FR2973802A1 - Fabricating composite material that is useful for forming articles and reinforced objects e.g. window frame, by immersing fibers in hydrosol polymer, and drying and gelling the hydrosol, where fibers are obtained from hemp and linen - Google Patents

Abstract

The process comprises immersing fibers in a hydrosol polymer, and drying and gelling the hydrosol. The fibers are obtained from the origin of plants such as hemp and linen, and are mineral fibers consisting of glass fibers. The fibers are present: in the form of bands, strips, ribbons, cloth, sheets and mat; in woven or non-woven form; and in the form of ordered network or non-ordered network. The glass fibers are arranged in mat in the form of warp and weft. The vinyl chloride homopolymer present in the dispersed phase of hydrosol is obtained by radical polymerization in aqueous emulsion. The process comprises immersing fibers in a hydrosol polymer, and drying and gelling the hydrosol. The fibers are obtained from the origin of plants such as hemp and linen, and are mineral fibers consisting of glass fibers. The fibers are present: in the form of bands, strips, ribbons, cloth, sheets and mat; in woven or non-woven form; and in the form of ordered network or non-ordered network. The glass fibers are arranged in mat in the form of warp and weft. The vinyl chloride homopolymer present in the dispersed phase of hydrosol is obtained by radical polymerization in aqueous emulsion. The fibers extend in a hydrosol bath (3) having a dimension to ensure their complete immersion in the hydrosol. The drying step is performed using air, and is heated at a temperature, which is lower than the temperature of decomposition of hydrosol and fibers. The gelling step is performed by applying an infrared radiation on the hydrosol at a temperature, which is higher than a glass transition temperature of polymer. Independent claims are included for: (1) a composite material; and (2) profiles reinforced by the composite material.

Description

FIELD OF THE INVENTION The present invention relates to a process for the manufacture of a composite material based on fibers and vinyl chloride polymer. It also relates to this composite material itself. It also relates to the use of this composite material for shaping articles or for reinforcing objects as well as these articles or objects reinforced themselves and reinforced profiles. Many joinery elements such as frames, frames, jambs and window sills, shutters, doors and gates are frequently shaped with PVC (polyvinyl chloride) which gives them durability, corrosion resistance and thermal insulating power, while requiring only a minimum of maintenance. However, they lack rigidity from certain dimensions. Indeed the PVC profiles used for the construction of these carpentry elements are generally hollow to lighten them and create rooms with a thermal insulation role. However, a problem inherent in PVC is its low elastic modulus and therefore its defornability under stress especially when the ranges between fixed points are high. The lack of rigidity can be overcome by reinforcing the frames by reinforcements of metals and in particular steel (see document DE 199 33 099) or aluminum. However the use of metal reinforcements creates thermal bridges inside the chassis sections resulting in significant heat losses, and this by increasing the thermal conductivity. In addition, the presence of these metal reinforcements complicates the recycling of profiles at the end of life. In order to remedy this increase in thermal conductivity, it has been proposed to use reinforcements (pultruded inserts) consisting of thermosetting resins with fibers, preferably continuous, glass, aramid or carbon fibers (GB 2 144 472 or EP 0 441 449). Nevertheless, the use of thermosetting resins with glass fibers is expensive. As for the thermoplastic composite materials reinforced with cellulose fibers described in US 2004/062915, they are much more sensitive to moisture and therefore less durable. 2973802 -2

Conventionally, the PVC profiles reinforced by introduction of a metal insert or a pultruded insert are not or difficult to recycle. Another disadvantage of the profiles reinforced by a pultruded insert is the fact that it is necessary, as for the metal reinforcements, to manually introduce the reinforcement, which increases their cost of manufacture. In the document EP 1 276 602, there are described carpentry elements comprising a PVC profile reinforced by at least one reinforcing tape composed of polyester fibers, in particular PET (polyethylene terephthalate) or PBT (polybutylene terephthalate) co -melted with continuous glass fibers; the polymer and glass fibers being arranged longitudinally and parallel. The fiber ribbons or rovings are heated to melt the polymer, pressed and finally embedded in the outer and opposite walls of the PVC final profile to ensure sufficient rigidity and thus avoid the use of metal inserts or pultruded. Even if high mechanical properties are obtained and the manual insertion of the metal or pultruded section avoided by the manufacturing method using coils for unwinding continuous son comprising continuous filaments of glass and a thermoplastic material co-mingled between this process has many disadvantages. One of the drawbacks of this system is to combine two melt-incompatible different thermoplastic materials, a polyester such as PET or PBT on the one hand and PVC on the other hand, in the final product making not only the recycling of the difficult section, but also the recycling of production falls as well as impossible cuts in the profile production line. Another disadvantage is the longitudinal fragility of the reinforcements which preferentially break along the fibers during a multiaxial impact. Finally, a major disadvantage is the difficulty of calibrating the profile during its cooling given that the PVC and the reinforcing tape have different coefficients of thermal expansion. In EP 0 179 688, it has been proposed to subject reinforcing elements (especially glass fibers) for composite materials to an electrostatic field induced by a very high voltage electric current, and then to impregnate them with a matrix material. liquid (or precursor liquid material), while they are still under the influence of the field. The very high voltages to implement for the execution of this process are not without danger for the operators and require a lot of electrical energy; it is not easy either to synchronize the swelling of the reinforcing fibers

