WO2019202151A1 - Fil composite, processus de fabrication et surface textile comprenant un tel fil - Google Patents

Fil composite, processus de fabrication et surface textile comprenant un tel fil Download PDF

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Publication number
WO2019202151A1
WO2019202151A1 PCT/EP2019/060238 EP2019060238W WO2019202151A1 WO 2019202151 A1 WO2019202151 A1 WO 2019202151A1 EP 2019060238 W EP2019060238 W EP 2019060238W WO 2019202151 A1 WO2019202151 A1 WO 2019202151A1
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WO
WIPO (PCT)
Prior art keywords
yarn
composite yarn
composite
matrix
reinforcing filler
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.)
Ceased
Application number
PCT/EP2019/060238
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English (en)
Inventor
François-Xavier DAMOUR
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MERMET
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MERMET
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Filing date
Publication date
Priority claimed from FR1853527A external-priority patent/FR3080387B1/fr
Priority to DK19718185.2T priority Critical patent/DK3781734T3/da
Priority to KR1020207030024A priority patent/KR20200144101A/ko
Priority to US17/048,600 priority patent/US11530497B2/en
Priority to EP25192715.8A priority patent/EP4617413A3/fr
Priority to CN201980025982.0A priority patent/CN111971427B/zh
Priority to SG11202009168PA priority patent/SG11202009168PA/en
Application filed by MERMET filed Critical MERMET
Priority to JP2021506064A priority patent/JP7427653B2/ja
Priority to AU2019254690A priority patent/AU2019254690B2/en
Priority to CA3097611A priority patent/CA3097611A1/fr
Priority to ES19718185T priority patent/ES3058258T3/es
Priority to BR112020021322-5A priority patent/BR112020021322B1/pt
Priority to IL277527A priority patent/IL277527B2/en
Priority to MX2020011056A priority patent/MX2020011056A/es
Priority to EP19718185.2A priority patent/EP3781734B1/fr
Priority to CN202410168694.3A priority patent/CN118029034A/zh
Publication of WO2019202151A1 publication Critical patent/WO2019202151A1/fr
Anticipated expiration legal-status Critical
Priority to ZA2020/07125A priority patent/ZA202007125B/en
Priority to US17/981,096 priority patent/US12091782B2/en
Priority to JP2024008588A priority patent/JP7756734B2/ja
Priority to US18/800,490 priority patent/US12497716B2/en
Priority to US19/389,707 priority patent/US20260071356A1/en
Ceased legal-status Critical Current

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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
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • D02G3/404—Yarns or threads coated with polymeric solutions

Definitions

  • the present invention which is disclosed below, relates to the general field of composite yarns, generally obtained by coating a continuous multifilament yarn with a matrix comprising at least one polymer; of textiles made from these yarns, and to sunblinds, or other sun-blocking, sun-screening or sun-shielding, made from such textiles or yarns.
  • Composite yarns are technical yarns that are well known and commonly used, which generally comprise:
  • a core including a continuous multifilament yarn (i.e. a yarn formed from several filaments) which is generally twisted;
  • a matrix containing at least one polymer material, for example a chlorinated polymer material such as polyvinyl chloride (PVC), a plasticizer, and usually a flame-retardant system composed of one or more mineral fire-retardant fillers; and
  • a chlorinated polymer material such as polyvinyl chloride (PVC)
  • PVC polyvinyl chloride
  • plasticizer a plasticizer
  • flame-retardant system composed of one or more mineral fire-retardant fillers
  • Mineral fire-retardant fillers are insoluble mineral solid substances and are usually intended to be dispersed by a mechanical means in an organic matrix. Fire-retardant fillers are used for improving the fire resistance of a material. Fire- retardant fillers are typically chosen from halogenated, organophosphorous (phosphonate, phosphinate, phosphate, etc.), boron-based or nitrogenous molecules, metal hydroxides of the (M(OFI)n) type, in which M is a metal, for instance aluminum or magnesium, or antimony oxides such as antimony trioxide or pentoxide. Many applications require flame-retardant materials (i.e., materials with fire-resistance properties).
  • At least one fire-retardant filler may be incorporated into the material. It is also necessary to adapt the formulation thus obtained to the application conditions. To do this, other materials may be present in the matrix, such as a viscosity reducer, which makes it possible to adjust the viscosity of the chemical preparation intended for the manufacture of the matrix of the composite yarn.
  • a composite yarn is generally obtained by depositing a polymer on the continuous multifilament yarn or "core yarn" (also known as the "fiber") which usually has a torsion.
  • plastisol Two techniques are mainly used for this purpose: the "plastisol” technique, comprising the coating of the core yarn with at least one layer of plastisol, said plastisol layer comprising the polymer, the plasticizer, and optionally other components such as fillers, followed by gelation of the plastisol around the core yarn; and the "extrusion-coating” technique, comprising the heating of the polymer from the solid form to the liquid form in an extruder followed by deposition on the core yarn and then calibration with a die.
  • the term "plastisol” designates a product obtained from a dispersion of a polymer in a plasticizer generally in the form of an oil.
  • the center of the composite yarn is formed from a zone in which all the filaments are concentrated. This zone is usually very poor in polymer. Therefore, the filaments are generally in direct contact with each other.
  • Patent application WO 2011/033130 itself describes an improvement of patent application WO 03/056082, in that the process for manufacturing the composite yarn comprises a preliminary step of mechanical opening; preferably splaying of the individual filaments of which the core yarn is composed (so as to allow the accessibility of the matrix to each of the filaments).
  • the process described in WO 2011/033130 is very complicated to implement.
  • the core yarn must be able to withstand a substantial mechanical stress generated by the mechanical opening of the individual filaments of which it is composed. This limits the choice of the core yarn.
  • Textiles obtained from composite yarns are subject to fire performance regulations in various jurisdictions.
  • Code B1 denotes the most stringent classification for an organic material. It is generally required for solar protection textiles especially in Germanophile regions and, by influence, in Northern Europe.
  • Standard NF P92-507 describes a class which utilizes tests carried out under standard NF P92-503. For meltable materials, additional tests are required according to the standards NF P92-504 and NF P92-505.
  • Combustibility is the heat emitted by total combustion of the material, whereas the flammability is the amount of flammable gas produced by the material.
  • Code M1 denotes non- flammable combustible materials, and applies especially to solar protection textiles intended for the French market and also, by influence, to the markets of Southern Europe.
