[go: up one dir, main page]

EP0900294B1 - Composite yarn - Google Patents

Composite yarn Download PDF

Info

Publication number
EP0900294B1
EP0900294B1 EP97915635A EP97915635A EP0900294B1 EP 0900294 B1 EP0900294 B1 EP 0900294B1 EP 97915635 A EP97915635 A EP 97915635A EP 97915635 A EP97915635 A EP 97915635A EP 0900294 B1 EP0900294 B1 EP 0900294B1
Authority
EP
European Patent Office
Prior art keywords
composite yarn
fire
ternary composition
composite
matrix
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
EP97915635A
Other languages
German (de)
French (fr)
Other versions
EP0900294A1 (en
Inventor
François Xavier DAMOUR
Yves Pronzati
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.)
Chavanoz Industrie SARL
Original Assignee
Chavanoz Industrie SARL
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=9492090&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0900294(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Chavanoz Industrie SARL filed Critical Chavanoz Industrie SARL
Publication of EP0900294A1 publication Critical patent/EP0900294A1/en
Application granted granted Critical
Publication of EP0900294B1 publication Critical patent/EP0900294B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • D02G3/404—Yarns or threads coated with polymeric solutions

Definitions

  • the present invention relates to a composite yarn with technical or industrial use, which can be assembled in all types of textile structures, especially surfaces suitable textiles, to meet all applications or particular specifications, for example for the manufacture of blinds or curtains.
  • the first is designated matrix fiber and is based on PVC and partially acetalized PVA, and further includes a inorganic flame retardant, consisting of an oxide hydrated tin, and hydrated antimony oxide.
  • the second fiber is based on polyester, acrylic or cotton.
  • such a wire is obtained by coating the core with a plastisol comprising the chlorinated polymeric material, by polyvinyl chloride example, and the plasticizer, then by gelation of plastisol around the core.
  • plasticizers particular, such as organic phosphates.
  • plasticizers particular, such as organic phosphates.
  • the use of such plasticizers deteriorates the processing characteristics (flexibility, sliding power, etc.) of these threads, which harms their posterior weaving, and makes it more difficult.
  • the incorporation of such plasticizers increases the smoke index.
  • a flame retardant filler comprising a chlorinated polyethylene, a compound chosen from in particular oxides and / or hydroxides antimony, and aluminum, and preferably a other compound chosen from certain zinc salts, including zinc borate.
  • the present invention relates to a thread composite, as previously defined, exhibiting globally and intrinsically fire behavior improved, expressed jointly by a decrease the temperature of the combustion fumes and by a substantial lowering of the ignition threshold residual of the different fabrics obtained with the yarn according to the invention, so that in particular such fabrics can meet both the ratings current B1 of German regulations (DIN standard N04102 Part 1), and M1 and F3 of French regulations (NFP 92503 standard), and all without harming processing characteristics of the same wire, required for weaving.
  • the weight composition total inorganic material of the sheath is included between 4% and 15%.
  • the flame retardant charge consists in said ternary composition.
  • chlorinated polymeric material one can use according to the invention, any PVC resin likely to be plasticized, and in particular capable of being therefore implemented in the form of plastisol.
  • polyvinyl chloride according to the present invention have a K WERT of between 65 and 75.
  • chlorinated polymeric material is meant, or a pure chlorinated polymer or a copolymer of vinyl chloride copolymerized with other monomers, or a chlorinated polymer which is alloyed with other polymers.
  • olefins such as ethylene, esters vinyl of saturated carboxylic acids, such as acetate vinyl or vinyl butyrate; drifts halogenated vinyls such as, for example, vinylidene, esters of acrylic or methacrylic acid like butyl acrylate.
  • chlorinated polymer there may be mentioned for example polyvinyl chloride but also superchlorinated PVC, polyvinylidene chlorides and polyolefins chlorinated.
  • the chlorinated polymeric material according to the present invention has a halogen content by weight of between 50 and 70%.
  • the continuous wire forming or included in the core of the composite wire can itself be made up by one or more continuous filaments.
  • Its chemical nature can be organic, for example polyester, or inorganic, for example glass or silica, it being understood that its melting temperature must be higher than that of implementation of the polymer material of the matrix constituting the sheath or envelope of the composite wire.
  • the invention it remains possible to use traditional plasticizers for the matrix plastic, for example comprising at least one phthalate organic, and therefore not to compromise processing properties of the wire, with respect to its subsequent weaving.
  • the invention also makes it possible to limit by weight the flame retardant charge, in proportions not exceeding not 65% of the plastic matrix, which promotes good weaving of the thread according to the invention. Beyond 65%, we witness dusting of the sheath, altering the properties in particular mechanical of the composite wire.
  • the present invention therefore provides a fire behavior of the same wire, very close to that of a inorganic thread. And the fabrics obtained with a composite yarn according to the invention do not need a subsequent treatment to improve their behavior at fire.
  • this thread is woven in different weaves, or specifications, specified below.
  • a composite yarn according to the present invention can be integrated into, or assembled according to all structures required textiles, two-dimensional (tablecloths, fabrics, etc ...) or three-dimensional (braids for example).
  • the composite wire can first be cut and divided into elementary threads, which can be intertwined and fixed to each other, in the form of structures non-woven textiles, for example matt.
  • the fixing of entangled elementary threads can be obtained by impregnation with a suitable adhesive substance, or again by thermofusion of the polymer material of the sheath.
  • the composite yarn can then be assembled on itself, in all appropriate knitted textile structures.
  • a very particular application of this invention relates to obtaining technical fabrics, intended for the realization or manufacture of blinds or both indoor and outdoor curtains.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Woven Fabrics (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Glass Compositions (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Reciprocating, Oscillating Or Vibrating Motors (AREA)
  • Multicomponent Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

PCT No. PCT/IB97/00413 Sec. 371 Date Nov. 5, 1998 Sec. 102(e) Date Nov. 5, 1998 PCT Filed Apr. 16, 1997 PCT Pub. No. WO97/42363 PCT Pub. Date Nov. 13, 1997A composite yarn includes a core composed of a continuous yarn, and a coated sheath composed of a matrix including at least one chlorinated polymer material, and a fire-retarding filler incorporated into and distributed within said matrix, wherein, in combination, the fire-retarding filler comprises a ternary composition which combines an oxygenated antimony compound, a hydrated metal oxide, the metal of which is chosen from aluminum, magnesium, tin, zinc and lead, and a zinc borate and, together with said ternary composition, the total weight content of inorganic matter in the yarn is between 4% and 65%.