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under the action of the electrostatic field and their impregnation by the liquid matrix material. The present invention aims to solve these problems by providing a method for manufacturing an easily recyclable composite material, which can be shaped into articles of superior rigidity and can also be easily implemented according to conventional methods and in particular by pultrusion, in particular for the production of reinforced objects. For this purpose, the main object of the invention is a process for the manufacture of a composite material based on fibers and at least one vinyl chloride polymer comprising immersing the fibers in a hydrosol of said polymer followed by drying. and gelation of said hydrosol. The term "composite material" is intended to define, in the present description, a solid material comprising at least two immiscible components, but having a high adhesion capacity; one of the components of this material consists of a fiber frame, conventionally called "network", which provides the mechanical strength; the other component, conventionally referred to as "matrix", is the vinyl chloride polymer (s) which ensures (s) the cohesion of the structure and the retransmission of the forces towards the network.

The composite material manufactured according to the invention is advantageously substantially two-dimensional. In the present description, the expression "essentially two-dimensional" defines a material of which one of the characteristic dimensions ("thickness") is considerably less than at least one of the other two characteristic dimensions ("length" and "thickness"). width ") By" considerably less "is meant more than 25 times less, and preferably more than 100 times less. Otherwise expressed, the non-zero thickness of the two-dimensional material according to the invention is advantageously considerably less than the square root of the surface determined by its length and width.

