MX2008008065A - Glass fibres and glass fibre structures provided with a coating containing nanoparticles - Google Patents

Abstract

The invention relates to reinforcing glass fibres and structures of such glass fibres with an improved resistance to damp ageing and provided with a coating composition which is obtained from a solution and/or a suspension and/or an emulsion comprising (in weight%of solid materials) between 60 and 95%of at least one polymer, and between 2 and 18%of nanoparticles. The invention also relates to a coating composition for coating said fibres and fibre structures, to the method for the production thereof, and to composites incorporating the inventive fibres and fibre structures.

Description

GLASS FIBERS AND GLASS FIBER STRUCTURES EQUIPPED WITH A COATING THAT INCORPORATES NANOPARTICLES The present invention relates to glass fibers and glass fiber structures equipped with a coating containing nanoparticles, especially clay, boehmite, proposed for the reinforcement of organic and / or inorganic materials. It also refers to the coating composition that may be applied on said yarns and said structures, the method of preparing said composition and the compounds incorporating such yarns and structures. Conventionally, reinforcing glass fibers are produced by mechanically attenuating molten glass streams flowing out of the numerous orifices in a network filled with molten glass, under gravity, through the effect of hydrostatic pressure due to the height of the liquid. , in order to form filaments that are coated with a sizing and are assembled into base yarns, these threads are then collected in a suitable support.

Glass fibers in their various forms (continuous, short or shredded yarns, nets, meshes, fabrics, etc.) are commonly used for the effective reinforcement of matrices of various types, for example, organic materials and inorganic thermoplastic or thermoset materials, for example cement. Although the sizing helps to a great extent to protect the filaments from chemical and environmental attacks, the level of thread protection is often more insufficient and should be improved. In particular, it is desired to increase the thermal relaxation resistance of glass fibers which are incorporated in corrosive matrices, for example, cementitious materials, or which are in contact with the aqueous medium or the medium containing organic solvents. The object of the present invention is to improve the thermal relaxation resistance in a humid environment of glass fibers and glass fiber structures intended to be incorporated as force components for organic and / or inorganic materials. This object is achieved according to the invention by means of glass fibers and fiberglass structures equipped with a coating based on a polymer containing nanoparticles. More precisely, a subject of the invention is reinforcing glass fibers and reinforcing glass fiber structures equipped with a coating composition, obtained from a solution and / or suspension and / or an emulsion comprising (in% in weight of solids): - 60 to 95% of at least one polymer; - 2 to 18% nanoparticles. In the present invention, the term "nanoparticles" is understood to mean particles of a material that are formed from a group of atoms or molecules, having one or more dimensions that may vary between 1 and 100 nanometers, preferably between 1 and 50 nanometers . The shape of these particles can vary widely, for example, they can have the appearance of a sphere, a tube, a needle, a leaflet or a platelet. Still within the context of the invention, the term "threads" should be understood to mean the base threads that result as a result of assembling a multitude of filaments, and the products derived from these yarns, especially assemblies of these base yarns in the form of rollers. Such assemblies can be obtained by simultaneously unrolling the base yarns of several packages and then assembling said yarns in hooks that are wound on a rotating support. They can also be "direct" rollers with a concentration (or linear density) equivalent to that of assembled rollers, obtained by gathering the filaments directly below the net and winding them on a rotating support. Also according to the invention, the term "coating composition" is understood to mean a composition capable of being deposited on filaments and wire structures and in which it is in the form of a solution and / or suspension and / or dispersion comprising at least 10% by weight of solvent, preferably at least 25% and at most 85%. Finally, the term "solvent" is understood to mean water, organic solvents that can help dissolve certain constituents of the coating composition and mixtures of water with one or more of these solvents. As examples of such solvents, mention may be made of alkanes, alcohols, ketones and esters. In most cases, the composition does not contain any organic solvents, especially in order to limit the emissions of volatile organic compounds (VOCs) in the atmosphere. The polymer according to the invention confers protection against wet thermal relaxation, provides the coating with the necessary mechanical cohesion by making the nanoparticles adhere to the glass fiber and by joining the nanoparticles together, and makes it possible to ensure the bond with the material to reinforce. The choice of polymer depends on the objective application. As a general rule, the polymer is an organic polymer, for example, a polyvinyl alcohol, a polyvinyl acetate (homopolymer or copolymer, such as a copolymer of ethyl acetate / vinyl), a polyvinyl chloride, a styrene -butadiene (SBR) or nitriio-butadiene polymer (NBR) or an acrylic polymer. Preferably, the polymer is polyvinyl alcohol, a SBR polymer or a polyacrylic polymer.