Description

La présente invention concerne un fil composite à usage technique ou industriel, pouvant être assemblé en tous types de structures textiles, notamment surfaces textiles appropriées, pour répondre à toutes applications ou spécifications particulières, par exemple pour la fabrication de stores ou rideaux.The present invention relates to a composite yarn with technical or industrial use, which can be assembled in all types of textile structures, especially surfaces suitable textiles, to meet all applications or particular specifications, for example for the manufacture of blinds or curtains.

Dans l'art antérieur, on connaít par le document US-A-4 127 698 la réalisation de fibres composites ignifuges comprenant un mélange de deux fibres. La première est désignée fibre matrice et est à base de PVC et PVA partiellement acétalisé, et comporte en outre un agent ignifugeant inorganique, constitué d'un oxyde d'étain hydraté, et un oxyde d'antimoine hydraté. La deuxième fibre est à base de polyester, acrylique ou coton.In the prior art, we know from the document US-A-4,127,698 the production of composite fibers flame retardants comprising a mixture of two fibers. The first is designated matrix fiber and is based on PVC and partially acetalized PVA, and further includes a inorganic flame retardant, consisting of an oxide hydrated tin, and hydrated antimony oxide. The second fiber is based on polyester, acrylic or cotton.

Dans le document EP-A-O 385 025 on décrit la fabrication d'un fil composite comportant une âme en fibres de verre, et une gaine obtenue par filage de fibres à basse température de fusion, par exemple en coton.In document EP-A-O 385 025, the manufacture of a composite wire comprising a core glass fibers, and a sheath obtained by spinning fibers at low melting temperature, for example cotton.

Toutefois, ces documents concernent essentiellement des fils obtenus par filage de mélanges de fibres, et ne conviennent pas aux applications envisagées ci-après.However, these documents concern essentially yarns obtained by spinning mixtures of fibers, and are not suitable for the intended applications below.

Par ailleurs, on connaít déjà, et la Demanderesse fabrique et vend des fils composites techniques, comprenant :

  • une âme comportant un fil continu, par exemple un fil de verre ;
  • et une gaine enduite comportant une matrice plastique, constituée par au moins un matériau polymère chloré, par exemple un polychlorure de vinyle ;
  • une charge minérale ignifugeante incorporée et distribuée dans ladite matrice ;
  • et un plastifiant.
Furthermore, we already know, and the Applicant manufactures and sells technical composite yarns, comprising:
  • a core comprising a continuous wire, for example a glass wire;
  • and a coated sheath comprising a plastic matrix, constituted by at least one chlorinated polymeric material, for example a polyvinyl chloride;
  • a flame retardant mineral filler incorporated and distributed in said matrix;
  • and a plasticizer.

Préférentiellement, mais de manière non exclusive, un tel fil est obtenu par enduction de l'âme avec un plastisol comprenant le matériau polymère chloré, par exemple polychlorure de vinyle, et le plastifiant, puis par gélification du plastisol autour de l'âme.Preferably, but not exclusively, such a wire is obtained by coating the core with a plastisol comprising the chlorinated polymeric material, by polyvinyl chloride example, and the plasticizer, then by gelation of plastisol around the core.

Les tissus techniques obtenus avec de tels fils, et lorsqu'ils sont mis en oeuvre dans différents environnements, notamment pour l'aménagement tant intérieur qu'extérieur d'immeubles ou constructions, par exemple à titre de stores, sont soumis à des exigences de comportement au feu, définies par des réglementations et/ou procédures d'homologation ou autorisation, nationales ou internationales.The technical fabrics obtained with such threads, and when implemented in different environments, especially for landscaping both interior and exterior of buildings or constructions, for example example as blinds, are subject to the requirements of fire behavior, defined by regulations and / or approval or authorization procedures, national or international.

Ainsi, la réglementation applicable à de tels tissus en République Fédérale d'Allemagne définit différents classements, caractérisés notamment par la longueur de l'échantillon détruite par le feu, et par la température des fumées de combustion, et identifiés par les lettres B1 à B3, la lettre B1 caractérisant le meilleur comportement au feu accessible par un matériau comprenant des matières organiques.Thus, the regulations applicable to such fabrics in the Federal Republic of Germany defines different classifications, characterized in particular by the length of the sample destroyed by fire, and by the combustion smoke temperature, and identified by the letters B1 to B3, the letter B1 characterizing the better fire behavior accessible by a material comprising organic matter.

Et la réglementation applicable en France définit quant à elle, également différents classements, d'une part caractérisés notamment par l'émission de fumées et identifiés par les lettres FO à F5, F3 étant le meilleur comportement accessible par un matériau contenant un polymère halogéné, et d'autre part caractérisés notamment par la température d'inflammation résiduelle du tissu, et identifiés par les lettres MO à M4, la lettre M1 identifiant le meilleur comportement au feu généralement accessible par un matériau comprenant des matières organiques.And the regulations applicable in France define on the other hand, also different rankings characterized in particular by the emission of smoke and identified by the letters FO to F5, F3 being the best behavior accessible by a material containing a halogenated polymer, and on the other hand characterized in particular by the tissue's residual ignition temperature, and identified by the letters MO to M4, the letter M1 identifying the best fire behavior generally accessible by a material comprising materials organic.