The composite material manufactured according to the invention can be flexible (and therefore can be wound) or be more or less rigid. The fibers, which may also be called filaments, constituting the framework of the composite material manufactured according to the invention may advantageously be filiform elements of small diameter and very great length and / or filamentary substances which are fine and very elongated in relation to each other. to their thickness and / or staple fibers and / or long and continuous fibers. 2973802 -4 The assembly of fibers to form the framework or network can be ordered or not and regular or not. The fibers may be arranged in a disordered manner and entangled in woven or non-woven form or arranged non-interlockingly longitudinally and parallel to one another. Preferably, the fibers used in the constitution of the composite material according to the invention are continuous fibers. In a particularly preferred manner, these continuous fibers are arranged in a non-entangled manner, longitudinally and parallel to one another. The fibers used in the constitution of the composite material according to the invention are advantageously substantially two-dimensional as defined for the composite material according to the invention. The fibers that can be used for carrying out the process according to the invention are advantageously in the form of single or multiple strips, strips, ribbons, widths, sheets, "mat" or "roving", in Wherein these fibers are in woven form or not and form an ordered network or not. Preferably, the fibers are in the form of strips, ribbons or roving. The fibers may be particularly preferably disposed longitudinally and parallel thereto. The fibers that can be used according to the invention can be any commercially available fiber. It may be organic fibers, mineral fibers, mixtures of organic fibers and mineral fibers, mixtures of different organic fibers with each other and mixtures of different mineral fibers with each other. As examples of organic fibers, mention may be made of fibers derived from natural products of plant or animal origin, such as hemp, flax, cotton, wood and silk, for example, or synthetic products such as polymeric fibers. Examples of mineral fibers include asbestos fibers, glass fibers, metal fibers and basalt fibers, for example. Preferably, the fibers that can be used according to the invention come from products of vegetable origin chosen from hemp and flax or are mineral fibers chosen from glass fibers. Glass fibers are particularly preferred. Very good results have been recorded with fibers in the form of roving in which fiberglass is arranged in warp and weft. The fibers that can be used according to the invention may have been coated with a coupling agent during the cycle of their manufacture, thus improving the homogeneity of their subsequent impregnation with the vinyl chloride polymer hydrosol and the mechanical properties. composite material. Among the coupling agents usually used, mention may be made, in a non-exhaustive manner, of silanes, polyesters, acrylic or methacrylic polymers, waxes and epoxides. Of these, silanes are preferred. Examples that may be mentioned include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane and their derivatives such as gamma-methacryloxypropyltrimethoxysilane, N-benzyl-N-aminoethyl-3-aminopropyltrimethoxysilane and the corresponding hydrochloride, N-phenyl-3 -aminopropyltrimethoxysilane, N-2- (vinylbenzylamino) -ethyl-3-aminopropyltrimethoxysilane. The "matrix" of the composite material made according to the invention comprises at least one vinyl chloride polymer. In the present description, the term "polymer of vinyl chloride" or, more briefly, "polymer" is intended to mean any polymer containing at least about 50% by weight, preferably at least 60%, particularly preferably at least 70% by weight of monomeric units and most preferably at least 85% by weight of monomeric units derived from vinyl chloride, thus both homopolymers of vinyl chloride (containing 100% by weight of monomeric units derived from vinyl chloride) than copolymers of vinyl chloride with one or more ethylenically unsaturated monomers. As examples of ethylenically unsaturated monomers copolymerizable with vinyl chloride, there may be mentioned chlorinated monomers such as vinylidene chloride, fluorinated monomers such as vinylidene fluoride, vinyl esters such as vinyl acetate, vinyl ethers such as vinyl methyl ether, dialkyl maleates such as dibutyl maleate, (meth) acrylic monomers such as n-butyl acrylate and methyl methacrylate, styrenic monomers such as styrene, olefinic monomers such as ethylene, propylene and butadiene. Of all the vinyl chloride polymers mentioned above, preference is given to homopolymers of vinyl chloride. Vinyl chloride polymers, preferably homopolymers of vinyl chloride, having a melt viscosity number or K number (typically called Kw or 2973802 -6 K-wert) are advantageously used in the context of the invention. ), measured according to the ISO 1628-2 standard, greater than 55, preferably greater than 60. This K number is advantageously less than 85, preferably less than 80. For practical reasons (commercial availability), it is particularly advantageous to use Preferred polymers having a K number between 65 and 75. The terms "at least one vinyl chloride polymer" mean, in the present description, that the "matrix" of the composite material made according to the invention may contain a single polymer or more polymers of vinyl chloride; in the latter case, they may be mixtures of homopolymers of different melt viscosity indexes, mixtures of homopolymers and copolymers or mixtures of copolymers of different monomeric compositions. Most often, the "matrix" of the composite material made according to the invention contains a single polymer which is preferably a homopolymer. In carrying out the process according to the invention, the vinyl chloride polymer is in the form of a hydrosol. In the present description, the term "hydrosol" is intended to mean a fluid and colloidal system in which the dispersed phase comprises the polymer and in which the continuous phase is water. The vinyl chloride polymer present in the dispersed phase of the hydrosol is advantageously obtained by radical polymerization in aqueous emulsion. The hydrosol which can be used according to the invention advantageously also contains at least one plasticizer such as a dialkyl phthalate or an alkyl adipate, as well as, optionally, other conventional additives, such as stabilizers, foaming agents, anti-crusting agents, thickeners, pigments, dyes, etc. The radical polymerization in aqueous emulsion which typically uses, in addition to an aqueous polymerization medium, emulsifiers and radical initiators, constitutes a polymerization technique which is particularly well suited to the manufacture of aqueous dispersions (latices) of polymers derived from chloride. vinyl, as well as any other (co) monomers ethylenically unsaturated mentioned above, which are the basis of the hydrosols used according to the invention. The aqueous dispersions thus produced contain elemental polymeric particles having very low average diameters ranging from about 10 to about 5000 minutes (nanometers), preferably from about 50 to about 1500 minutes. By radical polymerization in aqueous emulsion is meant 2973802 -7 in the present description any radical polymerization process taking place in an aqueous medium in the presence of emulsifying agents (for example, alkylsulfates and alkyl-arylsulfonates sodium ...) and radical initiators. This definition specifically encompasses so-called "conventional" aqueous emulsion polymerization in which water-soluble radical initiators are used (for example, water-soluble peroxides such as alkali metal or ammonium persulfates, hydrogen peroxide, perborates, t-butyl hydroperoxide, etc.) as well as microsuspension polymerization, also called a homogenized aqueous dispersion, in which oil-soluble initiators (for example, oil-soluble organic peroxides and oil-soluble diazocompounds) are used. ..) and an emulsion of monomer droplets is achieved by powerful mechanical agitation and the presence of emulsifying agents. The solids content of the hydrosol is preferably greater than 15% by weight, preferably greater than 20% by weight, most preferably greater than 25% by weight. It is advantageously less than 50% by weight, preferably less than 40% by weight, more particularly less than 35% by weight. For carrying out the process according to the invention, the fibers are immersed in the hydrosol. For this purpose, the fibers, advantageously in one of the physical forms mentioned above (tape, tape, tape, web, tablecloth, "mat" or "roving") may be optionally first submitted to one or more following treatments: - passage through a device to spread the fibers in the transverse direction; Passing through voltage regulating means; - antistatic treatment. The fibers are then advantageously immersed in a hydrosol bath of suitable dimensions to ensure their total immersion, leading to their complete coating with the hydrosol. This immersion is advantageously carried out at a temperature of between 0 ° C. and the glass transition temperature of the polymer, preferably between 15 and 40 ° C. This immersion is advantageously carried out at a pressure of between 0.1 and 10 MPa, preferably around atmospheric pressure (0.1 MPa). The respective amounts of fibers and hydrosol used are advantageously such that the final composite material advantageously contains between 60 and 95%, preferably between 29.degree.