  • Euroclasses define fire performance. They are used, inter alia, to characterize products for construction and for the fitting of buildings. They are more complete than each of the French and German classes taken individually, since they take into account the fire performance of the material denoted A1 , A2, B, C, D or F according to the level of energy released, the opacity of the fumes released (amount and speed) denoted “s” for “smoke” (code s1 to s3) and also any projected enflamed droplets and debris denoted “cT for "droplets” (code dO to d2).
  • no commercial composite yarn obtained by coating a flame retardant PVC plastisol on a mineral core yarn such as glass textile yarn makes it possible to prepare solar protection textiles which meet the fire performance criteria of euroclass Bs2d0 or Bs3d0 of the standard EN 13-501 -1 .
  • fire-retardant fillers dispersed in the polymer of the matrix. These fire-retardant fillers are of very diverse size and form.
  • Patent EP 0900294 describes a composite yarn such that the polymer material which constitutes its matrix is chlorinated, and comprising a fire-retardant filler of ternary composition combining an oxygenated antimony compound (in general antimony trioxide), a hydrated metal oxide and a zinc borate, the total composition of inorganic material of the composite yarn being between 4 and 65%.
  • the plasticizer generally comprises at least one organic phthalate and is free of phosphate. However, certain phthalates are reputed to be toxic and antimony salts are suspected of having toxicity.
  • Patent application WO 2010/001240 describes an improvement of patent EP 0900294, in that the flame-retardant plastisol comprises a lead-free chlorinated polymer, in that the plasticizer is free of orthophthalate and in that the fire-retardant filler is free of antimony and comprises metal hydrate and a zinc salt.
  • the content of flame-retardant agent is high, whereas the content of plasticizer is relatively low to comply with the fire classes, which leads to stiffness of the composite yarn and thus to difficulties for obtaining, from such a composite yarn, blind fabrics that are also in accordance with the performance requirements prescribed by standard EN 13561 .
  • One aspect of the present disclosure is to present improvements in the fire performance of composite yarns.
  • Another aspect of the present disclosure is to provide a process for manufacturing composite yarns that is simple to perform.
  • Another aspect of the present disclosure is to allow the use of glass textile yarn, as core yarn, with low torsion and containing a standard sizing for the purpose, among other things, of reducing the composite yarn manufacturing costs.
  • Another aspect of the present disclosure is to provide a process which complies with the environmental standards and which, in particular, uses components that are not suspected of being toxic and which limits the emission of volatile organic compounds (VOCs).
  • VOCs volatile organic compounds
  • a composite yarn comprising a continuous multifilament core yarn incorporated in a matrix, is characterized in that the matrix comprises at least one polymer material and at least one reinforcing filler, the reinforcing filler being made of functionalized particles, said particles having a median size (d v so) of less than 40 pm.
  • the composite yarn has a titer (or count) which is less than the titer of the composite yarns of the prior art.
  • the composite yarn when the core yarn has a titer of 68 tex, has a titer of 135-140 tex whereas the composite yarns of the prior art have a titer of about 165 tex for the same core yarn.
  • This advantageously makes it possible to reduce the mass per unit area and the thickness of textiles made from composite yarns by, respectively, about 10 to 20%, and about 10 to 15%.
  • the continuous multifilament core yarn has preferably a torsion within the range of from 20 to 40 rounds per meter.
  • the torsion of the core yarn is between 28 and 40 turns per meter.
  • the torsion of the core yarn is 28 turns per meter.
  • the functionalized particles of the reinforcing filler are dispersed throughout the matrix of the composite yarn, the matrix being in contact with the core yarn filaments.
  • some of the reinforcing filler is present in the inter-filament interstices of the core yarn.
  • the smallest particles of the reinforcing filler are present in the inter-filament spaces interstices of the core yarn.
  • the matrix forms generally a continuous medium in which the functionalized particles are dispersed.
  • the dispersion of the functionalized particles in the matrix is homogeneous.
  • homogeneous it should be understood that the concentration in functionalized particles in the matrix is of the same order of magnitude at any point of said matrix.
  • the composite yarn is made of the core yarn, the matrix, and a sheath.
  • a and/or B means“A” or“B” or”A and B’’.
  • Tex means, as is usual for a person of ordinary skill in the art, the mass in grams of one kilometer of yarn.
  • matrix means an element comprising at least one polymer material in contact with the core yarn.
  • the particles have a hardness (Mohs) less than or equal to the hardness of the material constituting the core yarn.
  • Mohs hardness is a measurement of the hardness of minerals. Mohs scale is based on ten readily available minerals. The hardness scale ranges from 1 (for talc) to 10 (for diamond). It is measurable by comparison (capacity of one to scratch the other) of a mineral with two other minerals whose hardness is already known. In general, this value is given by the product suppliers. Thus, the hardness of textile glass yarn formed from multifilaments is 5.5. Textile glass yarn is commonly called silionne. Textile glass yarn is a twisted assembly of various filaments of sized silionne. The term "sized" will be explained herein below.
  • the Mohs hardness of the particles constituting the reinforcing filler is at least 1 and not more than 5.5, including for example increments of 0.5 between these values. In other words, this hardness is in the range from 1 to 5.5.
  • the reinforcing filler is generally friable and therefore it becomes destructured because it cannot withstand the shear during the manufacturing steps of the composite yarn. If the hardness of the reinforcing particles is greater than 5.5, the reinforcing filler may locally damage the filaments constituting the core yarn.
  • s/ze means, as is usual, the diameter which would be had by the theoretical sphere behaving in the same manner as a particle under consideration during the chosen particle size analysis operation.
  • diameter or “equivalent diameter” is also used.
  • the measurements are generally taken by screening with a succession of vibrating screens or by laser particle size analysis (using a diffraction laser).
  • the particle size is preferably measured by laser particle size analysis.
  • a machine that may be used for laser particle size measurement is typically a Malvern Instruments brand machine, for example a Malvern Masterizer 2000 Instrument machine.
  • This machine makes it possible, inter alia, to determine the volume distribution of the particles, and in particular the dimensions d v so, d vi o and dv9o explained hereinbelow. It is usual to combine, as is known to those of ordinary skill in the art, the use of a powder drier, for example of Scirocco 2000 type, which makes it possible to dry the dry powder which feeds the laser particle size analyzer.
  • a powder drier for example of Scirocco 2000 type
  • the median size (dvso), or size (dvso) gives the median size: 50% (by volume) of the particles have a smaller size, and 50% (by volume) of the particles have a larger size.
  • the particles have a median size (d v so) of less than 40 pm, and preferably less than 30 pm, and generally greater than 5 pm, and preferably greater than 15 pm.