Preferably, the polymer represents 75 to 90% by weight of the coating composition. The nanoparticles are essential for the coating because they make it possible to obtain an organic solvent and water barrier effect which results in a greater ability of the filament to be resistant to thermal relaxation in a humid environment. This is due to the fact that nanoparticles are obstacles that prevent the rapid penetration of these compounds by creating, in the coating, trajectories of torture diffusion towards the glass, which is protected in this way better. The degree of protection varies as a function of the amount and shape of the nanoparticles in the coating. Particles of various dimensions can give the aforementioned effects. In this regard, nanoparticles having a high aspect ratio (ratio of the largest dimension to the smallest dimension) such as platelets are particularly suitable as they are able to be oriented parallel to the surface of the filaments, which gives the yarn greater resistance to thermal relaxation in a humid environment The nanoparticles according to the invention are composed of a mineral material, mainly containing more than 30% by weight of such material, preferably more than 40%, and advantageously more than 45%. Preferably, the nanoparticles are based on clay or boehmite. The term "clay" here should be considered in its general definition accepted by those skilled in the art, it mainly defines luminescent hydrated ions of the general formula Al203. Si02 xH20, where x is the degree of hydration. Such clay consists of aluminosilicate sheets having a thickness of a few nanometers linked together by hydrogen bonds or ionic bonds between the hydroxide groups present in the leaves and water and / or the cations present between said sheets. By way of example, mention may be made of the mica types, such as smectites, montmori loni t, hectorite, bentonites, nontronite, beideiite, voionskoite, saponite, sauconite, magadiite, vermiculite, mica, keniaite and synthetic hectorites.

