Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/326—Polyureas; Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/25—Non-macromolecular compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

• the present invention relates to a sizing composition for glass strands, the glass strands obtained as well as the composites incorporating said glass strands. More specifically, it relates to an anhydrous sizing composition comprising compounds with reactive isocyanate functions and compounds with hydroxyl and / or amino functions capable of reacting to form polyurethanes and / or polyureas.
• reinforcing glass strands is carried out in a known manner from molten glass streaks flowing from the die orifices. These threads are drawn in the form of continuous filaments, then these filaments are gathered into basic threads which are then collected in various forms: coils of continuous threads, mats of continuous or cut threads, cut threads
• the filaments are coated with a size by passing over a sizing member.
• the application of a size is necessary on the one hand for obtaining the threads, and on the other hand for the production of composites associating the said threads as a reinforcing agent with other organic and / or inorganic materials. .
• the size serves first of all as a lubricant and protects the wires from abrasion resulting from the high-speed friction of the wires on the various members encountered in the above-mentioned process. It is important that the glass yarn has a sliding capacity ("a sliding") sufficient to withstand subsequent processing operations, such as unwinding and winding on suitable supports or weaving, so as to avoid as much as possible friction likely to break the filaments.
• a sliding a sliding capacity
• the size also has the function of imparting integrity to the abovementioned threads, that is to say of binding the filaments to one another within the threads.
• This integrity is more particularly sought after in textile applications where the threads are subjected to high mechanical stresses, in particular in traction.
• the filaments are not very integral with each other, they tend to break more easily when they are stressed, resulting in the formation of fluff which disturbs the operation of textile machines, or even requires their complete stop.
• the non-integral yarns are considered to be delicate to handle, in particular when it is a question of forming coils because then broken filaments appear on the sides. In addition to the unsatisfactory aesthetic appearance, it is more difficult to unwind the wires extracted from these coils.
• the size also has the role of promoting the wetting and / or impregnation of the wires with the materials to be reinforced by creating bonds between the wires and these materials.
• the mechanical properties of the resulting composites depend on the quality of the adhesion of the material to the wires and on the wetting and / or impregnation of the wires with the material. In most cases, the sizing makes it possible to obtain composites having improved mechanical properties.
• the sizing compositions must also be compatible with the conditions of production of the threads which in particular impose high drawing speeds of the filaments which can reach several tens of meters per second. They must also resist the shear forces induced by the passage of the filaments, in particular with regard to the viscosity which must not fluctuate significantly, and be capable of properly wetting the surface of the filaments in order to obtain uniform sheathing over their whole length.
• the sizing compositions which contain components capable of polymerizing after deposition on the glass must also remain stable at sub-die temperatures (of the order of 60 to 100 ° C). In particular, it is desirable to ensure that the polymerizable constituents have a low vapor pressure at the temperatures indicated in order to avoid the problems of variation in concentration resulting from the volatilization of certain constituents. It is also important to control the conversion rate defined by the ratio of the number of reacted functions in the size to the number of reactive starting functions to guarantee obtaining sized glass strands of constant quality. The conversion rate must in particular be very close to the expected theoretical rate to prevent the size from changing over time. In general, the sizing compositions are chosen so as to fulfill the functions mentioned above and not to undergo chemical reactions causing a significant increase in viscosity both during storage at room temperature and under the temperature conditions under higher die.
• the most commonly used sizes are low viscosity aqueous sizes. Very easy to implement, they do not, however, only have advantages. In particular, these sizes contain water in very high proportion, generally more than 80%, which must be eliminated after deposition on the glass because the water causes a reduction in the adhesion between the wires and the material to be to reinforce.
• a well-known means consists in drying the glass strands by the thermal route, but this is a long and costly operation which requires perfect adaptation to the conditions of manufacture of the strands. Furthermore, this treatment is not neutral with regard to the thread.
• the sized yarn is in the form of windings in particular, there may be a change in the distribution of the constituents of the sizing by irregular and / or selective migration, coloring of the yarn and deformation of the winding.
• EP-A-0 554 173 describes a size intended to coat glass strands used in the constitution of molded composite products in which the tackifying agent consists of one or more polyurethane resins, possibly associated with one or more polyepoxides.
• JP-2000044793 it is proposed to reinforce thermoplastic materials by means of glass strands treated with a sizing composition comprising a polyurethane resin in emulsion, a coupling agent and a lubricant.
• anhydrous sizing compositions that is to say compositions which comprise less than 5% by weight of solvent, and which consist of a basic system formed of polymerizable components.