Aujourd'hui, avec les fils composites définis précédemment, les tissus techniques obtenus présentent un comportement au feu ayant une certaine limite, illustrée par le fait que de tels tissus n'ont jamais pu obtenir, sans traitement chimique postérieur à leur tissage, le classement B1 de la réglementation allemande, conjointement avec le classement Ml de la réglementation française.Today, with defined composite yarns previously, the technical fabrics obtained have a fire behavior with a certain limit, illustrated by the fact that such fabrics were never able to obtain, without chemical treatment after their weaving, the classification B1 of the German regulations, together with the Ml classification of the regulations French.

La principale raison des limites précédemment constatées tient évidemment à la nature organique de certains constituants du fil composite, notamment le matériau polymère chloré, le plastifiant, voire certains additifs d'enduction.The main reason for the limits previously observed is obviously due to the organic nature of certain constituents of the composite yarn, in particular the chlorinated polymer material, plasticizer, or even some coating additives.

Différentes tentatives ont été faítes pour améliorer intrinsèquement le comportement au feu, de ces fils composites, par exemple en utilisant des plastifiants particuliers, comme des phosphates organiques. Malheureusement, l'utilisation de tels plastifiants détériore les caractéristiques de mise en oeuvre (souplesse, pouvoir glissant, etc...) de ces fils, ce qui nuit à leur tissage postérieur, et rend ce dernier plus difficile. Par ailleurs, l'incorporation de tels plastifiants augmente l'indice de fumée.Various attempts have been made to intrinsically improve the fire behavior of these composite yarns, for example using plasticizers particular, such as organic phosphates. Unfortunately, the use of such plasticizers deteriorates the processing characteristics (flexibility, sliding power, etc.) of these threads, which harms their posterior weaving, and makes it more difficult. Furthermore, the incorporation of such plasticizers increases the smoke index.

Il n'est pas possible, non plus, d'augmenter de manière significative la proportion pondérale de la charge ignifugeante, sauf à détériorer comme précédemment les caractéristiques de mise en oeuvre du fil composite.Nor is it possible to increase by significantly the weight proportion of the load flame retardant, except to deteriorate as previously the processing characteristics of the composite yarn.

S'agissant des performances de la charge ignifugeante proprement dite, différents documents ont proposé divers composés ou diverses compositions, susceptibles d'améliorer le comportement au feu des matrices plastiques dans lesquelles la charge ignifugeante est incorporée, sans que l'application ou la mise en forme de la matière plastique ignifugée, par exemple sous forme de fil, soit précisée.Regarding load performance flame retardant proper, various documents have proposed various compounds or various compositions, likely to improve the fire behavior of plastic matrices in which the flame retardant filler is incorporated, without the application or formatting fireproof plastic, for example in the form of wire, be specified.

Ainsi, selon le document JP-A-58185637, pour une matrice à base de polychlorure de vinyle, on a proposé une charge ignifugeante comprenant un polyéthylène chloré, un composé choisi parmi notamment les oxydes et/ou hydroxydes d'antimoine, et d'aluminium, et préférentiellement un autre composé choisi parmi certains sels de zinc, dont le borate de zinc.Thus, according to document JP-A-58185637, for a polyvinyl chloride matrix, we proposed a flame retardant filler comprising a chlorinated polyethylene, a compound chosen from in particular oxides and / or hydroxides antimony, and aluminum, and preferably a other compound chosen from certain zinc salts, including zinc borate.

Et conformément au document FR-A-2 448 554, toujours pour une matrice à base de polychlorure de vinyle, incorporant par ailleurs un stabilisant, un plastifiant constitué par un ester phosphorique, et une charge d'hydroxyde d'alumine, on a proposé une charge ignifugeante comprenant un oxyde d'antimoine, éventuellement associé à un borate de zinc.And in accordance with document FR-A-2 448 554, always for a matrix based on polychloride of vinyl, incorporating a stabilizer, a plasticizer consisting of a phosphoric ester, and a charge of alumina hydroxide, a charge has been proposed flame retardant comprising an antimony oxide, possibly associated with a zinc borate.

Aucune des charges ignifugeantes précédemment proposées ne convient pour améliorer le comportement au feu d'un fil composite tel que précédemment considéré.None of the flame retardants previously are not suitable for improving behavior at fire of a composite wire as previously considered.

La présente invention a pour objet un fil composite, tel que précédemment défini, présentant globalement et intrinsèquement un comportement au feu amélioré, exprimé conjointement par une diminution substantielle de la température des fumées de combustion et par un abaissement substantiel du seuil d'inflammation résiduelle des différents tissus obtenus avec le fil selon l'invention, de telle sorte qu'en particulier de tels tissus puissent satisfaire à la fois aux classements actuels B1 de la réglementation allemande (norme DIN N04102 Teil 1), et M1 et F3 de la réglementation française (norme NFP 92503), et tout cela sans nuire aux caractéristiques de mise en oeuvre du même fil, requises pour le tissage.The present invention relates to a thread composite, as previously defined, exhibiting globally and intrinsically fire behavior improved, expressed jointly by a decrease the temperature of the combustion fumes and by a substantial lowering of the ignition threshold residual of the different fabrics obtained with the yarn according to the invention, so that in particular such fabrics can meet both the ratings current B1 of German regulations (DIN standard N04102 Teil 1), and M1 and F3 of French regulations (NFP 92503 standard), and all without harming processing characteristics of the same wire, required for weaving.

