EP1386987A1 - Composite flame-retardant yarn comprising two types of fibres - Google Patents

Composite flame-retardant yarn comprising two types of fibres Download PDF

Info

Publication number
EP1386987A1
EP1386987A1 EP20030291896 EP03291896A EP1386987A1 EP 1386987 A1 EP1386987 A1 EP 1386987A1 EP 20030291896 EP20030291896 EP 20030291896 EP 03291896 A EP03291896 A EP 03291896A EP 1386987 A1 EP1386987 A1 EP 1386987A1
Authority
EP
European Patent Office
Prior art keywords
fibers
yarn
thermostable
textile
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20030291896
Other languages
German (de)
French (fr)
Other versions
EP1386987B1 (en
Inventor
Christian Paire
Thierry Lanier
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.)
Proline Textile
Sofileta
Original Assignee
Proline Textile
Sofileta
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 Proline Textile, Sofileta filed Critical Proline Textile
Publication of EP1386987A1 publication Critical patent/EP1386987A1/en
Application granted granted Critical
Publication of EP1386987B1 publication Critical patent/EP1386987B1/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
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D02G3/047—Blended or other yarns or threads containing components made from different materials including aramid fibres
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2631—Coating or impregnation provides heat or fire protection

Definitions

  • the invention relates to a fire-resistant composite yarn and a textile comprising at least a woven or knitted textile layer formed with such a yarn.
  • the textile is typically intended for the production of protective clothing, military clothing, firefighters or used in industry.
  • the use of the textile is adapted when the clothing must give the user some thermal protection.
  • yarns comprising fibers thermostable materials that give the garment good fire performance and mechanical resistance - especially in terms of abrasion resistance, toughness and stability when using or different washes than the garment will have to undergo-.
  • thermostable fibers are their impossibility to be dyed or printed in a simple way, in particular with a standard technique of fixed type washed.
  • the wires of the prior art are colored by a pigment type technique in which the dyes are coated on the wires.
  • thermostable fibers are particularly limiting for a military application in which the initial quality or after maintenance printed or tinted colors directly affect the quality of the camouflage conferred by the garment.
  • the invention therefore aims to remedy this drawback by proposing in particular a composite yarn comprising a lower percentage of thermostable fibers, and this without affecting either the mechanical properties or the fireproof properties of said thread.
  • the fabric when the fabric is printed or dyed in a single phase, i.e. using a single coloring process and thus using for example thermostable fibers dyed in the mass, the fabric presents a dichroism reduced in proportion to the decrease in the amount of thermostable fibers.
  • the proposed wire has a lower production cost per compared to those of the prior art.
  • the invention proposes a textile intended for the production protective clothing, said textile comprising at least one layer woven or knitted textile formed with such yarns.
  • the invention relates to an anti-fire composite wire composed of the combination of specific fibers, said yarn being in particular usable for the production of a textile for protective clothing, for example for military, fireman or used in the industry. Indeed, in such applications, constraints, particularly in terms of fire resistance and mechanical resistance, are more and more severe so that there is a significant demand for perfect the known wires, and this in a controlled cost.
  • the yarn comprises fibers that comprise a polymeric material based on of polyvinyl alcohol.
  • the flame-retarded fibers may comprise a polymeric material flame retardant.
  • the flame retardant material may be a vinyl polyhalide, in particular a polyvinyl chloride which, at its combustion, releases enough chlorine to make the fiber flammable.
  • the flame retarded fibers thus obtained therefore have, when they are subject to a flame or an important source of heat, the double property to not spread the flame and to delay the increase in yarn temperature due to the partial melting of the fibers.
  • thermostable fibers that are formed of a non-flammable material.
  • thermostable means fibers that retain their physical properties in temperatures where other fibers have lost them.
  • thermostable fibers have the function of reinforcing, besides thermal properties, the mechanical performance of the wire.
  • the use of these fibers makes it possible to obtain abrasion resistance, toughness and stability, especially when using or different washes, which is compatible with the production of protective clothing.
  • thermostable fibers make it possible to limit the formation of holes in the fabric when it is subjected to a flame, and thus to improve the fire protection provided by the garment.
  • thermostable fibers have also an advantageous effect on the limitation of the thermal shrinkage of the wire.
  • thermostable fibers were present in an amount equal to 10% relative to the total weight of the wire. This small percentage is particularly interesting because of the important part of the cost of these thermostable fibers and on the other hand, the impossibility of printing or dyeing them with simple techniques, especially with the techniques conventionally used for fireproof fibers. This constraint is particularly important in the military field because the quality of the colors printed or dyed directly affects the quality of camouflage conferred by the garment.
  • thermostable fibers needed in the wire according to the invention also makes it possible to use heat-stable fibers in which is integrated a specific color that is arranged to blend in the colors subsequently applied to the fabric, without altering the quality of the camouflage obtained.
  • thermostable fibers can be made from a material polymeric selected from the group consisting of para aramids, meta aramids, polybenzimidazole-imides, polybenzooxazoles, polyacrylates, polyphenols, polyamide-imides, poly-p-phenylenediamine terephthalamides (PPTA or M5).
  • a material polymeric selected from the group consisting of para aramids, meta aramids, polybenzimidazole-imides, polybenzooxazoles, polyacrylates, polyphenols, polyamide-imides, poly-p-phenylenediamine terephthalamides (PPTA or M5).
  • the fibers forming the yarn are intimately mixed by a conventional spinning technique.
  • the wire can between 10% and 20% of thermostable fibers to optimize the ratio between the technical advantages conferred by these fibers in relation to their cost and their coloring stress.
  • a yarn formed of 85% by weight of commercial PVA FR fibers i.e. formed fibers based on polyvinyl alcohol and an inclusion of polychloride vinyl
  • 15% by weight of meta-aramid fibers which has fire characteristics (in terms of LOI (Limit Oxygen Index), that is to say minimum concentration of oxygen required to cause inflammation of the wire in contact with a flame), mechanical strength and which are particularly interesting in the context of applications considered.
  • LOI Limit Oxygen Index
  • the wire has a LOI defined according to the ISO 4589-2 that is greater than 25%.
  • the composite yarn comprises two types of thermostable fibers, one to standard toughness-for example in aramid meta-and the other high-tenacity-by example in para aramid-.
  • high tenacity we mean typically a tenacity greater than 10cN / dtex, especially greater than 15CN / dtex.
  • the yarn can be formed by intimately mixing the fibers as previously exposed.
  • the wire can be made by a core-spun technique. Thread then comprises a core wire formed with thermostable fibers with high toughness and, associated around said core wire, a coating formed of the other fibers. The amount of thermostable fibers can then typically be set between 20% and 30% by weight of the yarn.
  • thermostable high-tenacity do not arise because they are arranged in the soul wire.
  • the invention therefore proposes a particular combination of fibers which makes it possible to optimally fill in particular the coloring constraints mentioned above, without affecting both fire and mechanical performance some thread.
  • the yarn according to the invention makes it possible to obtain a textile of flexibility enough to achieve a good touch, and in a cost compatible with an industrial production.
  • the son according to the invention are particularly intended for the realization a woven or knitted textile layer which is used in a textile for protective clothing.
  • the textile layer can be advantageously dyed or printed with a minimum of dichroism, especially in a single phase, that is to say using a single coloring process, for example fixed type washed.
  • the textile may comprise, associated on the textile layer, a layer waterproof-breathable-that is, waterproof and windproof, but permeable to water vapor - non-flammable so as to confer this property protective clothing made.
  • the breathable layer can be made in the form of a membrane or a microporous and / or hydrophilic coating, for example polyurethane or polytetrafluoroethylene (PTFE), and be associated with the textile layer by serigraphy coating of a network of adhesive dots.
  • PTFE polytetrafluoroethylene

