EP1216273A1 - Extrusible thermoplastic material and fibre micromodule made from same - Google Patents

Extrusible thermoplastic material and fibre micromodule made from same

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Publication number
EP1216273A1
EP1216273A1 EP00962641A EP00962641A EP1216273A1 EP 1216273 A1 EP1216273 A1 EP 1216273A1 EP 00962641 A EP00962641 A EP 00962641A EP 00962641 A EP00962641 A EP 00962641A EP 1216273 A1 EP1216273 A1 EP 1216273A1
Authority
EP
European Patent Office
Prior art keywords
parts
material according
vinyl acetate
ethylene
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00962641A
Other languages
German (de)
French (fr)
Inventor
Bertrand Ducroix
Daniel Bernier
Raymond Petrus
Bernard Poisson
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.)
Silec Cable SAS
Original Assignee
Sagem SA
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 Sagem SA filed Critical Sagem SA
Publication of EP1216273A1 publication Critical patent/EP1216273A1/en
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4479—Manufacturing methods of optical cables
    • G02B6/4486—Protective covering
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to an extrudable material making it possible to form thin films, comprising an olefinic polymer.
  • the invention finds a particularly important, although not exclusive, application in the constitution of sheaths of sheathed optical fiber micromodules incorporable in a cable such as that described in document EP-A-0 468 878 to which reference may be made.
  • micromodules having a bundle of optical fibers sheathed in mutual contact, enclosed with a sealing gel in an extruded support envelope, it is desirable to fulfill conditions which are in some contradictory measure. For example, we often look for both, especially in the case of the creation of micromodules:
  • an electrical insulating material comprising an alloy of at least partially crosslinked polymers, in particular containing an EVA (ethyl alkyl acetate) copolymer with more than 40% vinyl acetate, with inorganic fillers at a content sufficient to make the material flame retardant.
  • EVA ethyl alkyl acetate
  • the present invention aims in particular to provide an extrudable material in thin film representing a satisfactory compromise between the different results to be achieved.
  • the invention notably proposes for this purpose a thin film extrudable material, consisting of a composition containing at least one (possibly several) practically non-crosslinked thermoplastic olefin polymer and a content of fillers of between 25 to 65% by weight of the composition, said material in the undivided state having a tensile strength of between 6 and 20 Mpa and an elongation at break of between 50 and 300%.
  • the shore hardness of the material is advantageously between 35 and 55 D.
  • the choice of a Shore D hardness exceeding 35 makes it possible, when the material is used to form a micromodule sheath, to ensure satisfactory cylindricity and to avoid the so-called "straw" effect, formed by the formation of a brutal bend during the flexions necessary for making the connections.
  • the strippability is sufficient so as not to require the use of special tools.
  • the above minimum characteristics, in particular the tensile strength and the elongation at break avoid excessive brittleness of the material during handling. In particular, these minima allow manipulation during the manufacture of a cable or connections without excessive risk of damage.
  • the minimum filler content indicated above makes it possible to reduce the expansion and retraction of the materials during temperature variations which occur during the manufacture of a cable.
  • the presence of a sufficient content of fillers makes it possible to avoid the risk of bonding of the micromodules to each other, on sheathed fibers or on an external envelope.
  • the fillers will generally be mineral. It is possible in particular to use alumina (hydrated or not), chalk, kaolin, talc, silica, magnesium hydroxide and their mixtures. All these loads reduce the elongation at break and the expansion or retraction during temperature variations. In addition, they increase the thermal inertia and the heat capacity.
  • the maximum level of fillers envisaged above makes it possible to maintain the viscosity at a level compatible with thin film extrusion.
  • the olefin polymers which can be used are substantially the same as those commonly used at present.
  • the following products can be mentioned:
  • the second polymer is EVA, a compound having no more than 30% of vinyl acetate co-monomer will be used in order to maintain sufficient hardness and mechanical characteristics.
  • EBA, EEA or EMA have properties close to EVA.
  • EPR and EPR have properties close to EVA.
  • EPDM will be used with sufficiently high levels of ethylene to prevent them from having properties that approximate those of an elastomer.
  • the extrudable material will generally additionally contain plasticizers of low content, not exceeding a few percent by weight, such as aliphatic oils or phthalates (for example di-octyl or didecyl phthalate), adipates, trimellitates , etc.
  • plasticizers of low content such as aliphatic oils or phthalates (for example di-octyl or didecyl phthalate), adipates, trimellitates , etc.
  • silanes or aminosilanes will be added, such as:
  • silanes strengthen the bond between the fillers and the polymer. In the absence of crosslinking agent, the silane does not risk causing crosslinking which, moreover, would not be possible if the material were used to form optical fiber sheaths, the temperatures required for crosslinking not being then not reached during extrusion.
  • the invention also provides an optical fiber micromodule comprising a bundle of optical fibers and a sheath surrounding the bundle in a thin film of an extrudable material, characterized in that the sheath is made up of a composition containing a thermoplastic olefin polymer and a charge rate between 25 to 65% by weight of the composition, said material in the undivided state having a tensile strength of between 6 and 20 Mpa and an elongation at break of between 50 and 300%.
  • the following description refers to the single figure which shows a micromodule in a deformed state which it is likely to take when it is pressed against other micromodules by an external envelope.
  • the micromodule comprises several individually sheathed optical fibers 10 contained in a sheath 12 which must be easily tearable to allow the stripping of the ends of the fibers for connections.