Preferably, the clay is selected from type 2/1 types, advantageously smectites. The particularly preferred clay is montmor i loni ta. The clay can be a calcined clay, for example one that has undergone a heat treatment at a temperature of at least 750 ° C. The clay can also be a modified clay, for example one modified by cation exchange in the presence of a solution of an ammonium, phosphonium, pyridinium or imidazolium salt, preferably an ammonium salt. The clay nanoparticles are generally present in the form of platelets having a thickness of a few nanometers and a length which can be up to 1 micron, generally less than 100 nanometers, it being possible for these platelets to be individual platelets or aggregates. The clay nanoparticles can be obtained by subjecting a clay, possibly calcined and / or modified as mentioned above, to the action of at least one blowing agent, which has the function of separating the leaves from the clay. clay. For example, the blowing agent may be a hydrocarbon or an alcohol, such as ethanol, isopropanol, ethyl glycol, 1,3-propanediol, 1-butanediol and polyalkylene glycols, especially one with a molecular weight of less than of 1200. The term "boehmite" refers to alumina monohydrates. Preferably, boehmite is a synthetic boehmite obtained by a hydrothermal reaction of an aluminum hydroxide. The nanoparticles of boehmite may be in the form of beads, needles, ellipsoids or platelets, the latter form being preferred. Advantageously, the nanoparticles are treated by an agent that contributes to decrease the diffusion of water and thus makes it possible to increase the thermal relaxation resistance of the yarn in a humid environment, preferably a hydrophobic agent. The methods for making the hydrophobic particles are known. For example, nanoparticles can be reacted with a compound of the formula RaXY4_a in the presence of water and an acid, in such a formula: R represents a hydrogen atom or a hydrocarbon-based radical containing 1 to 40 carbon atoms, it being possible for said radical to be linear, branched or cyclic, saturated or unsaturated, possibly containing one or more heteroatoms O or N or substituting one or more amino groups, carboxylic acid, epoxy or amido, and the R groups being identical or different; X represents Si, Zr or Ti; Y is a hydrolysable group, such as an alkoxy containing 1 to 12 carbon atoms, possibly containing one or more O or N heteroatoms or a halogen, preferably Cl; and a is equal to 1, 2 or 3. Preferably, the compound corresponding to the aforementioned formula is an ilane organ, advantageously an organisolane containing two or three alkoxy groups. By way of example, mention may be made of? -aminopr opi 11 r ime t oxi s i tin? -aminopropyltriethoxysilane; N-phenyl-β-iTiinopropyltri ethoxysilane, N-styryl-ineethyl-y-aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, β-acryloxypropyltrimethoxysilane, vitamin I, methoxypropionate, vitamin I, butylcarbamate and methylphenidate, and (polyalkylene oxide) propylate toxins. Preferably, α-aminopropyltri ethoxysilane, N-phenyl-β-aminopropyltrimethoxysilane, N-styrylaminoethyl-α-aminopropyltrimethoxysilane, β-glycoidoxypropyltrimethoxy silane and α-methacryloxypropyltrimethoxysilane are selected. The grafting agent is added in an amount representing 15 to 75% by weight, preferably 30 to 70% by weight of the initial nanoparticles. Preferably, the nanoparticles represent 2.5 to 15% by weight of the coating composition. In addition to the abovementioned constituents that are essentially involved in the coating structure, one or more other constituents may be present. In this way, it is possible to introduce a positive temperature which decreases the glass transition temperature of the polymer, which gives flexibility to the coating and limits the shrinkage after drying. The amount of tabletting is preferably from 5 to 25% by weight of the coating composition. The coating may comprise a dispersing agent, which helps to disperse the nanoparticles and promotes compatibility between the other constituents and water. The dispersing agent may be chosen from: organic compounds, in particular: optionally halogenated, aliphatic or aromatic polyalkyl compounds, such as alkylphenols and oxylated / propoxylated, preferably containing 1 to 30 ethylene oxide groups and 0 to 15 propylene oxide groups , bisphenols ethoxy sides / propoxy sides, preferably containing 1 to 40 ethylene oxide groups and 0 to 20 propylene oxide groups, ethoxy side / propoxy side fatty alcohols, preferably the alkyl chain which comprises 8 to 20 carbon atoms, and containing 2 to 5 ethylene oxide groups and up to 20 propylene oxide groups. These polyalkoxylated compounds can be blocking copolymers or random copolymers. fatty acid esters polyalkoxy sides, for example, polyethylene glycol esters, the alkyl chain of which preferably comprises 8 to 20 carbon atoms, and containing 2 to 50 ethylene oxide groups and up to 20 propylene oxide groups and amine compounds , for example optionally alkoxylated amines, amine oxides, optionally alkylated and / or alkoxylated amidoamines, sodium, potassium or ammonium succinates and taurates, sugar derivatives, especially sorbitan, and alkyl, potassium or ammonium alkyl sulfates, alkyl phosphates and ether phosphates; and ^ inorganic compounds, for example silica derivatives, these compounds possibly being used by themselves or as a mixture with the organic compounds mentioned above. In order to prevent stability problems with the coating composition and a homogeneous dispersion of the nanoparticles, it is preferred to use cationic or nonionic surfactants. Preferably, the amount of agent of dispersion represents from 0.01 to 60%, preferably from 0.25 to 50%, of the