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Woven Fabrics (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Multicomponent Fibers (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)

Abstract

Fire-resistant yarn comprises 70-90 wt.% flame-retarded polyvinyl alcohol fibers and 10-30 wt.% thermostable fibers made from a nonflammable material. An independent claim is also included for textiles for making protective clothing, comprising at least one textile layer woven or knitted from the fire-resistant yarn.

Description

L'invention concerne un fil composite anti-feu et un textile comprenant au moins une couche textile tissée ou tricotée formée avec un tel fil.The invention relates to a fire-resistant composite yarn and a textile comprising at least a woven or knitted textile layer formed with such a yarn.

Le textile est typiquement destiné à la réalisation de vêtements de protection, notamment de vêtements pour militaire, pour pompier ou utilisés dans l'industrie. De façon particulière, l'utilisation du textile est adaptée lorsque le vêtement doit conférer à l'utilisateur une certaine protection thermique.The textile is typically intended for the production of protective clothing, military clothing, firefighters or used in industry. In particular, the use of the textile is adapted when the clothing must give the user some thermal protection.

Pour de telles applications, il est connu d'utiliser des fils comprenant des fibres thermostables qui confèrent au vêtement de bonnes performances anti-feu et de résistance mécanique -en particulier en terme de résistance à l'abrasion, de ténacité et de stabilité lors de l'utilisation ou des différents lavages que le vêtement aura à subir-.For such applications, it is known to use yarns comprising fibers thermostable materials that give the garment good fire performance and mechanical resistance - especially in terms of abrasion resistance, toughness and stability when using or different washes than the garment will have to undergo-.

Toutefois, un problème qui se pose avec les fibres thermostables est leur impossibilité à être teintes ou imprimées de façon simple, notamment avec une technique standard de type fixé lavé.However, a problem with thermostable fibers is their impossibility to be dyed or printed in a simple way, in particular with a standard technique of fixed type washed.

C'est pourquoi, dans les applications considérées, les fils de l'art antérieur sont colorés par une technique de type pigmentaire dans laquelle les colorants sont enduits sur les fils.This is why, in the applications under consideration, the wires of the prior art are colored by a pigment type technique in which the dyes are coated on the wires.

Toutefois, cette technique ne permet pas d'obtenir une coloration suffisamment résistante, notamment vis-à-vis de l'abrasion, puisque l'enduction n'est que faiblement liée aux fils.However, this technique does not make it possible to obtain a sufficient coloration resistant, in particular with respect to abrasion, since the coating is only weakly related to the wires.