  • the median size (d v so) is between 5 pm and 40 pm, and still more preferably between 15 pm and 30 pm, or within the range from 15 pm to 30 pm, including for example increments of 1 pm therebetween.
  • the median size of the reinforcing particles (d v so) is less than 5 pm, too large an amount of particles of the reinforcing filler is present in the inter-filament interstices of the core yarn. In process terms, this generally results in the surface area of these particles being too great and leads to an increase in the viscosity of the polymer material constituting the matrix when it is deposited. If the median size (dvso) of these reinforcing particles is greater than 40 pm, too few of these reinforcing particles are present in the inter-filament interstices of the core yarn. In process terms, this generally results in the dispersion of the particles of the reinforcing filler in the inter-filament interstices of the core yarn being difficult and therefore insufficient. The breaking strength of the composite yarn is then generally judged insufficient.
  • the size (d vi o) gives the size below which 10% (by volume) of the particles have a smaller size, and 90% (by volume) of the particles have a larger size.
  • the particles generally have a size (d vi o) of less than 15 pm, and preferably within the range from 1 pm to 15 pm.
  • the size (d v io) of the reinforcing particles is less than 1 pm, too large an amount of particles of the reinforcing filler is present in the inter-filament interstices of the core yarn. In process terms, this generally results in the surface area of these particles being too great and leads to an increase in the viscosity of the polymer material constituting the matrix when it is deposited. If the size (dvio) of the reinforcing particles is greater than 15 pm, too few of these reinforcing particles are present in the inter-filament interstices of the core yarn. In process terms, this generally results in the dispersion of the particles of the reinforcing filler in the inter-filament interstices of the core yarn being difficult and therefore insufficient.
  • the breaking strength of the composite yarn is then generally judged insufficient.
  • the size (d V 9o) gives the size below which 90% (by volume) of the particles have a smaller size, and 10% (by volume) of the particles have a larger size.
  • the particles generally have a size (dv9o) of less than 90 pm, preferably within the range from 30 pm to 90 pm, and still more preferably from 30 pm to 80 pm.
  • the size (d V 9o) of the reinforcing particles is less than 30 pm, too large an amount of particles of the reinforcing filler is present within the inter-filament spaces of the core yarn. In process terms, this generally results in the surface area of these particles being too great and leads to an increase in the viscosity of the polymer material constituting the matrix when it is deposited. If the size (dvio) of the reinforcing particles is greater than 90 pm, too few of these reinforcing particles are present in the inter-filament interstices of the core yarn. In process terms, this generally results in the dispersion of the particles of the reinforcing filler in the inter-filament interstices of the core yarn being difficult and therefore insufficient.
  • the breaking strength of the composite yarn is then generally judged insufficient.
  • the nominal value of the average diameter of each of the filaments of the core yarn is generally within the range from 3.5 pm to 13 pm, typically in the range from 3.5 pm to 9 pm, still more preferably in the range from 6 pm to 9 pm, for example 6 pm or 9 pm.
  • This nominal value is generally given by the core yarn supplier.
  • Other nominal values may be envisaged for other uses of the composite yarn.
  • the ratio between the median size (d v so) of the reinforcing particles and the diameter of each of the filaments of the core yarn is generally in the range from 0.15 : 1 to 12 : 1 , preferably from 1 .5 :1 to 5 :1 .
  • the weight percentage of reinforcing filler present in the composite yarn is within the range of 0.5 to 30%. According to a more preferred embodiment, the weight percentage of reinforcing filler present in the composite yarn is within the range of 0.5 to 20%. According to an even more preferred embodiment, the weight percentage of reinforcing filler in the composite yarn is within the range of 1 to 10%.
  • the reinforcing filler is chosen from the group formed by functionalized fillers, preferably from the group formed by functionalized glass beads, functionalized calcium carbonate, and functionalized talc.
  • the functionalized glass beads have a hardness of 5.5.
  • the functionalized calcium carbonate has a hardness of 3.0.
  • the functionalized talc has a hardness of 1 .0.
  • the term “functionalized” means "surface-treated", i.e., a functionality has been added to the surface of the particle via at least one organic group.
  • This functionalization is performed with at least one compound, known as a functionalizing agent.
  • the functionalization makes it possible to create a "chemical bridge" between the filler and its environment, which in this case is the matrix. It is thus possible to chemically link (for example via covalent bonds) or physicochemically link (for example via hydrogen bonds) the filler, the core yarn, and the matrix.
  • this makes it possible to obtain a substantially homogeneous medium in which all the constituents are bound together via chemical bonds of organic type.
  • this gives the material substantial cohesion and homogeneity of the mechanical properties. This is coherent with the use of the term "reinforcing filler". In other words, the reinforcing filler is fully attached to the polymer constituting the matrix and also to the core yarn.
  • the reinforcing filler has a particle size that is small enough for some of them to be present in the inter-filament interstices of the core yarn, which advantageously allow fillings of the inter-filament interstices, preferably of all of the inter-filament interstices.
  • the functionalizing agent is generally chosen from the group formed by oxysilanes (or siloxanes) and oxygermanes bearing at least one organic group. This is described, for example, in WO 2014/207397.
  • the functionalized glass beads are generally made by chemical grafting, covalently and directly or indirectly, of a reagent onto the surface of the glass. This is described, for example, in WO 2014/083162. Functionalized glass beads are marketed by the company Sovitec under the name Microperl ® or Omicron ® . Calcium carbonate is generally functionalized by chemical grafting of reagents onto the surface. The processes performed are similar to those used for glass beads.
  • the reinforcing filler is functionalized with at least one compound chosen from silanized agents such as silanes, for example alkyl alkoxy silanes; epoxies, among which mention may be made of epoxysilanes and DGEBA (Bisphenol A diglycidyl ether); and polyisocyanates such as MDI derivatives (or 4,4’-MDI for 4,4’-diphenylmethane diisocyanate) or HDI (for hexamethylene diisocyanate).
  • silanized agents such as silanes, for example alkyl alkoxy silanes; epoxies, among which mention may be made of epoxysilanes and DGEBA (Bisphenol A diglycidyl ether); and polyisocyanates such as MDI derivatives (or 4,4’-MDI for 4,4’-diphenylmethane diisocyanate) or HDI (for hexamethylene diisocyanate).
  • the reinforcing filler is functionalized with at least one compound chosen from silanized agents, epoxies, and polyisocyanates, and even more preferably silanized agents.