  • This sheath 12 is generally formed by extrusion on the bundle of optical fibers 10 during the drawing of the latter and then takes an approximately circular shape when the bundle of fibers itself has a periphery whose shape does not deviate too much from the circle. circumscribed.
  • the sheath encloses the fibers and is indeed applied against them. Inside a cable, the pressure of the micromodules against each other can deform their cross-section and cause it, for example, to that illustrated.
  • the control material consists of polyethylene having a nominal density of 0.92 and a "melt flow index" of 0.3 g / 10 min at 190 ° C, under a pressure of 21.6 N. This material was used to form the sheath of a micromodule, by extrusion on a bundle of four optical fibers.
  • the sheath 12 formed had a diameter of 1 mm and a thickness of 0.12 mm. Extrusion is done without difficulty and the sheath obtained is well cylindrical.
  • composition comprising, by weight:
  • additives antioxidants, silane, lubricant
  • the ingredients are mixed for 10 minutes, up to 160 ° C. After calendering on a roller mixer, the material is cut, then molded at 180 ° C under pressure, in the form of plates making it possible to carry out measurements characterizing the material.
  • the composition was used to form micromodules. For this, it was put in the form of granules which are introduced into an extruder 45 mm in diameter, and 24 diameters in length. Extrusion temperatures are between 130 and 165 ° C, from the feed hopper to the extrusion head.
  • the first was a shaping at a speed of 100m / min, to obtain a tube of 0.90 mm in external diameter, and 0.12 mm in radial thickness.
  • the shaping was identical except that we introduce through the head of the extruder 4 colored optical fibers, and that we simultaneously inject a sealing gel to form a module which, after cooling of the extruded material, is collected in a tank where it freely winds up flat.
  • the composition of the material is identical to Example 1, except that the filler based on hydrated alumina is replaced by a filler based on calcium carbonate.
  • the mixing is carried out under the same conditions, and a micromodule with a diameter of 0.85 mm and a thickness of 0.11 mm is extruded at 100 m / min.
  • the characteristics below show how modules with a correct chemical resistance are obtained with such a formulation, despite the small thickness of the sheath of the module.
  • Example 2 A formulation identical to Example 1 is produced, except that the alumina-based filler is replaced by a kaolinic filler, and its concentration lowered to 65 parts.
  • the paraffinic plasticizer is replaced by an oil of isononyl adipate type.
  • the various ingredients are introduced in an internal mixer, mixed up to approximately 160 ° C., and granules.
  • the characteristics of the material on the plate are as follows:
  • the sealing gel is the "Macroplast CF 300" of the company

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention concerns a material for forming thin films. It consists of a composition containing an olefin polymer and a filler ratio ranging between 25 and 65 wt.% of the composition, said material in undivided state having a tensile strength ranging between 6 and 20 Mpa and an elongation at break ranging between 50 and 300 %.

Description

MATERIAU THERMOPLASTIQUE EXTRUDABLE ET MICROMODULE DE FIBRE FABRIQUE A PARTIR D'UN TEL MATERIAU EXTRUDABLE THERMOPLASTIC MATERIAL AND FIBER MICROMODULE MANUFACTURED FROM SUCH A MATERIAL
La présente invention a pour objet un matériau extrudable permettant de constituer des pellicules de faible épaisseur, comportant un polymère oléfinique. L'invention trouve une application particulièrement importante, bien que non exclusive, dans la constitution de gaines de micromodules de fibres optiques gainées incorporables dans un câble tel que celui décrit dans le document EP-A-0 468 878 auquel on pourra se reporter.The present invention relates to an extrudable material making it possible to form thin films, comprising an olefinic polymer. The invention finds a particularly important, although not exclusive, application in the constitution of sheaths of sheathed optical fiber micromodules incorporable in a cable such as that described in document EP-A-0 468 878 to which reference may be made.