Conformément à la présente invention, on a découvert que les objectifs précités pouvaient être satisfaits en combinant deux caractéristiques essentielles, à savoir :

  • (a) le choix d'une composition ternaire pour la charge ignifugeante, associant :
    • un composé oxygéné d'antimoine, par exemple du trioxyde (Sb2O3) ou pentoxyde d'antimoine ;
    • un oxyde métallique hydraté dont le métal est choisi dans le groupe constitué par l'aluminium, le magnésium, l'étain, le zinc, et le plomb, par exemple hydrate d'alumine (Al2O3.3H2O) ;
    • et un borate de zinc, hydraté ou non, par exemple (2ZnO.3B2O3.7/2 H2O) ;
  • (b) avec la composition ternaire précitée, le maintien de la composition pondérale totale en matières inorganiques du fil composite, y compris l'âme, dans une fourchette comprise entre 4 % et 65 %.
    • In accordance with the present invention, it has been discovered that the above-mentioned objectives can be satisfied by combining two essential characteristics, namely:
  • (a) the choice of a ternary composition for the flame retardant charge, combining:
    • an oxygenated antimony compound, for example trioxide (Sb 2 O 3 ) or antimony pentoxide;
    • a hydrated metal oxide, the metal of which is chosen from the group consisting of aluminum, magnesium, tin, zinc, and lead, for example alumina hydrate (Al 2 O 3 .3H 2 O);
    • and a zinc borate, hydrated or not, for example (2ZnO.3B 2 O 3 .7 / 2 H 2 O);
  • (b) with the aforementioned ternary composition, maintaining the total weight composition in inorganic matter of the composite yarn, including the core, in a range between 4% and 65%.

    • Préférentiellement, la composition pondérale totale en matières inorganiques de la gaine est comprise entre 4 % et 15 %.Preferably, the weight composition total inorganic material of the sheath is included between 4% and 15%.

    Avantageusement, la charge ignifugeante consiste en ladite composition ternaire.Advantageously, the flame retardant charge consists in said ternary composition.

    A titre de matériau polymère chloré, on peut utiliser conformément à l'invention, toute résine PVC susceptible d'être plastifiée, et notamment pouvant être de ce fait mise en oeuvre sous forme de plastisol.As chlorinated polymeric material, one can use according to the invention, any PVC resin likely to be plasticized, and in particular capable of being therefore implemented in the form of plastisol.

    Préférentiellement, les polychlorures de vinyle selon la présente invention ont un K WERT compris entre 65 et 75.Preferably, polyvinyl chloride according to the present invention have a K WERT of between 65 and 75.

    Par matériau polymère chloré, on entend, ou un polymère chloré pur ou un copolymère de chlorure de vinyle copolymérisé avec d'autres monomères, ou encore un polymère chloré qui est allié avec d'autres polymères.By chlorinated polymeric material is meant, or a pure chlorinated polymer or a copolymer of vinyl chloride copolymerized with other monomers, or a chlorinated polymer which is alloyed with other polymers.

    Parmi les monomères qui peuvent être copolymérisés avec le chlorure de vinyle, on citera notamment des oléfines comme par exemple l'éthylène, des esters vinyliques d'acides carboxyliques saturés, comme l'acétate de vinyle ou le butyrate de vinyle ; des dérivés vinyliques halogénés comme, par exemple, le chlorure de vinylidène, des esters d'acide acrylique ou méthacrylique comme l'acrylate de butyle.Among the monomers which can be copolymerized with vinyl chloride, particular mention may be made of olefins such as ethylene, esters vinyl of saturated carboxylic acids, such as acetate vinyl or vinyl butyrate; drifts halogenated vinyls such as, for example, vinylidene, esters of acrylic or methacrylic acid like butyl acrylate.

    A titre de polymère chloré, on citera par exemple le polychlorure de vinyle mais aussi les PVC surchlorés, les polychlorures de vinylidène et les polyoléfines chlorées. As chlorinated polymer, there may be mentioned for example polyvinyl chloride but also superchlorinated PVC, polyvinylidene chlorides and polyolefins chlorinated.

    De manière préférentielle, mais non exclusive, le matériau polymère chloré selon la présente invention a une teneur pondérale en halogène comprise entre 50 et 70 %.Preferably, but not exclusively, the chlorinated polymeric material according to the present invention has a halogen content by weight of between 50 and 70%.

    S'agissant du fil continu formant ou compris dans l'âme du fil composite, il peut être lui-même constitué par un ou plusieurs filaments continus. Sa nature chimique peut être organique, par exemple en polyester, ou inorganique, par exemple en verre ou silice, étant entendu que sa température de fusion doit être supérieure à celle de mise en oeuvre du matériau polymère de la matrice constituant la gaine ou enveloppe du fil composite.Regarding the continuous wire forming or included in the core of the composite wire, it can itself be made up by one or more continuous filaments. Its chemical nature can be organic, for example polyester, or inorganic, for example glass or silica, it being understood that its melting temperature must be higher than that of implementation of the polymer material of the matrix constituting the sheath or envelope of the composite wire.

    D'autres charges peuvent être incorporées et distribuées dans la matrice de la gaine, en plus de la charge ignifugeante, par exemple une charge pigmentaire et/ou une charge stabilisante. En pareil cas, la composition pondérale totale du fil composite, en matières inorganiques, se trouve évidemment modifiée ou affectée, également par le contenu en matières inorganiques de ces charges supplémentaires.Other charges may be incorporated and distributed in the sheath matrix, in addition to the flame retardant filler, for example a pigment filler and / or a stabilizing filler. In such a case, the total weight composition of the composite yarn, in materials inorganic, is obviously modified or affected, also by the inorganic matter content of these additional charges.

    Grâce à l'invention, il demeure possible de recourir à des plastifiants traditionnels pour la matrice plastique, par exemple comprenant au moins un phtalate organique, et par conséquent de ne pas compromettre les propriétés de mise en oeuvre du fil, vis-à-vis de son tissage ultérieur.Thanks to the invention, it remains possible to use traditional plasticizers for the matrix plastic, for example comprising at least one phthalate organic, and therefore not to compromise processing properties of the wire, with respect to its subsequent weaving.

    L'invention permet aussi de limiter pondéralement la charge ignifugeante, dans des proportions n'excédant pas 65 % de la matrice plastique, ce qui favorise un bon tissage du fil selon l'invention. Au-delà de 65 %, on assiste à un poudrage de la gaine, altérant les propriétés notamment mécaniques du fil composite.The invention also makes it possible to limit by weight the flame retardant charge, in proportions not exceeding not 65% of the plastic matrix, which promotes good weaving of the thread according to the invention. Beyond 65%, we witness dusting of the sheath, altering the properties in particular mechanical of the composite wire.