• the sizing composition is capable of polymerizing under the action of UV radiation or an electron beam.
• the polymerizable basic system contains at least one component of molecular mass less than 750 having at least one epoxy function and comprising at least 60% by weight of one or more component (s) of mass molecular less than 750 having at least one epoxy, hydroxy, vinyl ether, acrylic or methacrylic function.
• FR-A-2 772 369 describes a sizing composition for glass strands which does not require a heat treatment step after deposition on the strand. It comprises at least 60% by weight of components capable of polymerizing, these components being for at least 60% of them components of molecular mass less than 750 and these polymerizable components comprising at least one mixture of component (s) having at least at least one reactive acrylic and / or methacrylic function and of component (s) having at least one primary amine and / or secondary amine function, at least 20% by weight of these components having at least two reactive acrylic, methacrylic, primary amine and / or secondary amine.
• the object of the present invention is to propose a thermally polymerizable anhydrous sizing composition intended for coating glass strands which proceeds by reaction of compound (s) containing one or more isocyanate functions and of compound (s) containing one or more hydroxy functions , and optionally of compound (s) containing one or more amine functions.
• Another object of the present invention is to provide a sizing composition whose reaction time of the polymerizable system can be modulated to adapt to the application conditions, from a system which can crosslink relatively slowly, in one or more hours, up to an extremely reactive system having a gel time of the order of ten minutes.
• Another object of the invention is to propose a sizing composition which makes it possible to control the texture of the glass strands, that is to say their stiffness and their integrity.
• Another object of the invention is to provide glass strands coated with a size which makes them suitable for undergoing an operation intended to increase their volume (“volumization").
• the sizing composition according to the invention consists of a solution comprising less than 5% by weight of solvent and comprising a polymerizable base system, said system comprising at least 50% by weight of a mixture:
• component (s) containing at least one reactive hydroxy function • and optionally of component (s) containing at least one amine reactive function.
• solvent water and organic solvents capable of being used to dissolve certain polymerizable components.
• solvent in limited quantity does not require any special treatment to remove them.
• the sizes according to the invention are completely devoid of solvent.
• polymerize By “polymerize”, “polymerizable”, “polymerization”, .... is meant respectively “polymerize and / or crosslink”, “polymerizable and / or crosslinkable”, “polymerization and / or crosslinking”, ....
• reactive function is meant a function capable of intervening in the polymerization reaction of the size, the polymerization being able to be carried out at the usual temperature for producing the yarns (of the order of 20
• polymerizable basic system means all of the essential components which make it possible to obtain the polyurethane / polyurea structure expected from the size.
• isocyanate component (s) by “hydroxy component (s)” and by “amine component (s)” is meant respectively “component (s) containing at least one isocyanate reactive function", “ component (s) containing at least one reactive hydroxy function "and” component (s) containing at least one reactive amine function ".
• the sizing composition according to the invention is compatible with the conditions for obtaining glass strands imposed by the direct process, the viscosity of the composition being adapted as a function of the drawing speed and the diameter of the filaments brought to the to cross. As a general rule, it is desirable that the viscosity does not exceed 400 mPa.s, preferably 150 mPa.s, so that the sizing composition can be distributed homogeneously on the surface of the glass filaments.
• the composition according to the invention also has a wetting speed on the wire compatible with the drawing speed of the wires.
• the basic polymerizable system represents 50 to 100% by weight of the sizing composition according to the invention, mainly 60 to 100% by weight of the composition and, in most cases, 75 to 90% by weight. weight of the composition.
• the basic system is mainly made up (preferably 75% by weight and up to 100% by weight in the majority of cases) of isocyanate component (s) and hydroxy component (s), optionally of amine component (s), the use of this mixture of components making it possible to obtain polyurethane or poly (urethane-urea) polymers by reaction of the various isocyanate, hydroxy and amine functions of the starting constituents. It is these polymers which mainly participate in the structure of the size, and from this structure flow directly the properties of the sized glass strands.
• the basic system comprises a majority (preferably at least 70% by weight and better still at least 80% by weight) of component (s) of molecular weight less than 750, this component (s) making normally part, for most of the aforementioned isocyanate, hydroxy and amine components.
• the components of molecular mass less than 750 previously mentioned are of molecular mass less than 600.
• the basic system contains components of molecular mass greater than 750, it advantageously comprises one or more components isocyanate and / or hydroxy and / or amine with a molecular mass greater than 1000 (prepolymers).