Pour un certain nombre d'applications, et notamment pour la constitution de micromodules ayant un faisceau de fibres optiques gainées en contact mutuel, enfermé avec un gel d'étanchéité dans une enveloppe de maintien extrudee, il est souhaitable de remplir des conditions qui sont dans une certaine mesure contradictoires. Par exemple, on recherche souvent à la fois, notamment dans le cas de la constitution de micromodules :For a certain number of applications, and in particular for the constitution of micromodules having a bundle of optical fibers sheathed in mutual contact, enclosed with a sealing gel in an extruded support envelope, it is desirable to fulfill conditions which are in some contradictory measure. For example, we often look for both, especially in the case of the creation of micromodules:
- une aptitude à l'extrusion en pellicule mince (si possible vers 0,1 mm),- aptitude for extrusion in thin film (if possible around 0.1 mm),
- la compatibilité du matériau avec les gels habituels d'étanchéité,- the compatibility of the material with the usual sealing gels,
- une résistance suffisante du matériau mis sous forme de pellicule mince, afin de permettre une manipulation au cours d'opérations ultérieures sans risque de déchirure,- sufficient strength of the material in the form of a thin film, to allow handling during subsequent operations without risk of tearing,
- l'absence de collage de la pellicule de gaine du micromodule sur les fibres, lors du chauffage qui intervient du fait de la mise en place de l'enveloppe extérieure en matériau thermoplastique,the absence of bonding of the sheathing film of the micromodule on the fibers, during the heating which takes place due to the installation of the outer envelope of thermoplastic material,
- le maintien d'une cylindricité correcte lors de la fabrication du micromodule et de l'assemblage des micromodules pour constituer un câble,- maintaining a correct cylindricity during the manufacture of the micromodule and the assembly of the micromodules to form a cable,
- un retrait réduit au cours de l'extrusion de la gaine pour constituer le micromodule, et au cours du refroidissement, cela pour éviter des contraintes sur les fibres optiques,- a reduced shrinkage during the extrusion of the sheath to constitute the micromodule, and during cooling, this to avoid stresses on the optical fibers,
- une coloration aisée du matériau, permettant d'identifier les micromodules,- easy coloring of the material, making it possible to identify the micromodules,
- une extensibilité limitée permettant de dénuder facilement un micromodule afin de préparer les extrémités pour raccorder les fibres,- limited extensibility making it possible to easily strip a micromodule in order to prepare the ends for joining the fibers,
- enfin, une résistance élevée aux produits chimiques utilisés lors des opérations effectuées sur les câbles, par exemple au solvant de nettoyage. Dans le cas de la fabrication de câbles à fibres optiques, certaines des caractéristiques ci-dessus sont essentielles, notamment la résistance mécanique, y compris lors du vieillissement thermique, et la compatibilité avec les gels d'étanchéité et les solvants de nettoyage utilisés pour éliminer le gel et les salissures avant d'effectuer le raccordement des fibres optiques à un connecteur. Mais la résistance mécanique est défavorable à la commodité d'emploi, car une pellicule de gainage résistante et ayant un grand allongement avant rupture gêne le dénudage des micromodules pour libérer les parties terminales des fibres.- finally, high resistance to chemicals used during operations carried out on cables, for example cleaning solvent. In the case of the manufacture of optical fiber cables, some of the above characteristics are essential, in particular the mechanical strength, including during thermal aging, and the compatibility with the sealing gels and the cleaning solvents used to remove frost and dirt before connecting the optical fibers to a connector. However, the mechanical strength is unfavorable to the convenience of use, since a resistant sheathing film having a large elongation before rupture hinders the stripping of the micromodules to release the terminal parts of the fibers.
On connaît déjà (GB - A - 2 110 696) un matériau isolant électrique comportant un alliage de polymères au moins partiellement réticulés, contenant notament un copolymère EVA (éthyl acétate d'alkyl)à plus de 40% d'acétate de vinyle, avec des charges inorganiques à une teneur suffisante pour rendre le matériau ignifuge. La réticulation est destiné à permettre un taux de charges élevé.There is already known (GB - A - 2 110 696) an electrical insulating material comprising an alloy of at least partially crosslinked polymers, in particular containing an EVA (ethyl alkyl acetate) copolymer with more than 40% vinyl acetate, with inorganic fillers at a content sufficient to make the material flame retardant. Crosslinking is intended to allow a high charge rate.
La présente invention vise notamment à fournir un matériau extrudable en pellicule fine représentant un compromis satisfaisant entre les différents résultats à atteindre. L'invention propose notamment dans ce but un matériau extrudable en pellicule fine, constitué par une composition contenant au moins un (éventuellement plusieurs) polymère oléfinique thermoplastique pratiquement non réticulé et un taux de charges compris entre 25 à 65 % en poids de la composition, ledit matériau à l'état non divisé ayant une résistance à la traction comprise entre 6 et 20 Mpa et un allongement à la rupture compris entre 50 et 300 %.The present invention aims in particular to provide an extrudable material in thin film representing a satisfactory compromise between the different results to be achieved. The invention notably proposes for this purpose a thin film extrudable material, consisting of a composition containing at least one (possibly several) practically non-crosslinked thermoplastic olefin polymer and a content of fillers of between 25 to 65% by weight of the composition, said material in the undivided state having a tensile strength of between 6 and 20 Mpa and an elongation at break of between 50 and 300%.
On entendra par le terme "pratiquement non réticulé" un polymère présenté dans le commerce comme tel, n'ayant en conséquence pas de taux appréciable de réticulation et ne contenant pas d'agent de réticulation tel que des peroxydes, sauf à l'état de trace.The term "practically non-crosslinked" will be understood to mean a polymer presented on the market as such, consequently having no appreciable degree of crosslinking and containing no crosslinking agent such as peroxides, except in the state of trace.
Grâce à l'absence de réticulation, on évite la présence de "gels", très préjudiciables lors d'une extrusion en fine épaisseur, et on réduit le retrait post- extrusion, qui entraîne des contraintes sur les fibres.Thanks to the absence of crosslinking, the presence of “gels”, which is very harmful during a thin extrusion, is avoided, and post-extrusion shrinkage is reduced, which causes stress on the fibers.
La dureté shore du matériau est avantageusement comprise entre 35 et 55 D. Le choix d'une dureté Shore D dépassant 35 permet, en cas d'utilisation du matériau pour constituer une gaine de micromodule, d'assurer une cylindricité satisfaisante et d'éviter l'effet dit "de paille", constituée par la formation d'un coude brutal lors des flexions nécessaires à la réalisation des raccordements. Grâce à l'allongement limité à la rupture, dû notamment à la présence de charges, la dénudabilité est suffisante pour ne pas obliger à avoir recours à des outils spéciaux. Les caractéristiques minimales ci-dessus, notamment la résistance à la traction et l'allongement à la rupture, évitent une fragilité excessive du matériau lors de la manipulation. En particulier, ces minima permettent des manipulations lors de la fabrication d'un câble ou des raccordements sans risques excessifs de dommages.The shore hardness of the material is advantageously between 35 and 55 D. The choice of a Shore D hardness exceeding 35 makes it possible, when the material is used to form a micromodule sheath, to ensure satisfactory cylindricity and to avoid the so-called "straw" effect, formed by the formation of a brutal bend during the flexions necessary for making the connections. Thanks to the limited elongation at break, due in particular to the presence of fillers, the strippability is sufficient so as not to require the use of special tools. The above minimum characteristics, in particular the tensile strength and the elongation at break, avoid excessive brittleness of the material during handling. In particular, these minima allow manipulation during the manufacture of a cable or connections without excessive risk of damage.