  • Silanized agents are compounds comprising at least one silyl group, such as alkyl alkoxysilanes, alkylsilyl halides, for example such as trimethylsilyl chloride or diemethylsilyl dichloride, tetramethylsilane, tetraethoxysilane, dimethylsiloxane, 1 ,1 ,1 ,3,3,3-hexamethyldisilazane, etc.
  • silyl group such as alkyl alkoxysilanes, alkylsilyl halides, for example such as trimethylsilyl chloride or diemethylsilyl dichloride, tetramethylsilane, tetraethoxysilane, dimethylsiloxane, 1 ,1 ,1 ,3,3,3-hexamethyldisilazane, etc.
  • sil is meant a radical derived from silane.
  • alkyl is meant a radical derived from alkane, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and more preferably from 1 to 5, carbon atoms.
  • alcoxy silane is meant a compound comprising a divalent group -Si-0 and an alkyl group comprising from 1 to 20, preferably from 1 to 10, and more preferably from 1 to 5, carbon atoms.
  • Silanes are preferentially used, since there is a wide range of these products.
  • Silane is the molecule of formula SiH 4 .
  • the term "silane" here and as is usual refers to any compound whose central atom is silicon such as SiHCl3 (trichlorosilane) or tetramethylsilane Si(CH3)4 or tetraethoxysilane Si(OC2Hs)4.
  • the functionalized reinforcing filler is referred to as a silanate if it is functionalized with a silane, that is, a covalent bond is created between at least one silyl group of the silane and a particle of the reinforcing filler.
  • silanization by means of trimethylsilyl chloride creates trimethylsilyl groups covalently bonded to the particles
  • silanization by means of dimethylsilyl dichloride creates dimethylsilyl groups covalently bonded to the particles.
  • a person of ordinary skill in the art can readily identify a grade that is perfectly suited to the situation, as a function of the filler, of the core yarn and of the matrix. Epoxies and polyisocyanates are preferred most particularly in the case where the core yarns are of organic origin (polyesters, polyamides, polyvinyl alcohol, etc.).
  • the matrix further comprises at least one fire-retardant filler.
  • Fire-retardant fillers are well known to those of ordinary skill in the art. They are generally chosen from oxygenated antimony compounds, for example antimony trioxide, certain zinc salts, including zinc hydroxystannate or zinc borate, hydrated metal oxides, the metal of which is chosen from the group formed by aluminum, magnesium, tin and zinc, for example an alumina hydrate such as alumina trihydrate or a magnesium hydrate such as magnesium hydroxide, and phosphorus-based ceramics which act as intumescent systems.
  • oxygenated antimony compounds for example antimony trioxide
  • certain zinc salts including zinc hydroxystannate or zinc borate
  • hydrated metal oxides the metal of which is chosen from the group formed by aluminum, magnesium, tin and zinc, for example an alumina hydrate such as alumina trihydrate or a magnesium hydrate such as magnesium hydroxide, and phosphorus-based ceramics which act as intumescent systems.
  • the constituent material of the core yarn is preferably chosen from silionne, basalt, aramids, polyesters, polyamides, carbon, and polyvinyl alcohol.
  • the constituent material of the core yarn is silionne.
  • silionne has a Mohs hardness of 5.5.
  • the core yarn may be formed from a“standard” textile glass yarn or from a “specific” glass yarn.
  • Standard textile glass yarn has a torsion generally within the range from 20 to 40 turns per meter.
  • the torsion is typically 28 turns per meter for a core yarn tex of 33 tex or 68 tex, or 40 turns per meter for a core yarn of 22 tex.
  • Standard textile glass yarn further comprises a sizing generally based on starch, the purpose of which is to protect the silionne filaments and to ensure their cohesion. This is then referred to as a sized textile glass yarn.
  • the compositions of such sizing are in general developed by the companies which commercialize these core yarns, which do not disclose them.
  • the sizing is deposited on the individual filaments composing the textile glass yarn during what is called in this industry the“forming” operation which consists in spinning the filaments of molten glass through the holes of a die at high speed.
  • This sizing is generally deposited on the surface of the filaments in the form of an aqueous emulsion during the manufacture of the core yarn. It generally represents from 0.5% to 1 .5% of the weight composition of the core yarn.
  • the role of the sizing is to protect the filaments to allow their manipulation and to reduce the phenomenon of static electricity during weaving.
  • the textile sizing is usually composed of an adhesive agent (which is generally starch), and possibly at least one wetting agent (intended to improve the impregnation of the yarn) and/or at least one lubricant.
  • an adhesive agent which is generally starch
  • at least one wetting agent intended to improve the impregnation of the yarn
  • at least one lubricant in contrast with the specific textile glass yarn, the standard textile glass yarn does not include any coupling agent in its sizing.
  • the standard textile glass yarn is generally a textile glass yarn having a torsion in the range from 20 to 40 turns per meter, and comprising a sizing comprising, preferably being formed from, at least one adhesive agent, and possibly at least one wetting agent and/or at least one lubricant.
  • the specific textile glass yarn usually used in the applications for coating textile glass yarn with a PVC plastisol, has a torsion generally in the range from 40 to 80 turns per meter and/or what is referred to as specific sizing, which, in addition to the sizing of the standard textile glass yarn, contains at least one adhesion promoter and/or at least one coupling agent for the sizing.
  • the torsion value is generally linked to the final application concerned.
  • the adhesion promoter and/or the coupling agent is/are intended to allow adhesion (mainly by creating at least one chemical bond) between the constituent filaments of the textile glass yarn and the adhesion promoter(s) and/or coupling agent(s) and, furthermore, between the adhesion promoter(s) and/or coupling agent(s) and the polymer(s) constituting the matrix.
  • the constituent filaments of the textile glass yarn and the polymer(s) are thus chemically bonded.
  • the specific sizing further comprises at least one organic binder and/or at least one lubricant.
  • the adhesion promoters / coupling agents are generally silanes. Each textile glass yarn manufacturer has his own sizings, the exact chemical compositions of which are known only to him.
  • sizings that are specially developed for promoting silionne / PVC adhesion such as the sizings TD52 and TD53 from the company VETROTEX and sizings specially developed for promoting adhesion of silionne with various types of polymers such as the sizings TD22 and TD37 from the company VETROTEX.
  • the specific textile glass yarn is generally a textile glass yarn with a torsion in the range from 40 to 80 turns per meter, and/or comprising a sizing comprising, preferably formed from, at least one adhesive agent, and at least one adhesion promoter and/or at least one coupling agent.
  • the specific textile glass yarn is thus much more expensive than the standard textile glass yarn.