En outre, un autre problème qui se pose est celui du coût important des fibres thermostables.In addition, another problem that arises is the high cost of fiber thermostable.

C'est pourquoi, on a proposé d'utiliser des fils comprenant un mélange de fibres thermostables et de fibres ignifugées de coût moindre. Therefore, it has been proposed to use yarns comprising a blend of fibers thermostable and fireproof fibers of lower cost.

Toutefois, pour obtenir un fil composite qui satisfait les contraintes spécifiques des utilisations considérées, notamment en terme de résistance mécanique et de propriétés anti-feu, l'art antérieur propose d'utiliser des fibres ignifugées qui doivent être combinées à plus de 50% en poids de fibres thermostables.However, to obtain a composite yarn that satisfies the specific constraints uses considered, particularly in terms of mechanical strength and of fire-fighting properties, the prior art proposes to use flame-retardant fibers which must be combined with more than 50% by weight of thermostable fibers.

Mais, dans un tel pourcentage, les contraintes de coloration mentionnées ci-dessus demeurent, de sorte qu'on a proposé d'intégrer dans les fibres thermostables un colorant spécifique qui est agencé pour se fondre dans les couleurs appliquées ultérieurement sur le tissu.But in such a percentage, the coloring constraints mentioned above remain, so it has been proposed to integrate into the fibers thermostable a specific dye that is arranged to blend into the colors subsequently applied to the fabric.

Cette solution ne donne que partiellement satisfaction, notamment du fait du pourcentage important de fibres thermostables, et est particulièrement limitante pour une application militaire dans laquelle la qualité initiale ou après entretien des couleurs imprimées ou teintes influe directement sur la qualité du camouflage conféré par le vêtement.This solution is only partially satisfactory, particularly because of high percentage of thermostable fibers, and is particularly limiting for a military application in which the initial quality or after maintenance printed or tinted colors directly affect the quality of the camouflage conferred by the garment.

L'invention vise donc à remédier à cet inconvénient en proposant notamment un fil composite comprenant un pourcentage moindre de fibres thermostables, et ce sans affecter ni les propriétés mécaniques ni les propriétés anti-feu dudit fil.The invention therefore aims to remedy this drawback by proposing in particular a composite yarn comprising a lower percentage of thermostable fibers, and this without affecting either the mechanical properties or the fireproof properties of said thread.

Ainsi, lorsque le tissu est imprimé ou teint en une seule phase, c'est-à-dire en utilisant un seul procédé de coloration et donc en utilisant par exemple des fibres thermostables teintes dans la masse, le tissu présente un dichroïsme réduit en proportion de la diminution de la quantité de fibres thermostables.Thus, when the fabric is printed or dyed in a single phase, i.e. using a single coloring process and thus using for example thermostable fibers dyed in the mass, the fabric presents a dichroism reduced in proportion to the decrease in the amount of thermostable fibers.

En outre, toujours du fait de la réduction du pourcentage des fibres thermostables, le fil proposé présente un coût de production moindre par rapport à ceux de l'art antérieur.In addition, still due to the reduction of the percentage of fibers thermostable, the proposed wire has a lower production cost per compared to those of the prior art.

A cet effet, et selon un premier aspect, l'invention propose un fil composite anti-feu comprenant :

  • entre 70% et 90 % en poids de fibres ignifugées, lesdites fibres comprenant un matériau polymérique à base d'alcool polyvinylique ;
  • entre 10% et 30% en poids d'au moins un type de fibres thermostables qui sont formées d'un matériau ininflammable.
For this purpose, and according to a first aspect, the invention proposes an anti-fire composite wire comprising:
  • between 70% and 90% by weight of flame retarded fibers, said fibers comprising a polymeric material based on polyvinyl alcohol;
  • between 10% and 30% by weight of at least one type of thermostable fibers which are formed of a non-flammable material.

Selon un deuxième aspect, l'invention propose un textile destiné à la réalisation de vêtements de protection, ledit textile comprenant au moins une couche textile tissée ou tricotée formée avec de tels fils.According to a second aspect, the invention proposes a textile intended for the production protective clothing, said textile comprising at least one layer woven or knitted textile formed with such yarns.

D'autres objets et avantages de l'invention apparaítront au cours de la description qui suit.Other objects and advantages of the invention will appear during the description which follows.

L'invention concerne un fil composite anti-feu composé de la combinaison de fibres spécifiques, ledit fil étant notamment utilisable pour la réalisation d'un textile pour vêtement de protection, par exemple pour militaire, pour pompier ou utilisé dans l'industrie. En effet, dans de telles applications, les contraintes, notamment en terme de propriétés anti-feu et de résistance mécanique, sont de plus en plus sévères de sorte qu'il existe une demande importante pour perfectionner les fils connus, et ce dans un coût maítrisé.The invention relates to an anti-fire composite wire composed of the combination of specific fibers, said yarn being in particular usable for the production of a textile for protective clothing, for example for military, fireman or used in the industry. Indeed, in such applications, constraints, particularly in terms of fire resistance and mechanical resistance, are more and more severe so that there is a significant demand for perfect the known wires, and this in a controlled cost.

Le fil comprend des fibres qui comprennent un matériau polymérique à base d'alcool polyvinylique.The yarn comprises fibers that comprise a polymeric material based on of polyvinyl alcohol.