La teneur minimale en charges indiquée plus haut permet de réduire la dilatation et la rétraction des matériaux lors des variations de température qui interviennent lors de la fabrication d'un câble. La présence d'une teneur suffisante de charges permet d'éviter le risque de collage des micromodules entre eux, sur des fibres gainées ou sur une enveloppe externe.The minimum filler content indicated above makes it possible to reduce the expansion and retraction of the materials during temperature variations which occur during the manufacture of a cable. The presence of a sufficient content of fillers makes it possible to avoid the risk of bonding of the micromodules to each other, on sheathed fibers or on an external envelope.
Les charges seront généralement minérales. On peut notamment utiliser l'alumine (hydratée ou non), la craie, le kaolin, le talc, la silice, l'hydroxyde de magnésie et leurs mélanges. Toutes ces charges réduisent l'allongement à la rupture et la dilatation ou la rétraction lors des variations de température. Au surplus, elles augmentent l'inertie thermique et la capacité calorifique. Le taux maximum de charges envisagé plus haut permet de maintenir la viscosité à un niveau compatible avec l'extrusion en pellicule mince.The fillers will generally be mineral. It is possible in particular to use alumina (hydrated or not), chalk, kaolin, talc, silica, magnesium hydroxide and their mixtures. All these loads reduce the elongation at break and the expansion or retraction during temperature variations. In addition, they increase the thermal inertia and the heat capacity. The maximum level of fillers envisaged above makes it possible to maintain the viscosity at a level compatible with thin film extrusion.
Les polymères oléfiniques utilisables sont sensiblement les mêmes que ceux couramment utilisés à l'heure actuelle. En particulier, on peut citer les produits suivants :The olefin polymers which can be used are substantially the same as those commonly used at present. In particular, the following products can be mentioned:
- PE : polyéthylènes- PE: polyethylenes
- PP : polypropylènes- PP: polypropylenes
- EPR : Ethylène Propylène Rubber (Caoutchouc d'ethylène propylène) - EPDM : Ethylène propylène Diène Monomère- EPR: Ethylene Propylene Rubber - EPDM: Ethylene propylene Diene Monomer
- EVA : copolymères ethylène-acétate d'alkyl inférieur ( notamment acétate de vinyl)- EVA: ethylene-lower alkyl acetate copolymers (in particular vinyl acetate)
- EBA : copolymères ethylène - acrylate d'alkyl inférieur- EBA: ethylene copolymers - lower alkyl acrylate
- EEA : Ethylène Ethyl Acrylate- EEA: Ethylene Ethyl Acrylate
- EMA : Ethylène Méthyl Acrylate - VLDPE : Very Low Density Polyethylène (polyethylène à très basse densité)- EMA: Ethylene Methyl Acrylate - VLDPE: Very Low Density Polyethylene (very low density polyethylene)
- polymères greffés d'acide acrylique ou d'anhydride maléique- grafted polymers of acrylic acid or maleic anhydride
- PVC : chlorure de polyvinyl- PVC: polyvinyl chloride
- leurs mélanges et co-polymères. Les différents polymères ne sont pas pleinement équivalents les uns aux autres Souvent on utilisera un mélange de polymères oléfiniques dont un des composants est PE ou PP et l'autre choisi parmi les autres polymères cités ci-dessus.- their mixtures and co-polymers. The different polymers are not fully equivalent to each other Often a mixture of olefin polymers will be used, one of the components of which is PE or PP and the other chosen from the other polymers mentioned above.
Si le second polymère est EVA,on utilisera un composé n'ayant pas plus de 30% de co-monomère vinyl acétate afin de conserver une dureté et des caractehstiqus mécaniques suffisantes. EBA, EEA ou EMA ont des propriétés proches de EVA. EPR etIf the second polymer is EVA, a compound having no more than 30% of vinyl acetate co-monomer will be used in order to maintain sufficient hardness and mechanical characteristics. EBA, EEA or EMA have properties close to EVA. EPR and
EPDM seront utilisés avec des taux d'ethylène suffisamment élevés pour éviter qu'ils n'aient des propriétés qui se rapprochent de celles d'un élastomère.EPDM will be used with sufficiently high levels of ethylene to prevent them from having properties that approximate those of an elastomer.
En cas d'emploi de polymère constitué d'une part de PE ou PP, d'autre part de copolymere EVA, on utilisera avantageusement une composition ayant de 40 % à 80 % de EVA.When using a polymer consisting on the one hand of PE or PP and on the other hand of an EVA copolymer, a composition having 40% to 80% EVA will advantageously be used.