  • the composite yarn may comprise a core yarn which is a standard textile glass yarn, rather than mandatorily a specific textile glass yarn.
  • this thus advantageously makes it possible to replace the specific textile glass yarn with a standard textile glass yarn, which allows an appreciable reduction in the cost of manufacture of the composite yarn, of the order of 25%, and which opens the panel of potential suppliers of core yarns for the composite yarn manufacturer, especially towards those which have the largest worldwide production capacities, for example the Asiatic suppliers manufacturing textile glass yarns intended for producing printed circuit boards.
  • the raw material of the core yarn less expensive, in particular by avoiding the use of special and expensive organic products for the sizing (namely at least one adhesion promoter and/or at least one coupling agent), but also it is possible, by means of less twisting of the core yarns which are textile glass yarns, to limit the time of passage of these yarns on the twisting machines generally used in textile production.
  • the qualities of the composite yarn obtained by using a core yarn which is a standard textile glass yarn are not compromised, or are even superior to those of the composite yarns of the prior art using a core yarn which is a specific textile glass yarn.
  • the Applicant thinks that it is by virtue of easier access to the inter-filament interstices, permitted by the functionalized particles present in the matrix.
  • the core yarn of the composite yarn may thus be a standard textile glass yarn.
  • the core yarn of the composite yarn may also be a specific textile glass yarn.
  • the softening point or melting point of the constituent material of the core yarn must be higher than the temperature of implementation of the polymer material of the matrix of the composite yarn.
  • the softening point of the constituent material of the core yarn when it is a textile glass yarn is at least 20°C higher, preferably at least 30°C higher and even more preferably at least 50°C higher than the temperature of implementation of the polymer material of the matrix of the composite yarn.
  • the temperature of implementation of the polymer material of the matrix of the composite yarn is typically in a range from 50 to 180°C.
  • the softening point of the constituent material of the core yarn, when said yarn is a textile glass yarn is typically about 600°C.
  • the composite yarn further comprises at least one layer, also termed "sheath” or " envelope " enveloping said matrix, the layer comprising at least one polymer material and at least one reinforcing filler.
  • This layer is usually deposited in the same manner as the matrix, preferably by coating.
  • the composite yarn is formed from the core yarn, the matrix and the sheath.
  • the polymer material of this layer is of the same chemical nature as the polymer material of the matrix.
  • the term“same chemical nature” means of compatible chemical composition, as is known to those of ordinary skill in the art.
  • the reinforcing filler of said layer is of the same chemical nature as the reinforcing filler of said matrix.
  • this identity of chemical nature makes it possible to obtain a composite yarn which has better homogeneity, i.e., the core yarn, the matrix, and the layer of which it is composed interact in terms of sorption and adhesion.
  • At least one other additive may be incorporated and distributed in the matrix, in the layer or both (layer and matrix), such as one or more fire-retardant fillers, a pigmentary filler and/or a heat stabilizer and/or a UV stabilizer.
  • the sheath further comprises at least one fire-retardant filler.
  • a fire-retardant filler is chosen from the fire-retardant fillers known to those of ordinary skill in the art and described above.
  • the disclosure advantageously makes it possible to limit the amount (by weight) of fire-retardant filler present in the composite yarn
  • the amount (by weight) of fire-retardant filler in the composite yarn is generally more than 1 .5% and less than 7.5%, e.g., about 3% by weight relative to the total weight of the composite yarn, to obtain a level of flame retardancy similar to that of the composite yarns of the state of the art, for which the amount by weight of flame retardant filler is most often from 8 to 12% by weight relative to the total weight of the composite yarn.
  • the disclosure advantageously makes it possible to obtain a composite yarn which, for an identical amount (by weight) of fire-retardant filler, has fire resistance performance that is particularly improved relative to that of the composite yarns of the prior art.
  • it is permitted, for the first time, to manufacture a composite yarn whose core yarn is formed from silionne, which meets the criteria Bs2d0 or Bs3d0 of Euroclasse standard EN 13501 -1 .
  • the Applicant thinks that the inorganic nature of the reinforcing filler allows local dispersion of the heat supplied by the fire.
  • filling of the inter-filament interstices with the reinforcing particles makes it possible to eliminate a“chimney" effect associated with the existence of a lack of material at the center of the core yarn, which favors flame propagation.
  • the composite yarn comprises a continuous multi- filament core yarn and a matrix, the matrix comprising:
  • polymer material at least one polymer material, the polymer being chosen from the group consisting of PVCs, polyacrylates, polyolefins, polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers and polyamides, and
  • the reinforcing filler being constituted by particles dispersed in the polymer material of the matrix and present in the inter-filament interstices of the core yarn, said particles being functionalized and having a median size (d v so) less than 40 pm, the composite yarn further comprising a flame-retardant filler in an amount of approximately 0.5 to 5% by weight and being such that the textile surfaces obtained from said yarn meet the performance requirements prescribed by the standard EN 13561 (more than 10 000 cycles).
  • textile surface is meant a mechanical assembly of yarns, such as a fabric, a non-woven, a knit, a textile grid, etc.
  • textile surface obtained from said yarn is meant that the yarn assembly is the composite yarn.
  • the composite yarn comprises a continuous multi- filament core yarn and a matrix, the matrix comprising:
  • polymer material at least one polymer material, the polymer being chosen from the group consisting of PVCs, polyacrylates, polyolefins, polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers and polyamides, and
  • the reinforcing filler being constituted by particles dispersed in the polymer material of the matrix and present in the inter-filament interstices of the core yarn, said particles being functionalized and having a median size (d v so) less than 40 pm, the composite yarn further comprising a flame-retardant filler in an amount of approximately 0.5 to 5% by weight, and being such that the textile surfaces obtained from said yarn meet the fire performance requirements of class M1 of the standard NF P-92-507.
  • the composite yarn comprises a continuous multi- filament core yarn and a matrix, the matrix comprising:
  • polymer material at least one polymer material, the polymer being chosen from the group consisting of PVCs, polyacrylates, polyolefins, polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers and polyamides, and
  • the reinforcing filler being constituted by particles dispersed in the polymer material of the matrix and present in the inter-filament interstices of the core yarn, said particles being functionalized and having a median size (d v so) less than 40 pm, the composite yarn further comprising a flame-retardant filler in an amount of approximately 5 to 15% by weight, and being such that the textile surfaces obtained from said yarn meet the fire performance requirements of Euroclass Bs2d0 or Bs3d0 of the standard NF P13501 -1 .