    En restant avec un fil composite obtenu par enduction, la présente invention apporte donc un comportement au feu du même fil, très proche de celui d'un fil de nature inorganique. Et les tissus obtenus avec un fil composite selon l'invention n'ont pas besoin d'un traitement postérieur pour améliorer leur comportement au feu.By remaining with a composite wire obtained by coating, the present invention therefore provides a fire behavior of the same wire, very close to that of a inorganic thread. And the fabrics obtained with a composite yarn according to the invention do not need a subsequent treatment to improve their behavior at fire.

    Il résulte aussi des essais de la Demanderesse que les fils composites selon la présente invention ont une très bonne tenue à la lumière et aux intempéries.It also results from the Applicant's tests that the composite yarns according to the present invention have a very good resistance to light and weather.

    Préférentiellement :

    • la composition pondérale en plastifiant d'un fil composite selon l'invention n'excède pas 40 %, et est de préférence comprise entre 10 et 20 % ; au-delà de 35 % de plastifiant, ce dernier exsude de la matrice de l'enveloppe ou gaine ;
    • et/ou la composition ternaire de la charge ignifugeante associe à parts pondérales sensiblement égales, le composé oxygéné d'antimoine, l'oxyde métallique hydraté et le borate de zinc.
    Preferably:
    • the composition by weight of plasticizer of a composite yarn according to the invention does not exceed 40%, and is preferably between 10 and 20%; beyond 35% of plasticizer, the latter exudes from the matrix of the envelope or sheath;
    • and / or the ternary composition of the flame retardant filler combines in substantially equal weight shares, the oxygenated antimony compound, the hydrated metal oxide and the zinc borate.

    La présente invention s'appuie sur le protocole expérimental suivant.
    On a tout d'abord formulé un plastisol comprenant le matériau polymère et un plastifiant, selon la composition pondérale suivante :

    • 60 à 65 % d'une ou plusieurs résines de polychlorure de vinyle (référence commerciale ECKAVYL EF701 de la Société ATOCHEM) ;
    • 20 à 30 % d'un phtalate d'isononyle (référence commerciale JAYFLEX DINP de la Société EXXON) ;
    • additifs divers, pour le complément, dont stabilisant thermique inorganique (de 1,5 à 2 %).
    The present invention is based on the following experimental protocol.
    First of all, a plastisol comprising the polymer material and a plasticizer was formulated, according to the following weight composition:
    • 60 to 65% of one or more polyvinyl chloride resins (commercial reference ECKAVYL EF701 from the company ATOCHEM);
    • 20 to 30% of an isononyl phthalate (commercial reference JAYFLEX DINP from the company EXXON);
    • miscellaneous additives for the complement, including inorganic thermal stabilizer (1.5 to 2%).

    A ce plastisol a été incorporée une charge ignifugeante ternaire, associant à parts pondérales égales :

    • du trioxyde d'antimoine, Sb2O3 ;
    • de l'hydrate d'alumine, Al2O3.3H2O ;
    • du borate de zinc (2ZnO.3b2O3.7/2 H2O), noté ci-après BoZn.
    To this plastisol has been incorporated a ternary flame retardant filler, associating in equal weight shares:
    • antimony trioxide, Sb 2 O 3 ;
    • alumina hydrate, Al 2 O 3 .3H 2 O;
    • zinc borate (2ZnO.3b 2 O 3 .7 / 2 H 2 O), noted below BoZn.

    Puis, on enduit une âme en fil de verre avec le plastisol chargé, pour obtenir un fil composite selon la présente invention.Then, we coat a glass wire core with the filled plastisol, to obtain a composite yarn according to the present invention.

    Et ce fil est tissé selon différentes armures, ou spécifications, précisées ci-après.And this thread is woven in different weaves, or specifications, specified below.

    Conformément au tableau ci-après où Mi et B1 désignent les niveaux de classement le plus élevé, respectivement selon la réglementation allemande et selon la réglementation française, pour un matériau organique, on a tout d'abord découvert que l'association ternaire des trois composés ci-dessus, était nécessaire à l'obtention conjointe du classement M1 et du classement B1, et ceci pour les tissus obtenus avec un fil selon la présente invention, avec les armures suivantes :

    • satiné - contexture 18/14
    • natté - contexture 14/14
    M1 B1 Sb2O3 oui non Al2O3.3H2O non non BoZn non non Sb2O3 + (Al2O3.3H2O) non oui Sb2O3 + BoZn oui non BoZn + (Al2O3.3H2O) non non In accordance with the table below where Mi and B1 designate the highest classification levels, respectively according to German regulations and according to French regulations, for an organic material, it was first discovered that the ternary association of the three compounds above, was necessary to obtain the M1 classification and B1 classification jointly, and this for the fabrics obtained with a thread according to the present invention, with the following weaves:
    • satin - texture 18/14
    • braided - texture 14/14
    M1 B1 Sb 2 O 3 Yes no Al 2 O 3 .3H 2 O no no BoZn no no Sb 2 O 3 + (Al 2 O 3 .3H 2 O) no Yes Sb 2 O 3 + BoZn Yes no BoZn + (Al 2 O 3 .3H 2 O) no no

    Puis différents fils ont été obtenus, avec des compositions pondérales (en %) respectivement différentes, en fonction du titre désiré, selon le tableau ci-après : Titre 165 Tex 97 Tex Ame en verre 41,0 35,0 Enveloppe ou gaine 59,0 65,0 Polychlorure de vinyle 33 37 Charge ignifugeante 9,0 10 Plastifiant 13,5 15,0 Composition pondérale totale, en matières inorganiques 52 47 Then different yarns were obtained, with weight compositions (in%) respectively different, depending on the desired titer, according to the table below: Headline 165 Tex 97 Tex Glass core 41.0 35.0 Envelope or sheath 59.0 65.0 Polyvinyl chloride 33 37 Fire retardant charge 9.0 10 Plasticizer 13.5 15.0 Total weight composition, in inorganic matter 52 47

    Un fil composite selon la présente invention peut être intégré dans, ou assemblé selon toutes structures textiles requises, bidimensionnelles (nappes, tissus, etc... ) ou tridimensionnelles (tresses par exemple).A composite yarn according to the present invention can be integrated into, or assembled according to all structures required textiles, two-dimensional (tablecloths, fabrics, etc ...) or three-dimensional (braids for example).