70 and 90% by weight of fibers and preferably between 40 and 5%, preferably between 30 and 10% by weight of polymer. The step of immersing the fibers in the hydrosol can be carried out continuously or discontinuously. It is preferred to carry out this step continuously. In this case, if the fibers are packaged in roll or roll, they are previously unrolled for passage through the hydrosol bath. The immersion of the fibers in the hydrosol is then followed by drying. Any known drying method for removing water from a dispersion of a solid in an aqueous phase is suitable for drying the hydrosol. It being understood that, in the process according to the invention, the hydrosol to be dried is most often in the form of a film or layer coating the fibers and whose thickness is often between 0.1 and 1 mm, preferably between 0.2 and 0.6 mm, its drying can be advantageously carried out after optional scraping of the possible excess of hydrosol, for example by the following means applied alone or in combination: depressurization; microwave heating; application of infra-red radiation; application of hot air by blower or fans; passage between heated and rotating cylinders or between heating and fixed bars, etc. The drying of the hydrosol is preferably effected by the application of air, heated to a temperature below the decomposition temperatures of the hydrosol and fibers. This temperature is preferably less than 160 ° C., more particularly less than 150 ° C. Preferably, the temperature of the drying air of the hydrosol is greater than 80 ° C., more particularly greater than 110 ° C. The drying of the hydrosol can be carried out continuously or discontinuously. It is preferred to carry it out continuously. In the case where the drying of the hydrosol is carried out continuously by application of air, a drying tunnel or hot air generators regularly spaced along the path of the composite material in use is advantageously used. After drying the hydrosol, its gelation (that is to say the passage from its particles constituting a heterogeneous phase to a homogeneous phase (free of grain structure)), advantageously under the action heat. Gelation of the hydrosol can advantageously be carried out by applying infra-red radiation or laser radiation. Gelling of the hydrosol is preferably carried out by applying infra-red radiation carrying the hydrosol at a temperature above the glass transition temperature of the polymer it contains and below the decomposition temperature of the fibers. This temperature is preferably less than 250 ° C., more particularly less than 220 ° C. Preferably, this temperature is greater than 100 ° C., more particularly greater than 150 ° C. As the steps of dipping the fibers in the hydrosol and drying the hydrosol, the gelling step of the hydrosol can be carried out continuously or discontinuously. It is preferred to carry out this step continuously. The composite material, obtained at the end of the manufacturing process described above can then be subjected to treatments whose nature differs according to whether this material is intended, either to be stored for later use, or to be implementation directly (ie in line with its manufacture). In any case, the composite material obtained is advantageously given its final shape by subjecting it to a conformation treatment capable of ensuring a uniform thickness, for example calendering or rolling under a press or between cooled or non-cooled rolls, optionally combined with a mechanical treatment capable of ensuring the desired regular width, for example by passing between knives arranged parallel to the longitudinal axis of the progressing structure, or a combination of these two means. The thickness of the composite material obtained can advantageously vary between 0.1 and 3 mm, preferably between 0.15 and 2 mm, especially between 0.2 and 1 min. The width of the composite material obtained can be very variable, depending on whether it is in the form of a strip, a strip, a strip, a sheet or a plate. In the frequent case where the composite material obtained is in the form of a ribbon, this width is advantageously between 3 and 100 mm, preferably between 5 and 50 mm, most preferably between 5 and 25 mm. If the composite material is intended to be stored before it is used, it is advantageously, after optional additional cooling, wound on itself in the form of a reel or roll if it is flexible or stored by stacking sheets or cut plates if it is rigid. If the composite material is intended to be used directly, it is introduced into a suitable shaping device (see below).