weight of the nanoparticles. It is also possible to introduce a viscosity control agent, which makes it possible to adjust the viscosity of the composition with the conditions of application to the filaments, such viscosity is in general between 50 and 2000 mPa.s, preferably at least 150 mPa.s East The agent also makes it possible to adapt the viscosity of the nanoparticle dispersions to allow them to be treated under high cutting conditions to improve their state of exfoliation and / or dispersion, as will be explained in the rest of the text. The viscosity control agent is chosen from polyvinyl alcohols, polyvinyl pyrrolidones, hydroxymethyl celluloses, carboxymethylcelluloses and polyethylene glycols. The amount to regulate agent in the coating is preferably between 0.5 and 25% and advantageously between 1.5 and 18%. The coating may also include: 0.2 to 20% by weight, preferably 0.1 to 10%, by weight of a lubricant, for example a mineral oil, a fatty acid ester, such as isopropyl palmitate or butyl stearate, an alkylamine or a polyethylene wax; 0.25 to 20%, preferably 0.5 to %, by weight of a complexing agent such as derivative of EDTA, gallic acid or phosphoric acid; and 0.05 to 3%, preferably 0.1 to 2%. by weight of an antifoaming agent, such as a silicone, a polyol or a vegetable oil. All the aforementioned compounds contribute to the production of glass fibers and fiberglass structures that can be easily manufactured, are capable of being used as reinforcements, and are incorporated without any problem in the resin during the manufacture of the compounds and also possess high resistance to thermal relaxation in a humid environment. As a general rule, the amount of coating represents 8 to 200% of the weight of the final yarn or the final yarn structure, preferably 15 to 100%, and more frequently 20 to 60%. The yarn equipped with the coating according to the invention can be made of glass of any kind, for example class E, class C, class R, and class AR and glass with a low boron content (less than 6%). Class E and class AR are preferred. The diameter of the glass filaments constituting the yarns can vary widely, for example from 5 to 30 μm. Similarly, wide variations can occur in the linear density of the yarn, which can vary from 11 to 4800 tex depending on the proposed applications. Another subject of the invention is the coating composition that can be deposited on glass filaments and glass fiber structures. It comprises the constituents mentioned above and a solvent. The coating composition comprises (in% by weight): 8 to 90% of at least one polymer, preferably 10 to 75%; 1 to 15% of nanoparticles, preferably 1.5 to 10%; 0 to 10% of at least one lubricant, preferably 0.1 to 6%; - 0 to 15% of at least one agent of dispersion, preferably 0.1 to 8%; and 0 to 15% of at least one viscosity control agent, preferably 0.1 to 8%. The amount of solvent to be used is determined to obtain a solids content ranging from 8 to 90%, preferably from 15 to 75%. The preparation of the coating composition is carried out in the following manner: a) the nanoparticles are dispersed in the solvent, preferably in the presence of a dispersing agent and if necessary a viscosity control agent; and b) the polymer and optional constituents mentioned above are added to the nanoparticle dispersion. Advantageously, step a) is carried out with sufficient agitation to avoid the risk of nanoparticle sedimentation. The dispersion of nanoparticles based on a sheet-like material, which is clay or boehmite, can be obtained in various ways, all having the purpose of increasing the degree of exfoliation and / or dispersion of the material. According to a first modality, the 1 nanoparticles are introduced into the solvent containing a dispersing agent, and the mixture is treated under high cutting conditions for example in an Ultraturax® device and / or subjected to the action of ultrasound. To give an indication, a good nanoparticle dispersion is obtained by treating the mixture in an Ultraturax® operating at a speed of 3000 to 10000 rpm for 5 to 30 minutes or by ultrasound with an energy of 200W and a frequency of 20 kHz for 15 to 120 minutes. Advantageously, a viscosity control agent is introduced into the mixture before the treatment, in particular when the nanoparticles are subjected to shear force. Where appropriate, a part of the polymer of step b) may be added to the dispersion before the cutting treatment, which makes it possible to reduce the amount of dispersing agent and optionally to carry out a more suitable adjustment of the viscosity. According to a second embodiment, the nanoparticles are mixed with granules of a thermoplastic polymer, such as a polyvinyl acetate, a polyamide and a polyurethane, or a T erbery t abi 1 i zador, such as an epoxy, phenolic or acrylic resin, and a polyurethane, and the mixture is introduced into an extruder. The extrudates are then emulsified in the solvent under conditions known to those skilled in the art. The application of the coating on the reinforcing glass fiber and the structure of such glass fibers may be carried out by any known means. This means may consist in spraying the coating composition on the yarn, or in immersing the yarn in a bath of the coating composition and passing it, in leaving the bath, in a calibration nozzle that allows the quantity to be deposited on the thread is regulated. In the case of a wire structure, especially a mesh or a fabric, the coating composition can be applied by spraying, by immersion in a bath of said composition generally followed by a rolling operation, or by passing the structure on a device which operates by die coating, for example using a calibrating knife that fixes the thickness of the coating.