    Le fil composite peut tout d'abord être coupé et divisé en fils élémentaires, pouvant être entremêlés et fixés les uns aux autres, sous forme de structures textiles non tissées, mats par exemple. La fixation des fils élémentaires entremêlés peut être obtenue par imprégnation avec une substance adhésive appropriée, ou encore par thermo-fusion du matériau polymère de la gaine. Le -fil composite peut ensuite être assemblé sur lui-même, dans toutes structures textiles tricotées appropriées. mais il peut être assemblé avec d'autres fils, selon la présente invention ou non, pour constituer bidimensionnelles ; dans ce dernier cas, il peut s'agir de grilles dans lesquelles les fils selon la présente invention sont entrecroisés et fixés avec d'autres fils, selon la présente invention ou non, et de tissus, dans lesquels les fils composites selon l'invention sont tissés avec d'autres fils de chaíne et/ou trame, également selon l'invention ou non.The composite wire can first be cut and divided into elementary threads, which can be intertwined and fixed to each other, in the form of structures non-woven textiles, for example matt. The fixing of entangled elementary threads can be obtained by impregnation with a suitable adhesive substance, or again by thermofusion of the polymer material of the sheath. The composite yarn can then be assembled on itself, in all appropriate knitted textile structures. but it can be assembled with other wires, depending on the present invention or not, to constitute two-dimensional; in the latter case, it may be grids in which the wires according to this invention are intertwined and fixed with other wires, according to the present invention or not, and of fabrics, in which composite yarns according to the invention are woven with other warp and / or weft threads, also according to the invention or not.

    Une application toute particulière de la présente invention concerne l'obtention de tissus techniques, destinés à la réalisation ou fabrication de stores ou rideaux tant intérieurs qu'extérieurs.A very particular application of this invention relates to obtaining technical fabrics, intended for the realization or manufacture of blinds or both indoor and outdoor curtains.

    Pour l'obtention de stores, les fils obtenus selon le protocole expérimental précité ont été tissés selon les armures suivantes ou spécifications suivantes, à titre d'exemple :

    • satiné - contexture 18/14
    • natté - contexture 14/14
    To obtain blinds, the threads obtained according to the aforementioned experimental protocol were woven according to the following weaves or following specifications, for example:
    • satin - texture 18/14
    • braided - texture 14/14

    Après essais au feu, tous ces tissus ont montré qu'ils satisfaisaient, et à la règlementation allemande avec le classement B1, et à la règlementation française avec le classement M1 et F3.After fire tests, all of these fabrics showed that they satisfied, and to German regulations with the B1 classification, and with French regulations with the M1 and F3 classification.

    Claims (9)

    1. Composite yarn comprising a core composed of a continuous yarn, especially made of an inorganic material, for example glass, and a coated sheath composed of a matrix consisting of at least one chlorinated polymer material, for example a polyvinyl chloride or PVC, and a fire-retarding filler incorporated into and distributed within the said matrix, characterized in that, in combination, on the one hand the fire-retarding filler comprises a ternary composition which combines an oxygenated antimony compound, for example antimony trioxide, a hydrated metal oxide, the metal of which is chosen from the group consisting of aluminium, magnesium, tin, zinc and lead, for example an alumina hydrate, and a zinc borate and, on the other hand, together with the said ternary composition, the total weight content of inorganic matter in the yarn is between 4% and 65%.
    2. Composite yarn according to Claim 1, characterized in that the total weight content of inorganic matter in the sheath is between 4 and 15%.
    3. Composite yarn according to Claim 1, characterized in that the fire-retarding filler consists of the said ternary composition.
    4. Composite yarn according to Claim 1, comprising a plasticizer, characterized in that the said plasticizer comprises at least one organic phthalate.
    5. Composite yarn according to Claim 4, characterized in that the plasticizer weight content of the said yarn does not exceed 40% and is preferably between 10 and 20%.
    6. Composite yarn according to Claim 1, characterized in that the ternary composition of the fire-retarding filler combines, in approximately equal parts by weight, the oxygenated antimony compound, the hydrated metal oxide and zinc borate.
    7. Textile structure, characterized in that it is obtained from at least one composite yarn according to any one of Claims 1 to 6.
    8. Textile structure according to Claim 7, characterized in that it consists of a textile sheet, woven or nonwoven, especially a fabric obtained by warp and/or weft weaving of the said composite yarn.
    9. Blind or curtain comprising a cloth consisting of a woven fabric according to Claim 8.
    EP97915635A 1996-05-07 1997-04-16 Composite yarn Expired - Lifetime EP0900294B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    FR9605942A FR2748496B1 (en) 1996-05-07 1996-05-07 COMPOSITE YARN
    FR9605942 1996-05-07
    PCT/IB1997/000413 WO1997042363A1 (en) 1996-05-07 1997-04-16 Composite yarn

    Publications (2)

    Publication Number Publication Date
    EP0900294A1 EP0900294A1 (en) 1999-03-10
    EP0900294B1 true EP0900294B1 (en) 1999-11-24

    Family

    ID=9492090

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP97915635A Expired - Lifetime EP0900294B1 (en) 1996-05-07 1997-04-16 Composite yarn

    Country Status (9)