• the total content of these components is generally less than 20% by weight of the sizing composition, preferably less than 15%, because beyond the viscosity as well as the reactivity of the composition becomes too high to allow the deposition of the sizing on the glass strands under the conditions of the abovementioned process.
• the reactivity of the basic system is modulated to adapt to the application conditions.
• the freezing time has an important influence on the quality of the removal of the size and on the construction of the windings when the wire is collected in the form of coils.
• the freezing time must not be less than approximately 10 minutes to allow the sizing to be deposited under the die by means of sizing rollers without major risk of gelling on the rollers.
• the freezing time must not exceed 1.5 hours in order to be able to obtain windings of manipulable wires at the outlet of the winder. Freezing times varying from 15 to 45 minutes prove entirely satisfactory.
• the basic system according to the invention may optionally comprise a small proportion (less than 20%) of component (s) participating in the structure of the polymerized size but having no isocyanate, hydroxy or amine and / or molecular weight greater than or equal to 1000.
• the proportion of these components is less than 15%.
• the basic system consists of isocyanate component (s) containing at least two isocyanate reactive functions, of hydroxy component (s) containing at least one function reactive hydroxy, and optionally of component (s) containing at least one reactive amine function.
• the basic system consists either of isocyanate component (s) containing three reactive isocyanate functions and of hydroxy component (s) containing one to three reactive hydroxy functions, or of isocyanate component (s) containing three reactive isocyanate functions , of hydroxy component (s) containing a reactive hydroxy function and of amine component (s) containing two reactive primary amine functions.
• all or part of the hydroxy components of the basic system may contain one or more reactive hydroxy functions and one or more reactive amine functions.
• the isocyanate component (s) of the basic system can in particular be chosen from:
• - aliphatic or cycloaliphatic isocyanates such as hexylisocyanate, dodecylisocyanate, hexadecylisocyanate, cyclohexylisocyanate, 1-adamantylisocyanate, 1, 6-hexamethylene diisocyanate (HDI), 1, 12-dodecamethylisocyanate (diocyanide IPDI), 1, 1-methylenebis (4-isocyanatocyclohexane)
• HMDI transcyclohexane-1, 4-diisocyanate (CHDI), esters such as butyl isocyanatoacetate and ethyl 3-isocyanatopropionate, or ethers such as trifluoroacetylisocyanate, - aromatic isocyanates such as 3,5-dimethylphenylisocyanate, 4-methoxybenzylisocyanate, 4-dimethylaminophenylisocyanate, 4-methoxyphenylisocyanate, 4-ethoxyphenylisocyanate, xylylene diisocyanate (XDI), tolylene diisocyanate (TDI) 1,5-diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI) and tetramethylxylene diisocyanate (TMXDI),
• prepolymers for instance Tolonate ® HDT and Tolonate ® HDB (NCO content: 20-25%; marketed by Rhodia), polyethers of the reaction products and isocyanates such as TDI prepolymers polytetramethylene glycol, e.g. Castomer E ® 1009 and
• Castomer ® E 1004 (NCO rate: 4.2 and 9.3% respectively; marketed by BAXENDEN); polypropylene glycol / TDI prepolymers, for example Trixene ® DP9B / 1534 (NCO rate: 4.4%; marketed by BAXENDEN) and reaction products of polyesters and isocyanates, in particular TDI, for example Castomer ®
• the isocyanates which have just been mentioned, some are monomers whose vapor pressure is relatively high, which makes them potentially toxic to humans. This is why, the isocyanates which are in the form of prepolymers of molecular mass at least equal to 400 and preferably at least equal to 450 are preferred.
• the molecular mass is less than or equal to 2000, preferably less or equal to
• the prepolymer has a content of free isocyanate reactive function (level of NCO) at least equal to 3%, and preferably less than 25%, and advantageously greater than or equal to 5%.
• the proportion of isocyanate component (s) in the basic system represents 15 to 75% by weight, and preferably 30 to 60
• isocyanate component (s) is generally between 10 and 50% by weight, and preferably between 20 and 40%.