The solvent is usually removed by drying the yarn and yarn structure prior to collection in the form of a container, for example, by a thermal path using hot air or by contacting one or more drying rollers, or by means of a treatment of infrared radiation. The yarn or wire structure equipped with the coating obtained in this way can overcome an additional coating operation with a coating composition that is identical or different from the previous one, especially it can or can not comprise nanoparticles. Another subject of the invention is a composite comprising at least one organic and / or inorganic material and glass fibers or one or more reinforcing glass fiber structures, said yarns or structure (s) being made completely or particularly of glass fibers or fiberglass structure (s) equipped with the composition according to the invention. The organic material may consist of one or more thermoplastic or thermoset polymers, and the organic material may be, for example, a Cementitious material, plaster or mortar, especially contained in front facing assemblies. The glass content within the compound is generally between 5 and 75% by weight, preferably 5 to 50%. The examples given below illustrate the invention, however without limiting it. In the examples, the following raw materials are used to prepare the coating compositions and the sizing compositions: polymer (re-stretching): "polyvinyl alcohol (degree of hydrolysis: 98%), sold under the reference" CELVOL® 325"by Vinamul, with a solids content of 97.5%; • styrene / butadiene rubber (SBR), sold under the reference "STYRONAL® D157" by BASF, with a solids content of 50%; degradation agent (coating): "epoxy polyamide, sold under the reference" POLYCUP® 172LX "by Hercules, with a solids content of 13.5%. film-forming agents (ens imaje) "bisphenol A epoxy resin, sold under the reference" EPIREZ® 3510 W 60"by Resolution, with a solids content of 60%;" bisphenol A epoxy resin / 1-methoxy mixture " 2 -propanol, sold under the reference "NEOXIL® 962D" by DSM, with a solids content of 40%; "ETS4, mixture containing 30.7% by weight of epoxy bisphenol A resin (sold under the reference" ARALDITE CY 207"by Huntsman) and 10% by weight of polyester resin (sold under the reference" NORSODYNE So56"by Cray Valley) with a solids content of 64%, nanoparticles: B clay A: montmor i loni ta modified by an ion exchange with a quaternary ammonium, sold under the reference "Dellite® 67G" by Laviosa Chimica Mineraria, with a solids content of 100%; "clay B: mon tmor illoni ta modified by exchange of ions with a quaternary ammonium (sold under the reference "Dellite® 67G" by Laviosa Chimica Mineraria) treated in dispersion in water with N-es tr i laminoe t il -? - aminopropi 11 rime t oxi si tin (sold under the reference "SILQUEST A-1128" by GE Silicones), with a solids content of 100%; 1 clay C: montmor i loni ta modified by ion exchange with a quaternary ammonium (sold under the reference "Dellite® 67G" by Laviosa Chimica Mineraria) treated in ethylene glycol dispersion with N-t-styrylaminoet il-α-aminopropi 11 r imet oxi si lño (sold under the reference "SILQUEST A-1128" by GE Silicones), with a solids content of 100%; 'D clay: montmori loni t a modified by ion exchange with a quaternary ammonium (sold under the reference "Dellite® 67G" by Laviosa Chimica Mineraria) treated in dispersion in PEG 300 with N-es t i r i laminoe t i 1 -? - aminopropi lmetoxisi laño (sold under the reference "SILQUEST A-1128" by GE Silicones), with a solids content of 100%; "clay E: montmor i loni t a (sold under the reference" Dellite® HPS "for Laviosa Chimica Mineraria) treated in dispersion in PEG 300 with N-styrylaminoethyl-α-aminopropylmethoxylated (sold under the reference "SILQUEST A-1128" by GE Silicones), with a solids content of 100% "boehmite in the form of a platelet, obtained by hydrothermal synthesis of the hydroxy lumina; Boehmite A: particles smaller than 50 nm, with a solids content of 28%; Boehmite B: modified by a? -aminopr opi 11 retatoxi siño (sold under the reference "SILQUEST® A-1100" by GE Silicones) in formic acid, 1% by weight of the nanoparticles, with a solids content of 25%; Boehmite C: modified by? - aminopropy lt riet oxy siilane (sold under the reference "SILQUEST® A-1100" by GE Silicones), 2% of the weight of the nanoparticles, with a solids content of 100%; Boehmite D: modified by α-methacryloxypropyltrimethoxysilane (sold under the reference "SILQUEST® A-174" by GE Silicones), 1% by weight of the nanoparticles, with a solids content of 100%; coupling agents (sizing): "? -methacryloxypropyltriethoxysilane, sold under the reference" SILQUEST® A-174NT "by GE Silicones, with a solids content of 80% The compound was first hydrolysed in the presence of acetic acid;" Polyazamide sililatada, sold under the reference "SILQUEST® A-1387" by GE Silicones, with a solids content of fifty% . pias t i ficante: "Ethoxylated fatty alcohols, sold under the reference "SETILON® KN" for Cognis, with a solids content of 57% "Copolymer of acetate et i leño / vini lo, sold under the reference" MOWILITH® 1871"by Vinamul, with a solids content of 53%; viscosity control agent:" Hydroxyethyl cellulose, sold under the reference "NATROSOL® 250 HBR" by Aqualon, with a solids content of 100%; dispersing agents and lubricants: "Alqui lamidoamine, sold under the reference" SODAMINE® P45"by Arkema, with a solids content of 100%;" Polyether phosphate mixture sold under the regency "TEGO DISPERS® 651" by Degusta, with a solids content of 30%; "Mixture of ethoxylated alcohol and glycerol esters, sold under the reference" TEXLUBE® NI / CS2"by Achitex, with a solids content of 100%;" Alkyl acetate lamidoamine, sold under the reference "CATIONIC SOFTENER FLAKES®" by Goldschmidt, with a solids content of 100%; "Modified polyethylene wax, sold under the reference" HYDROCER® 145"by Shamrock, with a solids content of 50%, and anti-foaming agent:" Polyether, sold under the reference "TEGO FOAMEX 830" by Degusta, with a solids content of 100%. In these examples, the tensile strength of the yarn was measured after a moist thermal relaxation treatment in a chamber saturated with water vapor at 80 ° C. EXAMPLE 1 to 7 These examples illustrate glass fibers coated with coating compositions containing clay nanoparticles. The coating compositions contain the raw materials given in Table 1 (in weight percent). The compositions were prepared under the following conditions: The polyvinyl alcohol (CELVOL® 325) was dispersed in water at room temperature (20-25 ° C), with stirring, then the dispersion was heated to 80 ° C until a solution was obtained. The nanoparticles were dispersed in water containing the anti-foaming agent (TEGO FOAMEX® 830) and the lubricant (HYDROCER® 145), then the dispersion was treated in an Ultraturax® (5 minutes at 9000 rpm / min). The dispersion obtained in this way was added to the first dispersion, then the plasticizer (MOWILITH®) and the degradation agent (POLYCUP® 172LX) were introduced with vigorous stirring for at least 30 minutes. The viscosity of the dispersion was between 300 and 800 mPas.s to allow the correct application in the yarn. If necessary, the viscosity can be adjusted by adding water to the dispersion. The coating composition was applied on a yarn made of glass filaments E of 13 μm in diameter (300 tex), unrolling from a package in the form of a cake, by dipping into a bath of said composition and passing through of a calibration nozzle (volatile solids: 12 to 18%).