Toutefois, ce type de matériau n'est pas ininflammable en tant que tel. C'est pourquoi, pour obtenir un fil anti-feu, les fibres utilisées doivent être ignifugées.However, this type of material is not non-flammable as such. It is why, to obtain a fireproof wire, the fibers used must be fireproofed.

A cet effet, les fibres ignifugées peuvent comprendre un matériau polymérique ignifugeant. Dans un exemple particulier, le matériau ignifugeant peut être un polyhalogénure de vinyle, notamment un polychlorure de vinyle qui, lors de sa combustion, dégage une quantité de chlore suffisante pour rendre la fibre ininflammable. For this purpose, the flame-retarded fibers may comprise a polymeric material flame retardant. In a particular example, the flame retardant material may be a vinyl polyhalide, in particular a polyvinyl chloride which, at its combustion, releases enough chlorine to make the fiber flammable.

Les fibres ignifugées ainsi obtenues présentent donc, lorsqu'elles sont soumises à une flamme ou à une source importante de chaleur, la double propriété de ne pas propager la flamme et de retarder l'augmentation en température du fil grâce à la fusion partielle des fibres.The flame retarded fibers thus obtained therefore have, when they are subject to a flame or an important source of heat, the double property to not spread the flame and to delay the increase in yarn temperature due to the partial melting of the fibers.

Le problème qui se pose avec de telles fibres ignifugées est celui de leur stabilité thermique. En effet, l'absorption d'énergie thermique est obtenue grâce à la fusion partielle des fibres, ce qui entraíne une déformation de celles-ci.The problem that arises with such fire-resistant fibers is that of their thermal stability. Indeed, the absorption of thermal energy is obtained thanks to the partial melting of the fibers, which causes a deformation thereof.

Pour pallier cet inconvénient, les fibres ignifugées sont associées à au moins un type de fibres thermostables qui sont formées d'un matériau ininflammable. Par thermostable, on entend des fibres qui conservent leurs propriétés physiques dans des températures où les autres fibres les ont perdues.To overcome this drawback, the fire-resistant fibers are associated with at least one type of thermostable fibers that are formed of a non-flammable material. By thermostable means fibers that retain their physical properties in temperatures where other fibers have lost them.

Les fibres thermostables ont notamment pour fonction de renforcer, outre les propriétés thermiques, les performances mécaniques du fil. En particulier, l'utilisation de ces fibres permet d'obtenir une résistance à l'abrasion, une ténacité et une stabilité, notamment lors de l'utilisation ou des différents lavages, qui est compatible avec la réalisation de vêtements de protection. En outre, les fibres thermostables permettent de limiter la formation de trous dans le tissu lorsque celui-ci est soumis à une flamme, et donc d'améliorer la protection anti-feu conférée par le vêtement. Enfin, les fibres thermostables ont également un effet avantageux sur la limitation du retrait thermique du fil.In particular, the thermostable fibers have the function of reinforcing, besides thermal properties, the mechanical performance of the wire. In particular, the use of these fibers makes it possible to obtain abrasion resistance, toughness and stability, especially when using or different washes, which is compatible with the production of protective clothing. In In addition, thermostable fibers make it possible to limit the formation of holes in the fabric when it is subjected to a flame, and thus to improve the fire protection provided by the garment. Finally, thermostable fibers have also an advantageous effect on the limitation of the thermal shrinkage of the wire.

La demanderesse a fait des essais et a constaté que, en combinaison avec les fibres ignifugées particulières utilisées, la contribution des fibres thermostables était intéressante dès qu'elles étaient présentes en une quantité égale à 10% par rapport au poids total du fil. Ce faible pourcentage est particulièrement intéressant du fait d'une part du coût important de ces fibres thermostables et d'autre part de l'impossibilité de les imprimer ou de les teindre avec des techniques simples, notamment avec les techniques classiquement utilisées pour les fibres ignifugées. Cette contrainte est particulièrement importante dans le domaine militaire du fait que la qualité des couleurs imprimées ou teintes influe directement sur la qualité du camouflage conféré par le vêtement. Et, le faible pourcentage minimum de fibres thermostables nécessaire dans le fil suivant l'invention permet en outre d'utiliser des fibres thermostables dans lesquelles est intégrée une couleur spécifique qui est agencée pour se fondre dans les couleurs appliquées ultérieurement sur le tissu, et ce sans altérer notablement la qualité du camouflage obtenu.The plaintiff has tested and found that, in combination with the particular fireproof fibers used, the contribution of thermostable fibers was interesting when they were present in an amount equal to 10% relative to the total weight of the wire. This small percentage is particularly interesting because of the important part of the cost of these thermostable fibers and on the other hand, the impossibility of printing or dyeing them with simple techniques, especially with the techniques conventionally used for fireproof fibers. This constraint is particularly important in the military field because the quality of the colors printed or dyed directly affects the quality of camouflage conferred by the garment. And the low minimum percentage of thermostable fibers needed in the wire according to the invention also makes it possible to use heat-stable fibers in which is integrated a specific color that is arranged to blend in the colors subsequently applied to the fabric, without altering the quality of the camouflage obtained.

