilayer nonwoven and multilayer nonwoven
    DE102021006353A1 (en) * 2021-12-27 2023-06-29 Mondi Ascania GmbH Process for producing a nonwoven element for hygiene articles

    Family Cites Families (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    JPS59223350A (en) * 1983-05-26 1984-12-15 株式会社クラレ Nonwoven fabric and production thereof
    US4950531A (en) * 1988-03-18 1990-08-21 Kimberly-Clark Corporation Nonwoven hydraulically entangled non-elastic web and method of formation thereof
    US5328759A (en) * 1991-11-01 1994-07-12 Kimberly-Clark Corporation Process for making a hydraulically needled superabsorbent composite material and article thereof

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR3128775A1 (en) * 2021-10-29 2023-05-05 Sofitec Air diffusion duct with high acoustic performance, in particular for motor vehicles

    Also Published As

    Publication number Publication date
    FR2752248B1 (en) 1998-09-25
    DE69716689D1 (en) 2002-12-05
    ES2183111T3 (en) 2003-03-16
    DE69716689T2 (en) 2003-03-20
    EP0826811A2 (en) 1998-03-04
    EP0826811A3 (en) 1999-12-15
    FR2752248A1 (en) 1998-02-13

    Similar Documents

    Publication Publication Date Title
    EP0826811B1 (en) Absorbent nonwoven composite material with a soft surface and a rough surface, and method for its production
    EP1117860B1 (en) Method for producing a complex nonwoven material and resulting novel material
    EP0504368B1 (en) Hydraulically bound nonwoven and manufacturing method thereof
    CA2208117C (en) Non-woven tablecloth formed with very thin endless threads
    AU667536B2 (en) Apertured abrasive absorbent composite nonwoven web
    EP0166060B1 (en) Cleaning material and method for its manufacture
    JP4521274B2 (en) Multilayer nonwoven fabric
    EP2456585B1 (en) High cellulose content, laminiferous nonwoven fabric
    EP1167605B1 (en) Process and device for manufacturing an hydrophilic cotton article
    FR2803604A1 (en) METHOD FOR PRODUCING A COMPLEX NON-WOVEN MATERIAL AND A NEW TYPE OF MATERIAL THUS OBTAINED
    CA2018567A1 (en) Fibrous sheet multilayer textile complex of various features and manufacturing process
    FR2473077A1 (en) NON-WOVEN DISPOSABLE CLOTH
    CA2046651A1 (en) Process for fabrication of hydrophilic non-woven materials, including natural fibres; especially grey cotton; non-woven materials thus obtanied
    FR2705698A1 (en) A method of manufacturing a nonwoven web consisting of continuous filaments bonded together and web thus obtained.
    CA2061805C (en) Composite covering textile and manufacturing process
    US20030207636A1 (en) Nonwoven laminate wiping product and proces for its manufacture
    FR2911616A1 (en) Plant for producing non-woven fibrous sheet, comprises first fluid-permeable moving element, second moving element and device for projecting jet through which first element moves
    JP2003520307A (en) Nonwoven laminated wipe product and method of manufacturing the same
    FR2868683A1 (en) 3D TEXTILES WITH EMERGING HAIR; MAINTENANCE AND / OR CLEANING TOOLS; MANUFACTURING
    JP4916978B2 (en) Method for producing spunlace nonwoven fabric comprising short fibers
    EP1420097A1 (en) Microfibrous nonwovens, complexes and manufacturing processes
    EP1497488B1 (en) Non-woven with partially joined layers and methods and machine for the production thereof
    JP2022087399A (en) Method for producing wide filter substrate
    CA3143696A1 (en) Composite nonwoven sheet material
    FR2533597A1 (en) Synthetic fabrics upgraded by covers of higher quality fibres

    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

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): BE CH DE ES FI FR GB IT LI NL SE

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    17P Request for examination filed

    Effective date: 20000110

    AKX Designation fees paid

    Free format text: BE CH DE ES FI FR GB IT LI NL SE

    17Q First examination report despatched

    Effective date: 20010716

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: AHLSTROM BRIGNOUD S.A.

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): BE CH DE ES FI FR GB IT LI NL SE

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REF Corresponds to:

    Ref document number: 69716689

    Country of ref document: DE

    Date of ref document: 20021205

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20021202

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2183111

    Country of ref document: ES

    Kind code of ref document: T3

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

    Ref country code: LI

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

    Effective date: 20030731

    Ref country code: CH

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

    Effective date: 20030731

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

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

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

    26N No opposition filed

    Effective date: 20030731

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

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

    Ref country code: IT

    Payment date: 20080620

    Year of fee payment: 12

    Ref country code: FI

    Payment date: 20080617

    Year of fee payment: 12

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

    Ref country code: ES

    Payment date: 20080709

    Year of fee payment: 12

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

    Ref country code: NL

    Payment date: 20080619

    Year of fee payment: 12

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

    Ref country code: BE

    Payment date: 20080709

    Year of fee payment: 12

    BERE Be: lapsed

    Owner name: S.A. *AHLSTROM BRIGNOUD

    Effective date: 20090731

    NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

    Effective date: 20100201

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

    Ref country code: FI

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

    Effective date: 20090729

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

    Ref country code: BE

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

    Effective date: 20090731

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20090730

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

    Ref country code: ES

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

    Effective date: 20090730

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

    Ref country code: IT

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

    Effective date: 20090729

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

    Ref country code: NL

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

    Effective date: 20100201

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R082

    Ref document number: 69716689

    Country of ref document: DE

    Representative=s name: KUHNEN & WACKER PATENT- UND RECHTSANWALTSBUERO, DE

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: 732E

    Free format text: REGISTERED BETWEEN 20140731 AND 20140806

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R082

    Ref document number: 69716689

    Country of ref document: DE

    Representative=s name: KUHNEN & WACKER PATENT- UND RECHTSANWALTSBUERO, DE

    Effective date: 20140804

    Ref country code: DE

    Ref legal event code: R081

    Ref document number: 69716689

    Country of ref document: DE

    Owner name: SUOMINEN CORPORATION, FI

    Free format text: FORMER OWNER: AHLSTROM BRIGNOUD S.A.S. (SOCIETE PAR ACTIONS SIMPLIFIEE), BRIGNOUD, FR

    Effective date: 20140804

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: TP

    Owner name: SUOMINEN CORPORATION, FI

    Effective date: 20141006

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 20

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

    Ref country code: DE

    Payment date: 20160722

    Year of fee payment: 20

    Ref country code: GB

    Payment date: 20160721

    Year of fee payment: 20

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

    Ref country code: SE

    Payment date: 20160720

    Year of fee payment: 20

    Ref country code: FR

    Payment date: 20160721

    Year of fee payment: 20

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R071

    Ref document number: 69716689

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: PE20

    Expiry date: 20170728

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

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

    Effective date: 20170728