    Country Link
    US (1) US6032454A (en)
    EP (1) EP0900294B1 (en)
    JP (1) JP4369996B2 (en)
    AT (1) ATE186953T1 (en)
    AU (1) AU715198B2 (en)
    DE (1) DE69700842T2 (en)
    ES (1) ES2140969T3 (en)
    FR (1) FR2748496B1 (en)
    WO (1) WO1997042363A1 (en)

    Cited By (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2010001240A1 (en) * 2008-07-02 2010-01-07 Porcher Industries Pvc-based flame-retardant composition
    US9920458B2 (en) 2014-04-22 2018-03-20 Mermet Process for manufacturing flame-retardant yarns
    WO2020112363A1 (en) 2018-11-29 2020-06-04 Eastman Kodak Company Aqueous composition for making yarns and fabrics
    US10870768B2 (en) 2018-11-29 2020-12-22 Eastman Kodak Company Composition for making coated yarn
    US10927483B2 (en) 2018-11-29 2021-02-23 Eastman Kodak Company Fabric substrates
    US11091874B2 (en) 2018-11-29 2021-08-17 Eastman Kodak Company Yarn with coating over yarn core
    WO2023278134A1 (en) 2021-07-02 2023-01-05 Eastman Kodak Company Non-foamed aqueous composition, coated textile and method of making

    Families Citing this family (17)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US6279644B1 (en) 1997-12-24 2001-08-28 St. Gobain Bayform America Inc. Screen and frame assembly in which the screen is adhesively secured to the frame
    US6991693B2 (en) 1997-12-24 2006-01-31 Saint-Gobain Bayform America, Inc. Screen cloth insertion apparatus and method
    FR2791353B1 (en) * 1999-03-23 2001-05-25 Chavanoz Ind FLAME RETARDANT PLASTIC COMPOSITION, WIRE AND TEXTILE STRUCTURE COATED WITH THE SAME
    US6315499B1 (en) * 1999-04-01 2001-11-13 Saint Cobain Technical Fabrics Canada, Ltd. Geotextile fabric
    US7365032B1 (en) 1999-11-04 2008-04-29 Kaneka Corporation Flame-retardant union fabric
    US9045845B2 (en) * 2001-12-28 2015-06-02 Chavanoz Industrie Composite yarn, method for obtaining same and resulting textile structure
    FR2834302B1 (en) * 2001-12-28 2005-05-06 Chavanoz Ind COMPOSITE WIRE, PROCESS FOR OBTAINING AND TEXTILE STRUCTURE OBTAINED
    US6977021B2 (en) * 2003-07-09 2005-12-20 Alumaroll Specialty Co., Inc. Screen assembly and method
    AT503675B1 (en) * 2006-05-15 2008-09-15 Lenzing Plastics Gmbh CHEMICALLY RESISTANT AND FORM-RESISTANT MONOFILAMENTS, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE
    FR2923500B1 (en) * 2007-11-14 2009-11-27 Porcher Ind FLEXIBLE, FLAME RETARDANT WITH PHOTOCATALYTIC COATING, AND PROCESS FOR PRODUCING THE SAME
    US20100003879A1 (en) * 2008-07-02 2010-01-07 Porcher Industries Composition ignifugee a base de PVC
    FR2939152B1 (en) 2008-12-01 2011-05-06 Porcher Ind PHOTOLUMINESCENT COMPOSITE FIL, PROCESS FOR OBTAINING AND TEXTILE STRUCTURE OBTAINED
    PT2875069T (en) 2012-07-17 2017-12-29 Italmatch Chemicals Spa Pvc flame retardant compositions
    DE102017123922A1 (en) * 2017-10-13 2019-04-18 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Multi-component fiber and method of manufacture
    WO2019202151A1 (en) 2018-04-20 2019-10-24 Mermet Composite yarn, manufacturing process and textile surface comprising such a yarn
    FR3080387B1 (en) 2018-04-20 2020-11-13 Mermet REINFORCED COMPOSITE YARN, PREPARATION PROCESS AND TEXTILE INCLUDING SUCH YARN
    TWI824157B (en) * 2019-06-10 2023-12-01 日商日東紡績股份有限公司 Resin-coated inorganic multifilament fiber fabric and sunshade using the same

    Family Cites Families (10)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    IL36371A (en) * 1970-03-17 1975-06-25 Chiarotto N Flameproof composite yarns
    JPS536617A (en) * 1976-07-07 1978-01-21 Kohjin Co Ltd Composite fibers
    IT1084174B (en) * 1977-09-01 1985-05-25 Bobkowicz E Three-component yarn having inner layer of glass fibre - is used for fabric with fire-retardant properties
    US4381639A (en) * 1980-06-19 1983-05-03 Record Industrial Company Sheath-core yarn for severe thermal protecting fabrics and method therefor
    FR2494313A1 (en) * 1980-11-14 1982-05-21 Brochier Fils Sa J Industrial fabric used as window blind - comprising coated and wrapped glass fibres, in woven fabric which is heat treated
    JPS58185637A (en) * 1982-04-23 1983-10-29 Hitachi Cable Ltd polyvinyl chloride composition
    US4921456A (en) * 1988-07-29 1990-05-01 Amp Incorporated Electrical assemblies including female electrical terminal
    US4921756A (en) * 1989-03-03 1990-05-01 Springs Industries, Inc. Fire resistant balanced fine corespun yarn and fabric formed thereof
    JPH0359134A (en) * 1989-07-26 1991-03-14 Unitika Ltd Core-sheath type composite yarn
    US5506043A (en) * 1989-08-18 1996-04-09 Norfab Corporation Thermal protective fabric and core-spun heat resistant yarn for making the same, said yarns consisting essentially of a fiberglass core and a cover of modacrylic fibers and at least one other flame retardant fiber