  • the present disclosure also covers a process for manufacturing a composite yarn according to the first aspect, said process comprising at least one step of depositing, by coating or extrusion, a matrix comprising at least one polymer material and at least one reinforcing filler, onto a core yarn.
  • the matrix incorporates, in addition to the polymer material, at least one reinforcing filler and possibly at least one other additive such as a flame-retardant filler.
  • the polymer used for the deposition is a conventional polymer such as a PVC, a polyacrylate, a polyolefin, a polyester, a polyvinyl, a polystyrene, a polyurethane, an ethylene-vinyl acetate (or EVA) polymer or a polyamide.
  • PVCs and polyacrylates are generally used by the deposition by coating, typically with plastisol technology.
  • Polyolefins, polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers and polyamides are generally used by extrusion deposition.
  • the reinforcing filler is dispersed throughout the polymer before deposition.
  • the reinforcing filler is mixed with the polymer, in particular when the latter is heated for the deposition if the polymer is deposited in liquid form. It may be mixed as a mixture of powders when the polymer is in powder form. It may also be intimately mixed with the polymer by an extrusion operation ("compounding") when the polymer is in the form of granules.
  • Such deposition is carried out particularly preferably such that a proportion of the filler is disposed in the inter-filament interstices of the core yarn. This is generally carried out by adjusting the rheological characteristics of the matrix during deposition, as is known to the person of ordinary skill in the art.
  • the depositing step is performed by coating with a plastisol on the filaments of the core yarn, the plastisol more preferably being based on polyvinyl chloride (PVC) or alternatively based on acrylic resin (polyacrylate).
  • PVC polyvinyl chloride
  • acrylic resin polyacrylate
  • Plastisols are well known to the person of ordinary skill in the art. They are generally pastes at room temperature obtained by dispersing a powdery synthetic resin (which is the polymer) in a liquid plasticizer. Various plastisols are described, for example, in patent application WO 2010/001240.
  • the manufacturing process further comprises at least one step of coating, onto the composite yarn manufactured at the depositing step, at least one layer of polymer material in which is dispersed at least one reinforcing filler.
  • the layer further comprises at least one fire-retardant filler.
  • This coating step is typically performed by coating with a plastisol onto the composite yarn obtained at the depositing step or by extrusion of a compound onto the composite yarn obtained at the depositing step, preferably by coating with a plastisol onto the composite yarn obtained at the depositing step.
  • the layer incorporates at least one reinforcing filler, and possibly at least one other additive such as a fire-retardant filler.
  • the polymer used for the coating is generally similar to the polymer used for the deposition.
  • the polymer used for the coating is generally chosen from the group consisting of PVCs, polyacrylates, polyolefins, polyesters, polyvinyls, polystyrenes, polyurethanes, EVA polymers and polyamides.
  • the parameters of this coating step are generally similar to the parameters of the depositing step explained above, including addition by mixing one or more additives into the polymer before the coating.
  • the term“compound” means a compound (which is generally granular) of a plasticized polymer (PVC, polyacrylate, etc.), or a compound (which is generally granular) of a polymer (polyolefin, polyester, polyvinyl, polystyrene, polyurethane, EVA, polyamide, etc.) of low glass transition temperature, said compound also optionally comprising at least one additive such as a stabilizer and/or a fire- retardant filler.
  • the term“compound’ is well known to those of ordinary skill in the art.
  • the term“plasticized polymer” means, as it is understood to those of ordinary skill in the art, that there is intimate mixing between the polymer and a plasticizer which has been used to plasticize it.
  • the coating step is performed by extrusion of a compound
  • the coating step is performed by extrusion-coating of a composite yarn obtained in the depositing step with a compound in which is dispersed at least one reinforcing filler.
  • the reinforcing filler has been described above.
  • the disclosure also relates, in a third aspect, to a textile surface comprising at least one composite yarn according to the first aspect or manufactured according to the second aspect.
  • said textile surface is prepared by weaving.
  • EXAMPLE 1 Two composite yams according to one embodiment were manufactured, from PVC plastisol, by coating a non-flame-retardant matrix comprising silanized glass microbeads as reinforcing filler, followed by coating with a flame-retardant layer itself also containing silanized glass microbeads as reinforcing filler on a core yarn.
  • the core yarn was composed of a textile glass yarn from two different sources.
  • the silanized glass beads had a hardness of 5.5 Mohs.
  • a control composite yarn was also made on the basis of the teaching of patent EP 0900294, with two successive coatings of the same PVC plastisol on the same core yarn.
  • Core yarns textile glass yarns
  • the textile glass yarns are characterized by the chemical composition of the silionne, their titer expressed in tex, the diameter and the number of filaments of which the yarn is composed, their torsion and the type of sizing used:
  • the sizing is the protective coating deposited immediately after spinning the silionne, the final use of the textile glass yarn conditions the chemical nature of the sizing.
  • the core yarn was coated using a first non-flame-retardant coating containing silanized glass microbeads and then a second sparingly flame- retardant coating also containing silanized glass microbeads.
  • the compositions of the two plastisols used are given in Tables 1 and 2 below.
  • Plastisol 1 ( matrix )
  • RV-type Brookfield viscosity of this plastisol was: 1200 mPa.s (measured with a No. 3 spindle at 23°C).
  • the temperature of the yarn exiting the coating line was: 125°C.
  • RV-type Brookfield viscosity of this plastisol was: 1350 mPa.s (measured with a No. 3 spindle at 23°C).
  • Plastisols 1 and 2 contain no viscosity reducer. This absence of viscosity reducer is one advantage, which is very beneficial for the conservation of the plastisol and participates in reducing the emission of VOCs during the production of the composite yarn.
  • the composition of the plastisol used is given in Table 4 below. Table 4
  • the RV-type Brookfield viscosity of this plastisol was: 1300 mPa.s (measured with a No. 3 spindle at 23°C). This value was obtained with the addition of 5.4% of a volatile viscosity reducer, the presence of which generated VOCs during the transformation of the plastisol.
  • the temperature of the yarn at the outlet of the coating line was: 135°C.
  • yarn B includes an amount of fire-retardant filler equal to about 25% (i.e., the ratio of 1.9% to 7.5%) by weight of the amount of fire-retardant filler of the control yarn C, for the same fire resistance class.
  • the amount of fire-retardant filler was able to be reduced by about 75% to obtain a level of flame retardancy similar to that of the control composite yarn.