Le matériau extrudable comportera généralement, de plus, des plastifiants à teneur faible, ne dépassant pas quelques pour cent en poids, tels que des huiles aliphatiques ou des phtalates (par exemple phtalate de di-octyle ou de didécyle), des adipates, des trimellitates, etc.The extrudable material will generally additionally contain plasticizers of low content, not exceeding a few percent by weight, such as aliphatic oils or phthalates (for example di-octyl or didecyl phthalate), adipates, trimellitates , etc.
Des produits de protection contre la chaleur ou les ultraviolets sont incorporés lorsqu'une exposition ou le rayonnement solaire est à craindre.Protective products against heat or ultraviolet rays are incorporated when exposure or solar radiation is to be feared.
Dans certains cas, on ajoutera un ou des silanes ou aminosilanes, tels que :In certain cases, one or more silanes or aminosilanes will be added, such as:
- vinyl trimethoxysilane - amino propylsilane- vinyl trimethoxysilane - amino propylsilane
- amino trimethoxysilane- amino trimethoxysilane
Si on utilise un trialkoxy silane, il sera souhaitable de ne pas aller au-delà d'un composé ayant plus de cinq atomes de carbone.If a trialkoxy silane is used, it will be desirable not to go beyond a compound having more than five carbon atoms.
Les silanes renforcent la liaison entre les charges et le polymère. En l'absence d'agent de réticulation, le silane ne risque pas de provoquer une réticulation qui au surplus ne serait pas possible en cas d'utilisation du matériau pour constituer des gaines de fibre optique, les températures requises pour la réticualtion n'étant alors pas atteintes lors de l'extrusion.The silanes strengthen the bond between the fillers and the polymer. In the absence of crosslinking agent, the silane does not risk causing crosslinking which, moreover, would not be possible if the material were used to form optical fiber sheaths, the temperatures required for crosslinking not being then not reached during extrusion.
L'invention propose également un micromodule de fibres optiques comprenant un faisceau de fibres optiques et une gaine entourant le faisceau en une pellicule mince d'un matériau extrudable, caractérisé en ce que la gaine est constituée en une composition contenant un polymère oléfinique thermoplastique et un taux de charges compris entre 25 à 65 % en poids de la composition, ledit matériau à l'état non divisé ayant une résistance à la traction comprise entre 6 et 20 Mpa et un allongement à la rupture compris entre 50 et 300 %.The invention also provides an optical fiber micromodule comprising a bundle of optical fibers and a sheath surrounding the bundle in a thin film of an extrudable material, characterized in that the sheath is made up of a composition containing a thermoplastic olefin polymer and a charge rate between 25 to 65% by weight of the composition, said material in the undivided state having a tensile strength of between 6 and 20 Mpa and an elongation at break of between 50 and 300%.
On donnera maintenant, à titre d'exemple, les propriétés de plusieurs matériaux conformes à l'invention, en même temps qu'une comparaison avec un matériau témoin classiquement utilisé à ce jour pour constituer une gaine de micromodule.We will now give, by way of example, the properties of several materials in accordance with the invention, at the same time as a comparison with a control material conventionally used to date for constituting a micromodule sheath.
La description qui suit fait référence à la figure unique qui montre un micromodule dans un état déformé qu'il est susceptible de prendre lorsqu'il est pressé contre d'autres micromodules par une enveloppe externe.The following description refers to the single figure which shows a micromodule in a deformed state which it is likely to take when it is pressed against other micromodules by an external envelope.
Le micromodule comporte plusieurs fibres optiques 10 individuellement gainées contenues dans une gaine 12 qui doit être facilement déchirable pour permettre le dénudage des extrémités des fibres en vue de raccordements. Cette gaine 12 est généralement constituée par extrusion sur le faisceau de fibres optiques 10 lors du tirage de ces dernières et prend alors une forme approximativement circulaire lorsque le faisceau de fibres présente lui-même un pourtour dont la forme ne s'écarte pas trop du cercle circonscrit. La gaine enserre les fibres et s'applique en effet contre elles. A l'intérieur d'un câble, la pression des micromodules les uns contre les autres peut déformer leurs section et les amener par exemple à celle qui est illustrée.The micromodule comprises several individually sheathed optical fibers 10 contained in a sheath 12 which must be easily tearable to allow the stripping of the ends of the fibers for connections. This sheath 12 is generally formed by extrusion on the bundle of optical fibers 10 during the drawing of the latter and then takes an approximately circular shape when the bundle of fibers itself has a periphery whose shape does not deviate too much from the circle. circumscribed. The sheath encloses the fibers and is indeed applied against them. Inside a cable, the pressure of the micromodules against each other can deform their cross-section and cause it, for example, to that illustrated.
Le matériau témoin est constitué par du polyethylène ayant une densité nominale de 0,92 et un "melt flow index" de 0,3 g/10 mn à 190°C, sous une pression de 21 ,6 N. Ce matériau a été utilisé pour constituer la gaine d'un micromodule, par extrusion sur un faisceau de quatre fibres optiques. La gaine 12 constituée avait un diamètre de 1 mm et une épaisseur de 0,12 mm. L'extrusion se fait sans difficulté et la gaine obtenue est bien cylindrique. Mais lors de la constitution du câble, par extrusion d'une enveloppe externe à base de polyethylène, la chaleur nécessaire à l'extrusion de l'enveloppe déforme les micromodules et les gaines tendent à se coller ensemble et à se coller à l'enveloppe extérieure, imposant des précautions particulières, comme par exemple l'interposition d'un ou plusieurs rubans séparateurs entre les micromodules et l'enveloppe.The control material consists of polyethylene having a nominal density of 0.92 and a "melt flow index" of 0.3 g / 10 min at 190 ° C, under a pressure of 21.6 N. This material was used to form the sheath of a micromodule, by extrusion on a bundle of four optical fibers. The sheath 12 formed had a diameter of 1 mm and a thickness of 0.12 mm. Extrusion is done without difficulty and the sheath obtained is well cylindrical. But during the constitution of the cable, by extrusion of an external envelope based on polyethylene, the heat necessary for the extrusion of the envelope deforms the micromodules and the sheaths tend to stick together and to stick to the envelope exterior, imposing special precautions, such as interposing one or more separating tapes between the micromodules and the envelope.