The yarns used were coated with a base sizing composition that was found free of nanoparticles (example 1) or contained nanoparticles (examples 2 to 7) in the amounts indicated below, expressed in% by weight: Base sizing composition: EPIREZ® 3510 60 4.00 SILQUEST® A-174 0.45 SILQUEST® A-1387 0.20 NATROSOL® 250 HBR 0.20 NEOXIL® 962D 2.50 SETILON® KN 0.10 TEXLUBE® NICS2 0.30 Water qsp 100% Nanoparticles The tensile strength of glass strips coated with the coating composition tested under the conditions of Moist thermal relaxation is given in Table 1 Table 1 In relation to example 1 which does not contain any of the nanoparticles, the yarns of examples 2 to 7 according to the invention have a better wet thermal relaxation resistance characterized by a very high tensile strength after 3 days and days. Threads containing nanoparticles grafted with a silane have a particularly high thermal relaxation resistance after 14 days with an improvement of 39.1% (example 5) to 53.2% (example 3) in relation to the thread that is free of nanoparticles. The thread of example 7 containing a higher level of nanoparticles than the yarn of example 2, has a worse resistance to thermal relaxation while having a better resistance than to the yarn of example 1 without nanoparticles. EXAMPLES 8 TO 15 These examples illustrate glass fibers coated with coating compositions containing boehmite nanoparticles. The coating compositions contain the raw materials in Table 2 (in% by weight). These compositions were prepared under the following conditions: The boehmite nanoparticles were poured into a mixture of dispersing agent (TEGO DISPERS® 651) and anti-foaming agent (TEGO FOAMEX® 830), then a part of the polymer (STYRONAL® 517) , was added, and the mixture was treated in an Ultraturax® (30 minutes at 5000 rpm).