In another aspect, the present invention relates to a composite material as described above in connection with the process. In particular, 2973802 -10-

the invention provides a composite material based on fibers coated with at least one vinyl chloride polymer by immersing said fibers in a hydrosol of said polymer followed by drying and gelling said hydrosol. The definitions, limitations and preferences stated and described above for the method of the invention according to the invention apply to the composite material according to the invention. The composite material according to the invention is advantageously obtained by the process according to the invention. Another aspect of the invention further relates to the use of the composite material according to the invention or the composite material made according to the invention for shaping articles or for the manufacture of reinforced articles. For this purpose, the composite material can be implemented by any known method compatible with its components, such as, for example, calendering, thermoforming, pultrusion, coextrusion, etc. The composite material according to the invention can serve as fibrous reinforcement, woven or not, for example for interior trim plates in the automotive industry, in the shipbuilding industry, in furniture, in the building industry; external reinforcement for tubes and pipes; reinforcement of injected parts; etc. Particularly advantageously, the composite material according to the invention can be used for the manufacture of reinforced profiles made of thermoplastic material, preferably rigid PVC, such as joinery elements, in particular of frames and / or shutters, and or doors and / or gates and / or window frames. In this application, the composite material according to the invention improves the stiffness of the profiles and their tensile strength in the longitudinal direction. In addition, the rigid PVC sections reinforced by composite structures of the invention are easily recyclable. Another aspect of the invention finally relates to the articles or reinforced objects obtained from the composite material described above or from the composite material obtained according to the method described above. This aspect of the invention relates more particularly to the profiles reinforced by the above composite material or the composite material obtained by the method described above. The process for producing a composite material according to the invention will now be illustrated with reference to the accompanying drawing. This drawing consists of the appended FIG. 1, schematically representing a practical embodiment of this object of the invention.

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A coil 1 delivered, at the speed of 2.51n / min approximately, a "roving" of glass fibers provided by Owens Coming Vetrotex under the name RO 99 P 192 of linear weight 4800 tex (measured according to the ISO standard 1889), treated with silane coupling agent and whose diameter of the constituent filaments was 24 μm. This "roving", progressing at a speed of 2.5 m / min was immersed, via the roller 2, in a hydrosol bath 3 in which were arranged cylindrical rods 4 staggered with respect to each other and whose respective heights and spacings are adjustable to impose the desired tension on the roving.

The hydrosol bath 3 had the following composition: 31.40% by weight of dispersion of PVC (polymerized in emulsion) marketed by Solvin under the name 072 GA; 12, 44% by weight of plasticizer (di-isononyl phthalate); 0.65% by weight of thermal stabilizer (di-n-octyltin thioglycolate); 15 - 0.91% by weight of anionic emulsifier (mixture of sodium salt of fatty acid and sodium dodecylbenzenesulphonate); 0.50% by weight of a nonionic emulsifier sold under the name Triton X 100 by Sigma Chemical; - 0.5% by weight of cellulose ether 20 - 53.6% by weight of water. The "roving" of glass fibers impregnated with the hydrosol was pulled out of the bath 3 by the series of cylindrical bars 5 which also ensured the correct tension and brought between the fans 6 blowing air at 120.degree. a flow rate of 33 1 / sec then between the fans 7 blowing air at 145 ° C at a rate of 25 171 / sec. The precursor of the composite material was then conducted, for gelling the hydrosol for about twenty seconds, between the IR radiation diffusers 8 whose faces radiating towards the structure are brought to a temperature of 220 ° C.