Dans le cas où l'on souhaite un fil composite à plus haute résistance mécanique, il est également possible d'intégrer jusqu'à 30% de fibres thermostables par rapport au poids total du fil.In the case where a higher strength composite yarn is desired mechanical, it is also possible to integrate up to 30% of fiber thermostable relative to the total weight of the wire.

Les fibres thermostables peuvent être réalisées à base d'un matériau polymérique choisi dans le groupe comprenant les para aramides, les méta aramides, les polybenzimidazole-imides, les polybenzooxazoles, les polyacrylates, les polyphénols, les polyamide-imides, les poly-p-phenylènediamine-terephtalamides (PPTA ou M5).The thermostable fibers can be made from a material polymeric selected from the group consisting of para aramids, meta aramids, polybenzimidazole-imides, polybenzooxazoles, polyacrylates, polyphenols, polyamide-imides, poly-p-phenylenediamine terephthalamides (PPTA or M5).

Selon une réalisation, les fibres formant le fil sont mélangées de façon intime par une technique de filature classique. Dans cette réalisation, le fil peut comprendre entre 10% et 20% de fibres thermostables pour optimiser le rapport entre les avantages techniques conférés par ces fibres par rapport à leur coût et à leur contrainte de coloration.In one embodiment, the fibers forming the yarn are intimately mixed by a conventional spinning technique. In this embodiment, the wire can between 10% and 20% of thermostable fibers to optimize the ratio between the technical advantages conferred by these fibers in relation to their cost and their coloring stress.

Dans un exemple particulier de fil selon cette réalisation de l'invention, on peut citer un fil formé de 85% en poids de fibres PVA FR commercial (c'est-à-dire de fibres formées à base d'alcool polyvinylique et d'une inclusion de polychlorure de vinyle) et de 15% en poids de fibres en meta aramide, qui présente des caractéristiques anti-feu (en terme de LOI (Limit Oxygen Index) c'est-à-dire de concentration minimum d'oxygène nécessaire pour entraíner l'inflammation du fil au contact d'une flamme), de résistance mécanique et de capacité de coloration qui sont particulièrement intéressantes dans le cadre des applications considérées. En particulier, le fil présente une LOI définie selon la norme ISO 4589-2 qui est supérieure à 25%. In a particular example of a wire according to this embodiment of the invention, it is possible quote a yarn formed of 85% by weight of commercial PVA FR fibers (i.e. formed fibers based on polyvinyl alcohol and an inclusion of polychloride vinyl) and 15% by weight of meta-aramid fibers, which has fire characteristics (in terms of LOI (Limit Oxygen Index), that is to say minimum concentration of oxygen required to cause inflammation of the wire in contact with a flame), mechanical strength and which are particularly interesting in the context of applications considered. In particular, the wire has a LOI defined according to the ISO 4589-2 that is greater than 25%.

Selon une réalisation, notamment dans le cas où l'on souhaite un fil à ténacité renforcée, le fil composite comprend deux types de fibres thermostables, l'un à ténacité standard -par exemple en meta aramide- et l'autre à haute ténacité-par exemple en para aramide-. Par le terme « haute ténacité » on entend typiquement une ténacité supérieure à 10cN/dtex, notamment supérieure à 15cN/dtex.According to one embodiment, particularly in the case where a tenacity yarn is desired reinforced, the composite yarn comprises two types of thermostable fibers, one to standard toughness-for example in aramid meta-and the other high-tenacity-by example in para aramid-. By the term "high tenacity" we mean typically a tenacity greater than 10cN / dtex, especially greater than 15CN / dtex.

Dans cette réalisation, le fil peut être formé par mélange intime des fibres tel qu'exposé précédemment. A titre d'exemple, on peut citer un fil formé de 85% en poids de fibres PVA FR commercial, de 10% en poids de fibres en meta aramide et de 5% en poids de fibres en para aramide.In this embodiment, the yarn can be formed by intimately mixing the fibers as previously exposed. By way of example, mention may be made of a yarn formed of 85% by weight of commercial PVA FR fibers, 10% by weight of meta fibers aramid and 5% by weight of para aramid fibers.

En variante, le fil peut être réalisé par une technique de type core-spun. Le fil comprend alors un fil d'âme formé avec les fibres thermostables à haute ténacité et, associé autour dudit fil d'âme, un enrobage formé des autres fibres. La quantité de fibres thermostables peut alors être typiquement fixée entre 20% et 30% en poids du fil.Alternatively, the wire can be made by a core-spun technique. Thread then comprises a core wire formed with thermostable fibers with high toughness and, associated around said core wire, a coating formed of the other fibers. The amount of thermostable fibers can then typically be set between 20% and 30% by weight of the yarn.

Notons que dans cette réalisation, les contraintes de coloration des fibres thermostables à haute ténacité ne se posent pas du fait qu'elles sont disposées dans le fil d'âme.Note that in this embodiment, fiber coloring constraints thermostable high-tenacity do not arise because they are arranged in the soul wire.