Then, the other part of the polymer was added and again treated in the Ultraturax® (5 minutes at 5000 rpm). The viscosity of the dispersion was between 300 and 800 mPa.s to allow a correct application in the yarn. If necessary, the viscosity can be adjusted by adding water to the dispersion. The coating composition was applied to a yarn made of glass filaments E of 13 μm in diameter (300 tex), unrolling from a package in the form of a cake, by dipping into a bath of said composition and passing through of a calibration nozzle (volatile solids 30 to 40%). The threads A and B were coated with the following sizing composition (in% by weight): Thread A Thread B SODAMINE® P 45 0.07 0.07 Boehmite C - 0.34 SILQUEST® A-174NT 0.21 0.21 SILQUEST® A-1387 0.28 0.28 CATIONIC SOFTENER FLAKES® 0.11 0.11 ETS4 5.04 5.04 Water qsp 100 The resistance to the tension of the fibers glass coated with the coating composition tested under the moist thermal relaxation conditions is given in Table 2. The yarns coated with a nanoparticle-containing sizing (examples 12 to 15) have a better resistance to wet thermal relaxation than the yarns in which the sizing does not contain nanoparticles (examples 8 to 11).

K (_p O < _p (i Table 2

Claims (10)

1. CLAIMS 1. Fiberglass reinforcement or reinforcing glass fiber structure equipped with a coating composition, obtained from a solution and / or a suspension and / or an emulsion comprising (in% by weight of solids): to 95% of at least one polymer; 2 to 18% of nanoparticles.
2. 2. Fiberglass or fiberglass structure as claimed in the claim 1, characterized in that the polymer is a polyvinyl alcohol, a polyvinyl acetate, a polyvinyl chloride, a styrene-butadiene (SBR) 0 Nitric oxide polymer (NBR) or an acrylic polymer.
3. 3. Fiberglass or fiberglass structure as claimed in the claim 1 or 2, characterized in that the nanoparticles are composed of more than 30% by weight of a mineral material, preferably more than 40%.
4. 4. Fiberglass or fiberglass structure as claimed in claim 1, characterized in that the nanoparticles are based on clay or boehmite.
5. 5. Fiberglass or fiber structure of glass as claimed in any of claims 1 to 4, characterized in that the nanoparticles are treated by an agent that helps to decrease the diffusion of water, preferably a hydrophobic agent.
6. 6. Fiberglass or fiberglass structure as claimed in claim 5, characterized in that the agent is a compound of the formula RaXY4_a in which: R represents a hydrogen atom or a hydrocarbon-based radical incorporating 1 to 40 carbon atoms, said radical possibly being linear, branched or cyclic, saturated or unsaturated, possibly containing one or more heteroatoms 0 or N or substituting one or more amino groups, carboxylic acid, epoxy or amido, and the R groups being identical or different, X represents SI, Zr or TI, Y is a hydrolysable group such as an alkoxy containing 1 to 12 carbon atoms, optionally containing one or more 0 or N heteroatoms, or a halogen, preferably Cl; and a is equal to 1, 2 or 3.
7. 7. Fiberglass or fiberglass structure as claimed in claim 6, characterized in that the compound is a organosilane, preferably incorporating two or three alkoxy groups.
8. 8. Fiberglass or fiberglass structure as claimed in any of claims 1 to 8, characterized in that the polymer represents 75 to 90% by weight of the coating composition.
9. 9. Fiberglass or fiberglass structure as claimed in any of claims 1 to 8, characterized in that the nanoparticles represent 2.5 to 15% by weight of the coating composition. 10. Fiberglass or fiberglass structure as claimed in any of claims 1 to 9, characterized in that the coating composition represents 8 to 200% of the weight of the final yarn or the final yarn structure. 11. Coating composition for the glass fiber or glass fiber structure, characterized in that it comprises: 8 to 90% of at least one polymer, preferably 10 to 75%; 1 to 15% of nanoparticles, preferably 1.5 to 10%; 0 to 10% of at least one lubricant, preferably 0.1 to 6%; 0 to 15% of at least one agent of dispersion, preferably 0.1 to 8%; and, 0 to 15% of at least one viscosity control agent, preferably 0.1 to 8%. 12. Coating composition as claimed in claim 11, characterized in that it has a solids content ranging from 8 to 90%, preferably 15 to 75%. 13. Method for preparing a coating composition as claimed in claim 11 or 12 comprising the following steps: a) the nanoparticles are dispersed in the solvent, preferably in the presence of a dispersant and if necessary a control agent of viscosity; and, b) the polymer and the optional constituents are added to the nanoparticle dispersion. 14. A method as claimed in claim 13, characterized in that the dispersion of step a) is carried out under high shear conditions, for example, in an Ultraturax® device and / or an ultrasound device. l o. Compound that comprises at least one organic and / or inorganic material and reinforcing glass fibers or one or more structures of reinforcing glass fiber, characterized in that said threads or structures are completely made in part of the glass fibers or structures equipped with a coating as claimed in one of claims 1 to
10. 10.