• the hydroxy component (s) of the basic system can be chosen from: - aliphatic or cycloaliphatic alcohols such as Phexanol, Poctanol, dodecanol, cyclohexanol, 1, 2-propanediol, 2-ethyl-2-hydroxymethyl-1, 3-propanediol, butanediol, butenediol, pentanediol, hexanediol, cyclohexanediol, 1, 4-cyclohexanedimethanol, glycerol, trimethylolpropane and pentaerythritol,
• - aliphatic or cycloaliphatic alcohols such as Phexanol, Poctanol, dodecanol, cyclohexanol, 1, 2-propanediol, 2-ethyl-2-hydroxymethyl-1, 3-propanediol, butanedi
• - tertiary alkanolamines such as 2- (diisopropylamino) ethanol, 3-dimethylamino-1-propanol, 3-diethylamino-1, 2-propanediol, 3-diisopropylamino-1, 2-propanediol, N-butyl -diethanolamine, triethanolamine and triisopropanolamine, - monohydroxylated components of the hydroxy-terminated polyester type obtained by reaction of fatty acid and of poly (alkylene oxide) such as polyethylene glycol or polypropylene glycol isostearate, components of the terminated polyether type hydroxy obtained by reaction of fatty alcohol and ethylene oxide and / or propylene oxide, for example lauric alcohol with 4 units of ethylene oxide, or by reaction of alkylphenol and oxide ethylene and / or propylene oxide, for example nonylphenol with 8 ethylene oxide units,
• poly (alkylene oxide) such as polyethylene glycol or polyprop
• poly (oxyalkylene) polyols for example poly (oxyethylene) polyols, poly (oxypropylene) polyols, poly (oxyethylene) (oxypropylene) - polyols, poly (tetrahydrofuran) polyols and poly (caprolactone) polyols, preferably whose molecular mass is less than 1500.
• hydroxylated compounds which have just been mentioned, preference is given to those which comprise more than 5 carbon atoms.
• Compounds having a lower number of carbon atoms can be used when it is desired to lower the viscosity of the basic system and / or limit the length of the chains during polymerization.
• the hydroxy components are chosen from alcohols containing at least two reactive hydroxy functions, and better still two or three hydroxy functions.
• the hydroxy components can comprise one or more amine functions. Examples of such components are shown below.
• hydroxy components components containing one or more epoxy functions, the epoxy ring of which can be opened under the action of a catalyst to generate a secondary hydroxyl.
• the catalyst which can be used for this purpose can be any catalyst known to a person skilled in the art, as indicated below.
• components containing an epoxy function such as cyclohexene monoxide, glycidyl ethers, in particular C 4 -C 20 alkyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ethers, monoglycidyl ethers of bisphenol derivatives A, in particular of acryloxybisphenol A, the components containing several epoxy functions such as polyglycidyl ethers, in particular 1, 4-butanedioldiglycidyléther, neopentylglycoldiglycidyléther, cyclohexanedimethanoldiglycidyléther, resorcinoldiglycidmatietheid or polybutylidher, trimethylolpropanetriglycidylether and polyglycidyl ethers of alkyl polyesters.
• an epoxy function such as cyclohexene monoxide, glycid
• the proportion of hydroxy component (s) varies from 15 to 60% by weight of the basic system, and preferably from 20 to 50%.
• hydroxy component (s) are components comprising at least two reactive hydroxy functions, and advantageously at least 20%.
• the content of hydroxy component (s) in the composition is generally between 15 and 55% by weight, and preferably between 25 and 45%.
• the number of reactive sites of hydroxy components which can react with reactive sites of isocyanate components can vary to a large extent.
• the ratio r of the number of isocyanate reactive sites to the number of hydroxy reactive sites varies from 0.1 to 6, and preferably from 0.3 to 4, it being understood that an isocyanate function counts for an isocyanate reactive site and that a hydroxy function counts for a reactive hydroxy site.
• the amine component (s) of the basic system can be chosen from the components containing one or more primary and / or secondary amine functions such as the components with a linear, branched or cyclic, for example N, N-dibutylamine, N, N-dicyclohexylamine, aminoethylpiperazine, 2 (2-aminoethoxy) ethanol, 3-amino-1-propanol, 2-amino-2-ethyl-1 -propanol, N- (2-aminoethyl) ethanolamine, 2-amino-2-ethyl-
• the amino components are chosen from the components containing at least two primary and / or secondary amine functions.
• a ketone in particular of a diketone such as pentanedione , dibenzoylmethane, 2,2,6,6-trifluoro-3,5-heptanedione, dimethyl-1,4-cyclohexanedione-2,5-dicarboxylate, 4,4,4-trifluoro-1- (2- naphthyl) -1, 3-butanedione, thenoyl-trifluoroacetone, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione, 3-methyl-2, 4-pentanedione, 1- (2-furyl) -1, 3-butanedione and
• the proportion of amine component (s) represents 0 to 30% by weight of the basic system and in most cases it is between 5 and 30%.