  • yam B according to the embodiment has a similar mineral materials/organic materials ratio (58.8% for the control yarn C; 50.5% maximum for yarn B), whereas the flame retardant/organic materials ratio is greatly reduced (15.2% for yarn C; 4.5% for yarn B).
  • yarn B makes it possible to obtain the same level of fire performance.
  • a composite yarn wherein the use of particles in a matrix enables the material, by virtue of the particles that are incorporated therein, to be present in the inter-filament interstices of the core yarn.
  • the particles interact both with the core yarn filaments and with the matrix polymer to provide one or more of the benefits described above, based on the disclosed parameters and the desired application.
  • One composite yam according to one embodiment (D) was manufactured, from PVC plastisol, by two successive coatings of the same PVC plastisol coating containing flame-retardant particles and silanized glass microbeads as reinforcing filler on a core yarn.
  • the core yarn is the standard textile glass yarn composed with a low torsion (28 rounds per meter) of Example 1 and a title of 68 tex.
  • Two types of silanized glass beads were used.
  • the silanized glass beads Microperl ® had a hardness of 5.5 Mohs.
  • the silanized glass beads Omicron ® had a hardness of 5.5 Mohs. They were spherical and had an average diameter of 5 pm, with a d v so of 7 pm, a d vi o of 2 pm and a dv9o of 15 pm, as measured for example by laser particle size measurement using a Malvern Masterizer 2000 Instrument machine.
  • One control composite yarn (E) was also used, which is a commercial product of the Applicant, made by two successive coatings of the same PVC plastisol on a core yarn.
  • the core yarn is the specific textile glass yarn with a high torsion (52 rounds per meter) of Example 1 and a title of 68 tex.
  • This commercial product has the best fire performance among the commercial products sold by the Applicant, thus meeting both the fire performance criteria“M1” of standard NF 92- 503 and the fire performance criteria“B1” of standard DIN 4102-1.
  • the RV-type Brookfield viscosity of this plastisol was: 900 mPa.s (measured with a No. 3 spindle at 23°C).
  • the temperature of the yarn at the outlet of the coating line was: 155°C.
  • the title of the composite yarn D according to the embodiment thus obtained was 139 tex.
  • the RV-type Brookfield viscosity of this plastisol was: 1300 mPa.s (measured with a No. 3 spindle at 23°C).
  • the temperature of the yarn at the outlet of the coating line was: 135°C.
  • Composite yarn D according to the embodiment gave textile surfaces having substantially similar weight, thickness and opening factors to that of the textile surface obtained by control composite yarn E, the mechanical properties of the two composite yarns are quite similar. Table 12
  • composite yarn D in comparison with the control yarn E, has a slightly lower flame retardant/organic materials ratio (15.4 % for control yarn E; 14% for composite yarn D), and a slightly lower flame retardant/plasticizer ratio (50.5% for control yarn E; 47.6% for composite yarn D).
  • Table 13 in comparison with the control yarn E, composite yarn D according to the embodiment has a slightly lower flame retardant/organic materials ratio (15.4 % for control yarn E; 14% for composite yarn D), and a slightly lower flame retardant/plasticizer ratio (50.5% for control yarn E; 47.6% for composite yarn D).
  • the FIGRA parameter measures the speed of the energetic production during the combustion.
  • FIGRA0.2 parameter provides the speed level to reach 0.2 MJ.
  • the FIGRA0.2 value for Euroclass“B” is less or equal than 120 W/s.
  • the TFIP parameter measures the total energetic production during the combustion.
  • the THIRboo parameter provides the energetic production level reached at 600s.
  • the THIRboo value for Euroclass“B” is less or equal than 7.5 MJ, whereas the THIRboo for Euroclass“C” is less or equal than 15.MJ.
  • the FIGRA0.2 value obtained with the textile made from composite yarn D according to the embodiment reflects, compared to the textile made from control yarn E, a very sharp decrease in energy production during combustion (90 W/s against 260 W/s) although they have very similar physical characteristics.
  • This level of performance (FIGRA0.2 ⁇ 100 W/s) cannot normally be achieved by glass-fiber-based textiles coated with plasticized PVC.
  • composite yarn D makes it possible to meet the requirements of Euroclass“B” of standard EN 13-501 -1 , the control yarn meeting only the requirement of Euroclass “C” of standard EN 13-501-1.
  • the textile surface obtained by composite yarn D according to the embodiment has a greatly improved fire performance although it has a lower flame retardant content than the textile surface obtained by control yarn E (5.6% against 7.8%) and a slightly lower flame retardant/plasticizer ratio (47.6% against 50.5%).
  • this is the first time that a composite yam obtained by coating a flame retardant plastisol on a glass textile yarn can meet the requirements of Euroclass“B” of standard EN 13-501 -1.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne un fil composite comprenant un fil d'âme multifilament continu incorporé dans une matrice, caractérisé en ce que la matrice comprend au moins un matériau polymère et au moins une charge de renforcement, la charge de renforcement étant formée à partir de particules fonctionnalisées, lesdites particules ayant une taille médiane (d v5o) inférieure à 40 µm. L'invention concerne également un processus de fabrication d'un tel fil composite, comprenant au moins une étape de dépôt, par enrobage ou extrusion, d'une matrice comprenant un polymère et d'une charge de renforcement, sur un fil d'âme. Une surface textile comprend au moins un tel fil composite.
PCT/EP2019/060238 2018-04-20 2019-04-19 Fil composite, processus de fabrication et surface textile comprenant un tel fil Ceased WO2019202151A1 (fr)

Priority Applications (20)

Application Number Priority Date Filing Date Title
IL277527A IL277527B2 (en) 2018-04-20 2019-04-19 Composite yarn, manufacturing process and textile surface comprising such yarn
ES19718185T ES3058258T3 (en) 2018-04-20 2019-04-19 Composite yarn, manufacturing process and textile surface comprising such a yarn
US17/048,600 US11530497B2 (en) 2018-04-20 2019-04-19 Composite yarn, manufacturing process and textile surface comprising such a yarn
EP25192715.8A EP4617413A3 (fr) 2018-04-20 2019-04-19 Fil composite, procédé de fabrication et surface textile comprenant un tel fil
CN201980025982.0A CN111971427B (zh) 2018-04-20 2019-04-19 复合纱、制造方法和包含此种纱的纺织品表面
SG11202009168PA SG11202009168PA (en) 2018-04-20 2019-04-19 Composite yarn, manufacturing process and textile surface comprising such a yarn
KR1020207030024A KR20200144101A (ko) 2018-04-20 2019-04-19 복합사, 제조 방법 및 이러한 복합사를 포함하는 직물 표면
JP2021506064A JP7427653B2 (ja) 2018-04-20 2019-04-19 複合ヤーン、製造プロセスおよびそのようなヤーンを含むテキスタイル表面
AU2019254690A AU2019254690B2 (en) 2018-04-20 2019-04-19 Composite yarn, manufacturing process and textile surface comprising such a yarn
CA3097611A CA3097611A1 (fr) 2018-04-20 2019-04-19 Fil composite, processus de fabrication et surface textile comprenant un tel fil
BR112020021322-5A BR112020021322B1 (pt) 2018-04-20 2019-04-19 Fio compósito, processo de fabricação e superfície têxtil compreendendo tal fio
DK19718185.2T DK3781734T3 (da) 2018-04-20 2019-04-19 Kompositgarn, fremgangsmåde til fremstilling og tekstiloverflade, der indeholder et sådant garn
CN202410168694.3A CN118029034A (zh) 2018-04-20 2019-04-19 复合纱、制造方法和包含此种纱的纺织品表面
MX2020011056A MX2020011056A (es) 2018-04-20 2019-04-19 Hilo compuesto, proceso de fabricacion y superficie textil que comprende tal hilo.