Ces difficultés sont écartées lors de la mise en œuvre d'un matériau conforme à l'invention. Exemple 1 :These difficulties are eliminated during the use of a material according to the invention. Example 1:
Dans un mélangeur, on a préparé une composition comprenant, en poids :In a mixer, a composition was prepared comprising, by weight:
- 50 parts de polyethylène de densité 0,92 ayant un Melt Flow Index à 190°C, sous 21.6 N, de 1.8g/10 min - 50 parts de copolymere EVA contenent 18 % d'acétate de vinyle - 130 parts d'hydrate d'alumine- 50 parts of density 0.92 polyethylene having a Melt Flow Index at 190 ° C, under 21.6 N, of 1.8 g / 10 min - 50 parts of EVA copolymer contain 18% vinyl acetate - 130 parts of hydrate alumina
- 5 parts de lubrifiant (huile paraffinique)- 5 parts of lubricant (paraffinic oil)
- 5 parts d'additifs (anti-oxydants, silane, lubrifiant)- 5 parts of additives (antioxidants, silane, lubricant)
Les ingrédients sont mélangés pendant 10 minutes, jusqu'à 160°C. Après calandrage sur un mélangeur à cylindres, le matériau est découpé, puis moulé à 180°C sous pression, sous forme de plaques permettant d'effectuer des mesures caractérisant le matériau.The ingredients are mixed for 10 minutes, up to 160 ° C. After calendering on a roller mixer, the material is cut, then molded at 180 ° C under pressure, in the form of plates making it possible to carry out measurements characterizing the material.
Les caractéristiques mécaniques obtenues sur les plaques sont les suivantes : Résistance à la rupture = 11.4 Mpa Allongement à la rupture = 125 % Dureté = 45 Shore DThe mechanical characteristics obtained on the plates are as follows: Breaking strength = 11.4 Mpa Elongation at break = 125% Hardness = 45 Shore D
La composition a été utilisée pour constituer des micromodules. Pour cela, on l'a mise sous forme de granulés qui sont introduits dans une extrudeuse de 45 mm de diamètre, et 24 diamètres de longueur. Les températures d'extrusion sont comprises entre 130 et 165°C, depuis la trémie d'alimentation, jusqu'à la tête d'extrusion.The composition was used to form micromodules. For this, it was put in the form of granules which are introduced into an extruder 45 mm in diameter, and 24 diameters in length. Extrusion temperatures are between 130 and 165 ° C, from the feed hopper to the extrusion head.
Pour caractériser la gaine obtenue, deux opérations ont été faites.To characterize the sheath obtained, two operations were carried out.
La première a été une mise en forme à une vitesse de 100m/min, pour obtenir un tube de 0.90 mm de diamètre externe, et de 0.12 mm d'épaisseur radiale. Pour la seconde, la mise en forme a été identique à cela près qu'on introduit à travers la tête de l'extrudeuse 4 fibres optiques colorées, et qu'on injecte simultanément un gel d'étanchéité pour former un module qui, après refroidissement de la matière extrudee, est recueilli dans un bac où il s'enroule librement à plat.The first was a shaping at a speed of 100m / min, to obtain a tube of 0.90 mm in external diameter, and 0.12 mm in radial thickness. For the second, the shaping was identical except that we introduce through the head of the extruder 4 colored optical fibers, and that we simultaneously inject a sealing gel to form a module which, after cooling of the extruded material, is collected in a tank where it freely winds up flat.
Les caractéristiques obtenues sur les gaines sont les suivantes :The characteristics obtained on the sheaths are as follows:
RT = Résistance à la Traction, exprimée en Newton AR = Allongement à la rupture, exprimé en % Va = VariationRT = Tensile strength, expressed in Newton AR = Elongation at break, expressed in% Va = Variation
Ces résultats indiquent d'une part la bonne résistance thermique, et d'autre part la bonne compatibilité avec les matériaux de remplissage des gaines du matériau conforme à l'invention.These results indicate on the one hand the good thermal resistance, and on the other hand the good compatibility with the filling materials of the sheaths of the material according to the invention.
Exemple 2Example 2
La composition du matériau est identique à l'exemple 1 , à ceci près que la charge à base d'alumine hydratée est remplacée par une charge à base de carbonate de calcium. On réalise le mélange dans les mêmes conditions, et on extrude à 100m/min un micromodule de diamètre de 0.85 mm, et d'épaisseur 0.11 mm. Les caractéristiques ci-dessous montrent comment on obtient avec une telle formulation des modules présentant une résistance chimique correcte, malgré la faible épaisseur de la gaine du module.The composition of the material is identical to Example 1, except that the filler based on hydrated alumina is replaced by a filler based on calcium carbonate. The mixing is carried out under the same conditions, and a micromodule with a diameter of 0.85 mm and a thickness of 0.11 mm is extruded at 100 m / min. The characteristics below show how modules with a correct chemical resistance are obtained with such a formulation, despite the small thickness of the sheath of the module.