    Cited By (8)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2010001240A1 (en) * 2008-07-02 2010-01-07 Porcher Industries Pvc-based flame-retardant composition
    FR2933418A1 (en) * 2008-07-02 2010-01-08 Porcher Ind Flame-retardant plastisol, useful e.g. for coating flame-retardant yarn containing filament yarn in textile structure, e.g. fabric, which is useful in sunscreen protection, comprises chlorinated polymer material e.g. PVC
    US9920458B2 (en) 2014-04-22 2018-03-20 Mermet Process for manufacturing flame-retardant yarns
    WO2020112363A1 (en) 2018-11-29 2020-06-04 Eastman Kodak Company Aqueous composition for making yarns and fabrics
    US10870768B2 (en) 2018-11-29 2020-12-22 Eastman Kodak Company Composition for making coated yarn
    US10927483B2 (en) 2018-11-29 2021-02-23 Eastman Kodak Company Fabric substrates
    US11091874B2 (en) 2018-11-29 2021-08-17 Eastman Kodak Company Yarn with coating over yarn core
    WO2023278134A1 (en) 2021-07-02 2023-01-05 Eastman Kodak Company Non-foamed aqueous composition, coated textile and method of making

    Also Published As

    Publication number Publication date
    DE69700842D1 (en) 1999-12-30
    ATE186953T1 (en) 1999-12-15
    AU2304297A (en) 1997-11-26
    ES2140969T3 (en) 2000-03-01
    FR2748496A1 (en) 1997-11-14
    AU715198B2 (en) 2000-01-20
    US6032454A (en) 2000-03-07
    JP2000509766A (en) 2000-08-02
    DE69700842T2 (en) 2000-03-16
    FR2748496B1 (en) 1998-06-26
    EP0900294A1 (en) 1999-03-10
    JP4369996B2 (en) 2009-11-25
    WO1997042363A1 (en) 1997-11-13

    Similar Documents

    Publication Publication Date Title
    EP0900294B1 (en) Composite yarn
    EP1687471B1 (en) Composite yarn comprising a filament yarn and a matrix comprising a foamed polymer
    US9045845B2 (en) Composite yarn, method for obtaining same and resulting textile structure
    KR102108340B1 (en) Superior See-Through and low heat gain Sunscreen Fabrics with Coated Yarn Containing Organic/Inorganic Hybrid Coating Layer and The Preparation Method Thereof
    KR102341200B1 (en) Net For Insect Screen Having Excellent UV-Blocking And Anti-static Property
    EP1458910B1 (en) Composite yarn, method for obtaining same and resulting textile structure
    FR2791353A1 (en) FLAME RETARDANT PLASTIC COMPOSITION, WIRE AND TEXTILE STRUCTURE COATED WITH THE SAME
    EP2300532B1 (en) Pvc-based flame-retardant composition
    EP2789732B1 (en) Resin-coated flame-retardant glass fiber bundle and resin-coated flame-retardant fiber woven fabric
    EP0296988B1 (en) Open work fabric with a fire-proof layer
    US7134266B2 (en) Jacketed yarn, textile and method of producing such a yarn
    EP2995717B1 (en) Resin-coated fire-resistant fibre thread, and resin-coated fire-resistant woven fabric using same
    JPS6028529A (en) Coated yarn for flame-retardant network structures
    US12247326B2 (en) Flexible ignition resistant non-electrically conductive biregional fibers, articles made from non-non-electrically conductive biregional fibers, and methods of manufacture
    AU2010297202B2 (en) Composite yarn, method for obtaining same and resulting textile structure
    JPH11152680A (en) Water permeable insect net
    FR2791352A1 (en) Halogen-free flame retardant plastic composition e.g. for coating yarn and textiles, comprising a plastisol of acrylic resin and intumescent agent dispersed in a plasticizer medium

    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: 19981027

    AK Designated contracting states

    Kind code of ref document: A1

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

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    17Q First examination report despatched

    Effective date: 19990514

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

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

    Ref country code: SE

    Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

    Effective date: 19991124

    Ref country code: GR

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

    Effective date: 19991124

    Ref country code: FI

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

    Effective date: 19991124

    REF Corresponds to:

    Ref document number: 186953

    Country of ref document: AT

    Date of ref document: 19991215

    Kind code of ref document: T

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: NV

    Representative=s name: MICHELI & CIE INGENIEURS-CONSEILS

    Ref country code: CH

    Ref legal event code: EP

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

    Effective date: 19991124

    REF Corresponds to:

    Ref document number: 69700842

    Country of ref document: DE

    Date of ref document: 19991230

    ITF It: translation for a ep patent filed
    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: FRENCH

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

    Ref country code: PT

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

    Effective date: 20000224

    Ref country code: DK

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

    Effective date: 20000224

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2140969

    Country of ref document: ES

    Kind code of ref document: T3

    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
    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: IF02

    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: LU

    Payment date: 20160324

    Year of fee payment: 20

    Ref country code: NL

    Payment date: 20160314

    Year of fee payment: 20

    Ref country code: MC

    Payment date: 20160318

    Year of fee payment: 20

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

    Ref country code: CH

    Payment date: 20160405

    Year of fee payment: 20

    Ref country code: GB

    Payment date: 20160418

    Year of fee payment: 20

    Ref country code: ES

    Payment date: 20160504

    Year of fee payment: 20

    Ref country code: DE

    Payment date: 20160413

    Year of fee payment: 20

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

    Ref country code: IT

    Payment date: 20160408

    Year of fee payment: 20

    Ref country code: AT

    Payment date: 20160323

    Year of fee payment: 20

    Ref country code: BE

    Payment date: 20160421

    Year of fee payment: 20

    Ref country code: FR

    Payment date: 20160330

    Year of fee payment: 20

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R071

    Ref document number: 69700842

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: MK

    Effective date: 20170415

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: PE20

    Expiry date: 20170415

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: LIMR

    Effective date: 20170413

    REG Reference to a national code

    Ref country code: AT

    Ref legal event code: MK07

    Ref document number: 186953

    Country of ref document: AT

    Kind code of ref document: T

    Effective date: 20170416

    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: 20170415

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20180508

    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 EXPIRATION OF PROTECTION

    Effective date: 20170417