L'invention propose donc une combinaison particulière de fibres qui permet de remplir de façon optimale notamment les contraintes de coloration mentionnées ci-dessus, et ce sans affecter les performances tant anti-feu que mécaniques du fil. En outre, le fil selon l'invention permet d'obtenir un textile de souplesse suffisante pour obtenir un toucher avantageux, et ce dans un coût compatible avec une production industrielle.The invention therefore proposes a particular combination of fibers which makes it possible to optimally fill in particular the coloring constraints mentioned above, without affecting both fire and mechanical performance some thread. In addition, the yarn according to the invention makes it possible to obtain a textile of flexibility enough to achieve a good touch, and in a cost compatible with an industrial production.

C'est pourquoi, les fils selon l'invention sont notamment destinés à la réalisation d'une couche textile tissée ou tricotée qui est utilisée dans un textile pour des vêtements de protection. Therefore, the son according to the invention are particularly intended for the realization a woven or knitted textile layer which is used in a textile for protective clothing.

Comme expliqué précédemment, la couche textile peut être avantageusement teint ou imprimé avec un minimum de dichroïsme, notamment en une seule phase, c'est-à-dire en utilisant un seul procédé de coloration, par exemple de type fixé lavé.As explained above, the textile layer can be advantageously dyed or printed with a minimum of dichroism, especially in a single phase, that is to say using a single coloring process, for example fixed type washed.

En outre, le textile peut comprendre, associé sur la couche textile, une couche imper-respirante -c'est-à-dire imperméable à l'eau liquide et au vent mais perméable à la vapeur d'eau- ininflammable de sorte à conférer cette propriété au vêtement de protection confectionné.In addition, the textile may comprise, associated on the textile layer, a layer waterproof-breathable-that is, waterproof and windproof, but permeable to water vapor - non-flammable so as to confer this property protective clothing made.

La couche imper-respirante peut être réalisée sous la forme d'une membrane ou d'une enduction micro poreuse et/ou hydrophilique, par exemple en polyuréthane ou en polytétrafluoroéthylène (PTFE), et être associée à la couche textile par enduction sérigraphie d'un réseau de points adhésifs.The breathable layer can be made in the form of a membrane or a microporous and / or hydrophilic coating, for example polyurethane or polytetrafluoroethylene (PTFE), and be associated with the textile layer by serigraphy coating of a network of adhesive dots.

Claims (12)

Fil composite anti-feu comprenant : entre 70% et 90 % en poids de fibres ignifugées, lesdites fibres comprenant un matériau polymérique à base d'alcool polyvinylique ; entre 10% et 30% en poids d'au moins un type de fibres thermostables qui sont formées d'un matériau ininflammable. Fire-resistant composite wire comprising: between 70% and 90% by weight of flame retarded fibers, said fibers comprising a polymeric material based on polyvinyl alcohol; between 10% and 30% by weight of at least one type of thermostable fibers which are formed of a non-flammable material. Fil selon la revendication 1, caractérisé en ce que les fibres ignifugées comprennent en outre un matériau polymérique ignifugeant.Yarn according to claim 1, characterized in that the flame-retarded fibers further comprise a flame retardant polymeric material. Fil selon la revendication 2, caractérisé en ce que le matériau polymérique ignifugeant est formé à base de polyhalogénure de vinyle, notamment de polychlorure de vinyle.Wire according to claim 2, characterized in that the flame retardant polymeric material is formed based on polyvinyl halide, especially polyvinyl chloride. Fil selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les fibres thermostables sont réalisées à base d'un matériau polymérique choisi dans le groupe comprenant les para aramides, les méta aramides, les polybenzimidazole-imides, les polybenzooxazoles, les polyacrylates, les polyphénols, les polyamide-imides, les poly-p-phenylènediamine-terephtalamides.Yarn according to any one of Claims 1 to 3, characterized in that the thermostable fibers are made based on a polymeric material chosen from the group comprising para-aramids, meta-aramids, polybenzimidazole-imides, polybenzooxazoles, polyacrylates, polyphenols, polyamide-imides, poly-p-phenylenediamine terephthalamides. Fil selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il comprend un type de fibres thermostables à haute ténacité.Yarn according to any one of claims 1 to 4, characterized in that it comprises a type of high-tenacity thermostable fibers. Fil selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les fibres formant le fil sont mélangées de façon intime.Yarn according to any one of claims 1 to 5, characterized in that the fibers forming the yarn are intimately mixed. Fil selon la revendication 6, caractérisé en ce qu'il comprend entre 10% et 20% en poids de fibres thermostables. Yarn according to claim 6, characterized in that it comprises between 10% and 20% by weight of thermostable fibers. Fil selon la revendication 5, caractérisé en ce qu'il comprend un fil d'âme formé des fibres à haute ténacité et, associé autour dudit fil d'âme, un enrobage formé des autres fibres.Yarn according to claim 5, characterized in that it comprises a core yarn formed of high-tenacity fibers and, associated around said core yarn, a coating formed of the other fibers. Fil selon la revendication 8, caractérisé en ce qu'il comprend entre 20% et 30% en poids de fibres thermostables.Yarn according to claim 8, characterized in that it comprises between 20% and 30% by weight of thermostable fibers. Textile destiné à la réalisation de vêtements de protection, caractérisé en ce qu'il comprend au moins une couche textile tissée ou tricotée formée avec des fils selon l'une quelconque des revendications 1 à 9.Textile for the production of protective clothing, characterized in that it comprises at least one woven or knitted textile layer formed with yarns according to any one of claims 1 to 9. Textile selon la revendication 10, caractérisé en ce que la couche textile est teinte ou imprimée.Textile according to claim 10, characterized in that the textile layer is dyed or printed. Textile selon la revendication 10 ou 11, caractérisé en ce qu'il comprend, associée à la couche textile, une couche imper-respirante ininflammable.Textile according to claim 10 or 11, characterized in that it comprises, associated with the textile layer, a non-flammable waterproof breathable layer.
EP20030291896 2002-07-31 2003-07-30 Composite flame-retardant yarn comprising two types of fibres Expired - Lifetime EP1386987B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0209769 2002-07-31
FR0209769A FR2843132B1 (en) 2002-07-31 2002-07-31 TWO-TYPE FIBER FIRE-RESISTANT COMPOSITE YARN