Caractéristiques initiales RT = 3.9N AR = 155 %Initial characteristics RT = 3.9N AR = 155%
Après une heure dans l'éthanol à 20°C Var RT = 1% Var AR = 3 %After one hour in ethanol at 20 ° C Var RT = 1% Var AR = 3%
Après une heure dans l'isopropanol à 20°C Var RT = 5% Var AR = 3 %After one hour in isopropanol at 20 ° C Var RT = 5% Var AR = 3%
Exemple 3Example 3
On réalise une formulation identique à l'exemple 1 , à ceci près que la charge à base d'alumine est remplacée par une charge kaolinique, et sa concentration abaissée à 65 parts. Le plastifiant paraffinique est remplacé par une huile de type adipate d'isononyle. Les différents ingrédients sont introduits en mélangeur interne, mélangés jusqu'à environ 160°C, et granulés. Les caractéristiques du matériau sur plaque sont les suivants :A formulation identical to Example 1 is produced, except that the alumina-based filler is replaced by a kaolinic filler, and its concentration lowered to 65 parts. The paraffinic plasticizer is replaced by an oil of isononyl adipate type. The various ingredients are introduced in an internal mixer, mixed up to approximately 160 ° C., and granules. The characteristics of the material on the plate are as follows:
Caractéristiques mécaniques initiales Résistance à la traction RT = 10.5 Mpa AR = 157 % Allongement à la ruptureInitial mechanical characteristics Tensile strength RT = 10.5 Mpa AR = 157% Elongation at break
Vieillissement 10 jours à 70°C Var RT = + 1% Var AR = -13%Aging 10 days at 70 ° C Var RT = + 1% Var AR = -13%
Vieillissement 42 jours à 80°C Var RT = + 7 % Var AR = -19%Aging 42 days at 80 ° C Var RT = + 7% Var AR = -19%
Compatibilité avec la gelée Macroplast CF 300 Var RT = -15% Var AR = -18% 10 jours à 70°C Variation masse : = 7%Compatibility with Macroplast CF 300 jelly Var RT = -15% Var AR = -18% 10 days at 70 ° C Mass variation : = 7%
Tenue en chaleur humide 42 jours à 40°C et 93 % HR Var RT= -4% Var AR = +2%Moist heat resistance 42 days at 40 ° C and 93% RH Var RT = -4% Var AR = + 2%
Immersion dans le kerdane 24 heures à 20°C Var RT = - 25% Var AR = -10%Immersion in kerdane 24 hours at 20 ° C Var RT = - 25% Var AR = -10%
Immersion dans l'éthanol 1 heure à 20°C Var RT = -4% Var AR = -10%Immersion in ethanol for 1 hour at 20 ° C Var RT = -4% Var AR = -10%
Immersion dans l'isopropanol 1 heure à 20°C Var RT = -6% Var AR = -4%Immersion in isopropanol 1 hour at 20 ° C Var RT = -6% Var AR = -4%
Immersion dans l'isopropanol 1 heure à 20°C Var RT = -4% VarAR = -10%Immersion in isopropanol 1 hour at 20 ° C Var RT = -4% VarAR = -10%
Dureté 45 Shore D A partir de cette formulation, on réalise dans les mêmes conditions que précédemment un micromodule à quatre fibres optiques avec une gaine de 0,11 mm d'épaisseur etHardness 45 Shore D From this formulation, a micromodule with four optical fibers with a sheath 0.11 mm thick is produced under the same conditions as above.
0,85 mm de diamètre. Le gel d'étanchéité est la "Macroplast CF 300" de la société0.85 mm in diameter. The sealing gel is the "Macroplast CF 300" of the company
Henkel.Henkel.
Les caractéristiques obtenues sur le module sont les suivantes :The characteristics obtained on the module are as follows:

Claims

REVENDICATIONS
1. Matériau extrudable permettant de constituer des pellicules de faible épaisseur, comportant au moins un polymère oléfinique, caractérisé en ce qu'il est constitué par une composition contenant au moins un polymère oléfinique thermoplastique pratiquement non réticulé et un taux de charges compris entre 25 à 65 % en poids de la composition, ledit matériau à l'état non divisé ayant une résistance à la traction comprise entre 6 et 20 Mpa et un allongement à la rupture compris entre 50 et 300 %.1. Extrudable material making it possible to form thin films, comprising at least one olefinic polymer, characterized in that it consists of a composition containing at least one practically non-crosslinked thermoplastic olefin polymer and a content of fillers of between 25 to 65% by weight of the composition, said material in the undivided state having a tensile strength of between 6 and 20 Mpa and an elongation at break of between 50 and 300%.
2. Matériau suivant la revendication 1 , caractérisé en ce qu'il présente une dureté Shore D entre 35 et 55 .2. Material according to claim 1, characterized in that it has a Shore D hardness between 35 and 55.