EP19718185.2A EP3781734B1 (fr) 2018-04-20 2019-04-19 Fil composite, processus de fabrication et surface textile comprenant un tel fil
ZA2020/07125A ZA202007125B (en) 2018-04-20 2020-11-16 Composite yarn, manufacturing process and textile surface comprising such a yarn
US17/981,096 US12091782B2 (en) 2018-04-20 2022-11-04 Composite yarn, manufacturing process and textile surface comprising such a yarn
JP2024008588A JP7756734B2 (ja) 2018-04-20 2024-01-24 複合ヤーン、製造プロセスおよびそのようなヤーンを含むテキスタイル表面
US18/800,490 US12497716B2 (en) 2018-04-20 2024-08-12 Composite yarn, manufacturing process and textile surface comprising such a yarn
US19/389,707 US20260071356A1 (en) 2018-04-20 2025-11-14 Composite Yarn, Manufacturing Process and Textile Surface Comprising Such a Yarn

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR1853527A FR3080387B1 (fr) 2018-04-20 2018-04-20 Fil composite renforce, procede de preparation et textile comprenant un tel fil
FR1853527 2018-04-20
FR1858616A FR3080386B1 (fr) 2018-04-20 2018-09-21 Fil composite, procede de fabrication et surface textile comprenant un tel fil
FR1858616 2018-09-21

Related Child Applications (2)

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US17/048,600 A-371-Of-International US11530497B2 (en) 2018-04-20 2019-04-19 Composite yarn, manufacturing process and textile surface comprising such a yarn
US17/981,096 Continuation US12091782B2 (en) 2018-04-20 2022-11-04 Composite yarn, manufacturing process and textile surface comprising such a yarn

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FR2548084A1 (fr) * 1983-06-28 1985-01-04 Ato Chimie Procede de fabrication d'objets composites et objets composites obtenus
FR2566324A1 (fr) * 1984-06-26 1985-12-27 Galichon Jean Realisation d'un preimpregne fibres/metal ou mineral pour la realisation d'objets composites de haute performance
FR2648957A1 (fr) * 1989-06-22 1990-12-28 France Etat Armement Materiau composite a caracteristiques modulables par preimpregnation d'une fibre continue
EP0900294A1 (fr) 1996-05-07 1999-03-10 Chavanoz Industrie Fil composite
WO2001009226A1 (fr) * 1999-07-30 2001-02-08 Ppg Industries Ohio, Inc. Brins a base de fibres de verre impregnees et produits les incorporant
WO2003056082A2 (fr) 2001-12-28 2003-07-10 Chavanoz Industrie Fil composite, procede d'obtention et structure textile obtenue
EP1605094A1 (fr) * 2003-03-05 2005-12-14 Teijin Fibers Limited Structure fibreuse deodorante et son procede de fabrication
WO2010001240A1 (fr) 2008-07-02 2010-01-07 Porcher Industries Composition ignifugee a base de pvc
WO2011033130A1 (fr) 2009-09-21 2011-03-24 Chavanoz Industrie Fil composite, procédé pour son obtention et structure textile résultante
WO2014083162A2 (fr) 2012-11-30 2014-06-05 Commissariat à l'énergie atomique et aux énergies alternatives Procédé pour préparer un verre à porosité bimodale, eventuellement fonctionnalisé et ledit verre
WO2014207397A1 (fr) 2013-06-27 2014-12-31 Centre National De La Recherche Scientifique (C.N.R.S.) Procédé de préparation d'une composition comprenant des particules minérales fonctionnalisées et composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2548084A1 (fr) * 1983-06-28 1985-01-04 Ato Chimie Procede de fabrication d'objets composites et objets composites obtenus
FR2566324A1 (fr) * 1984-06-26 1985-12-27 Galichon Jean Realisation d'un preimpregne fibres/metal ou mineral pour la realisation d'objets composites de haute performance
FR2648957A1 (fr) * 1989-06-22 1990-12-28 France Etat Armement Materiau composite a caracteristiques modulables par preimpregnation d'une fibre continue
EP0900294A1 (fr) 1996-05-07 1999-03-10 Chavanoz Industrie Fil composite
WO2001009226A1 (fr) * 1999-07-30 2001-02-08 Ppg Industries Ohio, Inc. Brins a base de fibres de verre impregnees et produits les incorporant
WO2003056082A2 (fr) 2001-12-28 2003-07-10 Chavanoz Industrie Fil composite, procede d'obtention et structure textile obtenue
EP1605094A1 (fr) * 2003-03-05 2005-12-14 Teijin Fibers Limited Structure fibreuse deodorante et son procede de fabrication
WO2010001240A1 (fr) 2008-07-02 2010-01-07 Porcher Industries Composition ignifugee a base de pvc
WO2011033130A1 (fr) 2009-09-21 2011-03-24 Chavanoz Industrie Fil composite, procédé pour son obtention et structure textile résultante
WO2014083162A2 (fr) 2012-11-30 2014-06-05 Commissariat à l'énergie atomique et aux énergies alternatives Procédé pour préparer un verre à porosité bimodale, eventuellement fonctionnalisé et ledit verre
WO2014207397A1 (fr) 2013-06-27 2014-12-31 Centre National De La Recherche Scientifique (C.N.R.S.) Procédé de préparation d'une composition comprenant des particules minérales fonctionnalisées et composition

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