Publications (2)

Publication Number Publication Date
EP1386987A1 true EP1386987A1 (en) 2004-02-04
EP1386987B1 EP1386987B1 (en) 2005-09-21

Family

ID=30011610

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20030291896 Expired - Lifetime EP1386987B1 (en) 2002-07-31 2003-07-30 Composite flame-retardant yarn comprising two types of fibres

Country Status (9)

Country Link
US (1) US20060234578A1 (en)
EP (1) EP1386987B1 (en)
CN (1) CN1671899A (en)
AT (1) ATE305061T1 (en)
AU (1) AU2003281834A1 (en)
CA (1) CA2493943A1 (en)
DE (1) DE60301652T2 (en)
FR (1) FR2843132B1 (en)
WO (1) WO2004012540A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007073539A1 (en) * 2005-12-16 2007-06-28 E.I. Du Pont De Nemours And Company Thermal performance garments comprising an outer shell fabric of pipd and aramid fibers
WO2007073540A1 (en) * 2005-12-16 2007-06-28 E.I. Du Pont De Nemours And Company Thermal performance garments comprising an ultraviolet light tolerant outer shell fabric of polypyridobisimidazole and polybenzobisoxazole fibers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2843133B1 (en) * 2002-07-31 2005-01-14 Proline Textile FIRE-FIGURING WIRE WITH THREE TYPES OF FIBERS
EP1960464B1 (en) * 2005-12-16 2011-06-08 E.I. Du Pont De Nemours And Company Fabrics made from a blend of polypyridobisimidazole/flame-retardant treated cellulose fibers and articles made therefrom
CN107938089A (en) * 2017-12-04 2018-04-20 四川航天五源复合材料有限公司 A kind of yarn for protective garment

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127698A (en) * 1976-07-07 1978-11-28 Kohjin Co., Ltd. Composite fiber
DE3307449A1 (en) * 1982-03-15 1983-09-22 Taunus Textildruck Zimmer GmbH & Co KG, 6370 Oberursel Flame-retardant textile fabric made from two or more chemical fibres
EP0533931A1 (en) * 1990-06-11 1993-03-31 Teijin Limited Fabric made from blended yarn comprising aromatic polyamide fiber and polyester fiber
EP0908546A1 (en) * 1996-05-13 1999-04-14 Kaneka Corporation Thermal resistance-improved flame retardant cloth
EP0943705A1 (en) * 1997-10-07 1999-09-22 Kuraray Co., Ltd. Flame-retardant polyvinyl alcohol base fiber

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0310201A3 (en) * 1987-10-02 1990-05-23 Dsm N.V. Combinations of polymer filaments or yarns having a low coefficient of friction and filaments or yarns having a high coefficient of friction, and use thereof
FR2673207B1 (en) * 1991-02-25 1994-07-22 Picardie Lainiere COMPOSITE FIRE PROTECTION LINING.
FR2843133B1 (en) * 2002-07-31 2005-01-14 Proline Textile FIRE-FIGURING WIRE WITH THREE TYPES OF FIBERS

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127698A (en) * 1976-07-07 1978-11-28 Kohjin Co., Ltd. Composite fiber
DE3307449A1 (en) * 1982-03-15 1983-09-22 Taunus Textildruck Zimmer GmbH & Co KG, 6370 Oberursel Flame-retardant textile fabric made from two or more chemical fibres
EP0533931A1 (en) * 1990-06-11 1993-03-31 Teijin Limited Fabric made from blended yarn comprising aromatic polyamide fiber and polyester fiber
EP0908546A1 (en) * 1996-05-13 1999-04-14 Kaneka Corporation Thermal resistance-improved flame retardant cloth
EP0943705A1 (en) * 1997-10-07 1999-09-22 Kuraray Co., Ltd. Flame-retardant polyvinyl alcohol base fiber

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007073539A1 (en) * 2005-12-16 2007-06-28 E.I. Du Pont De Nemours And Company Thermal performance garments comprising an outer shell fabric of pipd and aramid fibers
WO2007073540A1 (en) * 2005-12-16 2007-06-28 E.I. Du Pont De Nemours And Company Thermal performance garments comprising an ultraviolet light tolerant outer shell fabric of polypyridobisimidazole and polybenzobisoxazole fibers