3. Matériau suivant la revendication 1ou 2, caractérisé en ce que le polymère est choisi dans le groupe constitué par :3. Material according to claim 1 or 2, characterized in that the polymer is chosen from the group consisting of:
- PE : polyéthylènes- PE: polyethylenes
- PP : polypropylènes- PP: polypropylenes
- EPR : Ethylène Propylène Rubber (Caoutchouc d'ethylène propylène)- EPR: Ethylene Propylene Rubber
- EPDM : Ethylène propylène Diène Monomère - EVA : copolymères éthylène-acétate d'alkyl inférieur ( notamment acétate de vjnyl)- EPDM: Ethylene propylene Diene Monomer - EVA: ethylene-lower alkyl acetate copolymers (in particular vinyl acetate)
- EBA : copolymères ethylène - acrylate d'alkyl inférieur- EBA: ethylene copolymers - lower alkyl acrylate
- EEA : Ethylène Ethyl Acrylate- EEA: Ethylene Ethyl Acrylate
- EMA : Ethylène Méthyl Acrylate- EMA: Ethylene Methyl Acrylate
- VLDPE : Very Low Density Polyethylène (polyethylène à très basse densité) - polymères greffés d'acide acrylique ou d'anhydride maléique- VLDPE: Very Low Density Polyethylene (very low density polyethylene) - grafted polymers of acrylic acid or maleic anhydride
- PVC : chlorure de polyvinyle leurs mélanges et co-polymères.- PVC: polyvinyl chloride, their blends and co-polymers.
4. Matériau suivant la revendication 1 , 2 ou 3, caractérisé en ce que les charges sont choisies dans le groupe constitué par l'alumine (hydratée ou non), la craie, le kaolin, le talc, la silice, l'hydroxyde de magnésie, et leurs mélanges.4. Material according to claim 1, 2 or 3, characterized in that the fillers are chosen from the group consisting of alumina (hydrated or not), chalk, kaolin, talc, silica, hydroxide of magnesia, and mixtures thereof.
5. Matériau suivant l'une quelconque des revendications précédentes, caractérisé en ce que le polymère est un mélange de polymères oléfiniques dont un des composants est PE ou PP et l'autre choisi parmi EVA à 30% au plus de co-monomère vinyl acétate. EBA, EEA ou EMA, en plus éventuellement d'un lubrifiant et d'additifs.5. Material according to any one of the preceding claims, characterized in that the polymer is a mixture of olefin polymers, one of the components is PE or PP and the other chosen from EVA at most 30% of vinyl acetate co-monomer. EBA, EEA or EMA, optionally in addition to a lubricant and additives.
6. Matériau suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'il comporte, en plus éventuellement d'un lubrifiant et d'additifs autres que d'agents de réticulation:6. Material according to any one of the preceding claims, characterized in that it comprises, in addition optionally a lubricant and additives other than crosslinking agents:
- 50 parts de polyethylène de densité 0,92 ayant un Melt Flow Index à 190°C, sous 21.6 N, de 1.8g/10 min - 50 parts de copolymere EVA contenant 18 % d'acétate de vinyle 130 parts d'hydrate d'alumine- 50 parts of density 0.92 polyethylene having a Melt Flow Index at 190 ° C, under 21.6 N, of 1.8 g / 10 min - 50 parts of EVA copolymer containing 18% vinyl acetate 130 parts of hydrate d alumina
7. Matériau suivant l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il comporte, en plus d'un lubrifiant et d'additifs : 50 parts de polyethylène de densité 0,92 ayant un Melt Flow Index à 190°C, sous 21.6 N, de 1.8g/10 min7. Material according to any one of claims 1 to 4, characterized in that it comprises, in addition to a lubricant and additives: 50 parts of polyethylene of density 0.92 having a Melt Flow Index at 190 ° C, under 21.6 N, 1.8g / 10 min
50 parts de copolymere EVA contenant 18 % d'acétate de vinyle 130 parts de carbonate de calcium .50 parts of EVA copolymer containing 18% vinyl acetate 130 parts of calcium carbonate.
8. Matériau suivant l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il comporte, en plus d'un lubrifiant et d'additifs :8. Material according to any one of claims 1 to 4, characterized in that it comprises, in addition to a lubricant and additives:
50 parts de polyethylène de densité 0,92 ayant un Melt Flow Index à 190°C, sous 21.6 N, de 1.8g/10 min50 parts of 0.92 density polyethylene having a Melt Flow Index at 190 ° C, under 21.6 N, of 1.8g / 10 min
- 50 parts de copolymere EVA contenant 18 % d'acétate de vinyle - 65 parts de kaolin.- 50 parts of EVA copolymer containing 18% vinyl acetate - 65 parts of kaolin.
9. Matériau selon l'une quelconque des revendications 1 à 7, contenant un ou des silanes ou aminosilanes.9. Material according to any one of claims 1 to 7, containing one or more silanes or aminosilanes.
10. Micromodule de fibres optiques comprenant un faisceau de fibres optiques et une gaine entourant le faisceau en une pellicule mince d'un matériau extrudable, caractérisé en ce que la gaine est constituée en une composition contenant un polymère oléfinique thermoplastique et un taux de charges compris entre 25 à 65 % en poids de la composition, ledit matériau à l'état non divisé ayant une résistance à la traction comprise entre 6 et 20 Mpa et un allongement à la rupture compris entre 50 et 300 %. 10. Micromodule of optical fibers comprising a bundle of optical fibers and a sheath surrounding the bundle in a thin film of an extrudable material, characterized in that the sheath is made up of a composition containing a thermoplastic olefin polymer and a content of fillers between 25 to 65% in weight of the composition, said material in the undivided state having a tensile strength of between 6 and 20 Mpa and an elongation at break of between 50 and 300%.
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