The composite material thus obtained, containing about 80% by weight of glass fibers, was then passed between the rolling rolls 9 to conform to a strip 0.2 mm thick and 10 min. Wide which was collected on In order to determine the mechanical properties of the thus obtained ribbon-shaped composite material, these tapes were extruded and then the plate-shaped extrudates 1.7 mm thick were pressed. The impact strength of these plates, measured according to the ISO 6603 standard, was 7.6 J / mm. Their tensile modulus, measured according to ISO 527, was 47.6 GPa. Use of the thus obtained composite material for making reinforced protheads is illustrated with reference to another drawing accompanying the present specification. This drawing consists of the appended FIG. 2, schematically showing, in perspective, a partially exploded section of a shaping device 13 of the profiles. The section is made in a plane vertically traversing the device 13 in its middle (only the back half of which is thus visualized) perpendicular to the plane of the ribbon-shaped composite material 11 obtained as described above and in the running direction of this device. ribbon, indicated by the arrow F1. The shaping device 13 was fed, on the one hand, by the ribbon 11, via the adapter piece 17 provided with a passage slot 19 and, on the other hand, by a die 15, located at end of the screw head 14 of a conventional extruder (not shown) which has brought under pressure molten PVC, introduced in the direction of the arrow F2. The exploded part of the section of the shaping device 13 makes it possible to visualize the means 14 and 15 for feeding the molten PVC and the path of the latter in the shaping device 13, via the channels 16 and 16a, to open in front of the the passage slot 19 at the front end of the adapter piece 17, above and below the progressing ribbon 11. The passage slot 19 is lined with two walls 18 and 18 bis so that the PVC melted uniformly covers both sides of the strip 11 to lead to the profile 12 opening out of the device 13 in the direction of the arrow F3. A profile reinforced by the composite material according to the invention is illustrated with reference to another drawing accompanying the present description. This drawing consists of the appended FIG. 3 which represents a section of a PVC window sash. This opening was reinforced with a 2 mm thick ribbon composite material made as shown in Figure 1 and its description above. This structure has increased the length of the opening more than 60% compared to an unreinforced section and 10% compared to a profile reinforced by a steel reinforcement of 1 mm.

Claims (15)

CLAIMS1 - A method for producing a fiber-based composite material and at least one vinyl chloride polymer comprising immersing the fibers in a hydrosol of said polymer followed by drying and gelling said hydrosol. 2 - Process according to claim 1, characterized in that the fibers are fibers from products of plant origin chosen from hemp and flax. 3 - Process according to claim 1, characterized in that the fibers are mineral fibers selected from glass fibers. 4 - Process according to any one of claims 1 to 3, characterized in that the fibers are in the form of strips, strips, ribbons, widths, sheets, "mat" or "roving", single or multiple, in which these fibers are in woven form or not and form an ordered network or not. 5 - Process according to claim 1, characterized in that the fibers are in the form of roving in which fiberglass is arranged in a warp and weft 6 - Process according to claim 1, characterized in that the polymer of vinyl chloride is a homopolymer. 7 - Process according to claim 1, characterized in that the vinyl chloride polymer present in the dispersed phase of the hydrosol is obtained by radical polymerization in aqueous emulsion. 8 - Process according to claim 1, characterized in that the fibers are immersed in a hydrosol bath of suitable dimensions to ensure their total immersion, leading to their complete coating by the hydrosol. 9 - Process according to claim 1, characterized in that the drying of the hydrosol is carried out by applying air, heated to a temperature below the decomposition temperatures of the hydrosol and the fibers. 2973802 -14- 10 - Process according to claim 1, characterized in that the gelling of the hydrosol is carried out by applying infra-red radiation carrying the hydrosol at a temperature above the glass transition temperature of the polymer that it contains and less than the decomposition temperature of the fibers. 11 - composite material based on fibers coated with at least one vinyl chloride polymer by immersing said fibers in a hydrosol of said polymer followed by drying and gelling said hydrosol. 12 - Use of the composite material according to claim 1 or the composite material obtained by a process according to any one of claims 1 to 10 for shaping articles. 13 - Use of the composite material according to claim 1 or the composite material obtained by a method according to any one of claims 1 to 10 for the manufacture of reinforced objects. 15 14 - reinforced articles or objects obtained from the composite material according to claim 11 or the composite material obtained by a process according to any one of claims 1 to 10. 15 - Composite-reinforced profiles according to claim 11 or the composite material obtained by a process according to any one of claims 1 to 10.