Also Published As

Publication number Publication date
WO2004012540A3 (en) 2004-05-13
ATE305061T1 (en) 2005-10-15
AU2003281834A8 (en) 2004-02-23
EP1386987B1 (en) 2005-09-21
FR2843132A1 (en) 2004-02-06
FR2843132B1 (en) 2004-10-29
WO2004012540A2 (en) 2004-02-12
CN1671899A (en) 2005-09-21
US20060234578A1 (en) 2006-10-19
CA2493943A1 (en) 2004-02-12
AU2003281834A1 (en) 2004-02-23
DE60301652D1 (en) 2005-10-27
DE60301652T2 (en) 2006-06-22

Similar Documents

Publication Publication Date Title
EP2007943B1 (en) Ultraviolet-resistant fabrics and methods for making them
RU2326197C2 (en) Textile material from coloured fibre threads and its use for camouflage items manufacture
CA2427598A1 (en) High-visibility textile surface
EP3237659B1 (en) Fabric for manufacturing garments for fire protection
CA2763083C (en) Flame resistant fabric with tracing yarns
FR3046609A1 (en)
FR2883134A1 (en) FIRE PROTECTION FABRIC
EP1386987B1 (en) Composite flame-retardant yarn comprising two types of fibres
EP1386988B1 (en) Composite flame retardant yarn comprising three types of fibres
FR2581665A1 (en) Yarns of thermally stable textile materials
JP2783422B2 (en) Wholly aromatic polyamide composition
JP3728030B2 (en) Reinforced fabrics and fabric products with excellent light resistance
JP5243230B2 (en) Totally aromatic polyamide fiber structure
FR2987846A1 (en) HIGH TENACITY META-ARAMIDE BASED YARN AND TEXTILE USING THE SAME
FR3008434A1 (en) METHOD FOR COLORING A NON-FIRE TEXTILE SUPPORT IN HIGH VISIBILITY COLOR
KR101555038B1 (en) Glass fiber yarn coated with color additives and manufacturing method thereof
KR20200009876A (en) Meta-Aramid Fiber improved dyeability
FR2691721A1 (en) Textile articles with good mechanical properties.
EP1072703A1 (en) Woven fabric with certain elasticity and capable for making fire-proof or industry heat protecting garments
CN110424096B (en) High-strength object throwing umbrella rope with anti-burning and micro-buffering functions and manufacturing method thereof
FR3107906A1 (en) Fabric for personal protection and clothing comprising such a fabric
FR2876253A1 (en) Textile complex, useful as fire proof clothing, comprises two distinct layers such as primary layer formed of fabric with a base of material and secondary layer of fabric with a base of material dyed with fluorescent colors
JP2008038299A (en) Heat-resistant fabric having light resistance
EP2661973A1 (en) Bilayer fabric for protection against heat, and garment for protection against fire and/or heat using said fabric
FR2842077A1 (en) REINFORCEMENT TEXTILE COMPRISING A WIRE ARRAY

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: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

17P Request for examination filed

Effective date: 20040504

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050921

Ref country code: SI

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

Effective date: 20050921

Ref country code: FI

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

Effective date: 20050921

Ref country code: CZ

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

Effective date: 20050921

Ref country code: SK

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

Effective date: 20050921

Ref country code: RO

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

Effective date: 20050921

Ref country code: AT

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

Effective date: 20050921

Ref country code: IE

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

Effective date: 20050921

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REF Corresponds to:

Ref document number: 60301652

Country of ref document: DE

Date of ref document: 20051027

Kind code of ref document: P

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

Ref country code: DK

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

Effective date: 20051221

Ref country code: SE

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

Effective date: 20051221

Ref country code: GR

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

Effective date: 20051221

Ref country code: BG

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

Effective date: 20051221

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

Ref country code: ES

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

Effective date: 20060101

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: 20060221

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

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

Effective date: 20060322

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

Effective date: 20060315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: BE

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

Effective date: 20060731

Ref country code: MC

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

Effective date: 20060731

26N No opposition filed

Effective date: 20060622

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070330

REG Reference to a national code

Ref country code: FR

Ref legal event code: RN

REG Reference to a national code

Ref country code: FR

Ref legal event code: FC

BERE Be: lapsed

Owner name: SOFILETA

Effective date: 20060731

Owner name: PROLINE TEXTILE

Effective date: 20060731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: FR

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

Effective date: 20060731

Ref country code: LI

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

Effective date: 20070731

Ref country code: CH

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

Effective date: 20070731

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

Ref country code: EE

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

Effective date: 20050921

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

Ref country code: LU

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

Effective date: 20060730

Ref country code: TR

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

Effective date: 20050921

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: FR

Effective date: 20071017

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

Ref country code: CY

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

Effective date: 20050921

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: 20100730

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: IT

Effective date: 20110616

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

Ref country code: IT

Payment date: 20140731

Year of fee payment: 12

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: 20150730

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

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

Ref country code: GB

Payment date: 20170728

Year of fee payment: 15

Ref country code: DE

Payment date: 20170728

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60301652

Country of ref document: DE

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

Effective date: 20180730

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

Ref country code: GB

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

Effective date: 20180730

Ref country code: DE

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

Effective date: 20190201

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

Ref country code: FR

Payment date: 20230124

Year of fee payment: 20