• the content of amine component (s) in the composition is generally between 0 and 30% by weight, and preferably between 0 and 20%.
• the number of reactive sites of the amine components which can react with the reactive sites of the isocyanate components can vary to a large extent.
• the ratio r ′ of the number of isocyanate reactive sites to the sum of the number of hydroxy reactive sites and the number of amine reactive sites varies from 0.1 to 6, and preferably from 0.3 to 4, it being understood that an isocyanate function counts for an isocyanate site, that a hydroxy function counts for a reactive hydroxy site, that a primary amine function counts for two reactive amine sites and that a secondary amine function counts for an reactive amine site.
• the sizing composition may comprise, in addition to the basic system, at least one catalyst promoting the polymerization of the sizing. It can be for example a specific catalyst for the synthesis of polyurethanes such as 1, 4-diazabicyclo [2.2.2] octane and 1, 8-diazabiscyclo [5.4.0] undéc-7-ene, or a catalyst suitable for epoxy components , such as tris (N, N-dimethylaminomethyl) benzene, tris (N, N-dimethylaminopropyl) triazine, N, N-dimethylbenzylamine and 2-propylimidazole.
• a catalyst suitable for epoxy components such as tris (N, N-dimethylaminomethyl) benzene, tris (N, N-dimethylaminopropyl) triazine, N, N-dimethylbenzylamine and 2-propylimidazole.
• the level of components acting solely as catalysts of the basic system is generally less than 5% by weight of the size composition, preferably less than 3% by weight and in most cases of the order of 0.5%.
• the sizing composition can also comprise, within the limits indicated above, a solvent facilitating the dissolution of certain components of the basic system.
• a solvent facilitating the dissolution of certain components of the basic system.
• the size composition may comprise one or more components (hereinafter referred to as additives).
• additives give the sizing particular properties and, when the composition is deposited in two stages, as is preferred, they can be provided by one and / or the other of the compositions constituting the sizing.
• the composition according to the invention may comprise, as an additive, at least one coupling agent allowing the size to be attached to the glass.
• the coupling agent can be a component of the basic system, in which case it takes part in the polymerization reaction, or a component which acts only as an additive.
• the proportion of coupling agent (s) is generally between 0 and 30% by weight of the sizing composition and in most cases it is greater than 5% by weight. Preferably, it is between 10 and 25% of the composition.
• the coupling agent is generally chosen from silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-acryloxypropyltrimethoxy-silane, gamma-methacryloxypropyltrimethoxysilane, poly (oxyethylene / oxypropylene) trimethoxysilane, gamma-aminopropyltriethyl vinyl phenylaminopropyltrimethoxysilane, styrylaminoethyl- aminopropyltrimethoxysilane or terbutylcarbamoylpropyltrimethoxysilane, siloxanes, titanates, zirconates and mixtures of these compounds.
• the silanes are preferably
• the composition may comprise, as an additive, at least one textile processing agent essentially playing a role of lubricant, and it is in many cases necessary for the composition to have the functions of a size.
• the proportion of textile processing agent is generally between 0 and 30% by weight of the composition, and preferably is between 3 and 20%.
• the textile processing agent is generally chosen from fatty esters, optionally alkoxylated, such as decyl laurate, isopropyl palmitate, cetyl palmitate, isopropyl stearate, isobutyl stearate, trimethylolpropane trioctanoate, trimethylolpropane tridecanoate, alkylphenol derivatives such as ethoxylated nonylphenol, fatty alcohols, optionally alkoxylated, such as laurate or polyethylene glycol stearate with methyl endings advantageously comprising less than 10 oxyethylene units, mixtures with base of mineral oils, and mixtures of these compounds.
• the agents are preferably free of functions capable of reacting preferentially with the isocyanate, hydroxy and / or amine functions.
• composition according to the invention can be deposited on the glass filaments in one or more stages.
• the preferred solution in this embodiment consists in using polyisocyanates whose reactive isocyanate functions are blocked by protective groups and the functions which can be released by the addition of a release agent.
• composition according to the invention is preferably deposited in several stages, for example as indicated under the conditions of the process described in
• strands of molten glass flowing from orifices arranged at the base of one or more dies are drawn in the form of one or more plies of continuous filaments, and then they are combined the filaments in one or more threads which are collected on one or more moving supports.
• the size is deposited by applying to the filaments a first stable composition with a viscosity of between 0.5 and 300 mPa.s, and at least one second stable composition with a viscosity of between 0.5 and 250 mPa.s, brought separately from the first composition.
• the second composition can be deposited on the filaments at the earliest when the first composition is deposited or on the threads at the latest when they are collected on the supports.
• the viscosity difference between the compositions is generally less than 150 mPa.s.
• the composition according to the invention is preferably applied in two stages, the first composition preferably comprising the polyisocyanate component (s), and optionally one or more additives, and the second composition comprising the hydroxy component (s) and / or the amine component (s), and optionally one or more additives, in particular the polymerization catalyst (s).
• Depositing the size in two stages is particularly advantageous. It allows better control of polymerization reactions and therefore the sizing has a uniform quality over the entire length of the strands while ensuring high productivity with a reduced risk of breakage of the strands.
• the polymerization of the size deposited on the wire does not require additional energy input. It is however possible to subject the yarn after fiberizing to a heat treatment at different stages of the process in order to accelerate the polymerization. This treatment can be applied to yarns collected in the form of a winding, on sheets of continuous or cut yarns, or else on yarns in association with an organic material for producing composites.
• the sized threads are generally collected in the form of windings on rotating supports, such as cakes, rovings and "cops". Whatever the state of polymerization of the size and the crossing angle, even when the latter is small (less than 1.5 °), it is easy to unwind the wires coming from the windings and to handle them. Windings with straight edges retain their dimensional characteristics over time and do not undergo any deformation.
• the threads can also be used subsequently for the production of grids, fabrics, braids, ribbons, etc.
• the wires can also be collected on receiving supports in translation. They can in particular be projected by a member also serving to stretch them towards the collecting surface moving transversely to the direction of the projected threads in order to obtain a web of intermingled or "matt" continuous threads.
• the wires can also be cut before collection by an organ that also feels the need to stretch them.
• the presence of polyurethane or poly (urethane-urea) polymers in the size provides flexibility in bonding and allows the filaments to be able to move relative to one another. In this way, the integrity of the glass strands is improved.
• the yarns coated with the sizing composition according to the invention prove to be particularly advantageous for making fabrics or for applications requiring them to be cut, as in the technique of molding by simultaneous projection.
• the sized glass wire according to the invention is remarkable in that it can be treated in order to increase its volume and obtain what is commonly called a "voluminized" wire.
• the treatment consists in passing the wire through a system comprising one or more nozzles traversed by an air flow and then in collecting it. in the form of a winding on a suitable device. This wire can then be woven to form in particular wall fabrics to be painted.
• the glass filaments constituting these strands have a diameter which can vary to a large extent, most often from 5 to 30 ⁇ m. They can be made of any glass, the best known in the field of reinforcing wires being E glass and AR glass.
• the wires obtained according to the invention can be advantageously used to reinforce various materials with a view to obtaining composite parts having high mechanical properties.
• the composites are obtained by combining at least glass strands according to the invention and at least one organic and / or inorganic material, the content of glass in the final composite generally varying from 1 to 5% by weight (cement matrix) and 20 to 80% by weight, and preferably 30 to 70% (organic matrix).
• the viscosity is measured using a SOFRASER MIVI 4000 device sold by SOFRASER. It is expressed in mPa.s. the gel time, expressed in minutes, is measured on the mixture of compositions A and B using a TROMBOMAT device (marketed by PRODEMAT S.A.) which traces the viscosity curve of the sizing composition as a function of time. On this curve, the point of intersection between the tangent to the point of inflection and the abscissa axis corresponds to the freezing time.
• the quantity of flock makes it possible to assess the abrasion resistance of a thread. It is measured by weighing the quantity of material that comes off the wire after it has passed over a series of 8 cylindrical ceramic fixtures arranged so that the angle of deflection of the wire at each fixture is equal to 90 °. . The amount of fill is given in mg per 1 kg of yarn tested.
• the stiffness or stiffness is measured under the conditions defined by standard ISO 3375, on 10 test pieces, before and after submission to the abrasion resistance test mentioned above. The stiffness is expressed in mm and it is noted x (y), x and y representing the value measured respectively before and after passing over the tie-downs.
• a sized wire whose value of y is less than 100 mm, and preferably close to 60 mm (the lowest value that can be obtained) is rather used for applications requiring good impregnation by the matrix.
• a yarn having a value of x greater than or equal to 120 and a value of y greater than or equal to 100 is suitable for a use requiring high integrity of the yarn, for example for weaving and possibly for cutting.
• the tensile strength is measured under the conditions defined by standard ISO 3341. It is expressed in g / tex.
• the flexural breaking stress and the flexural modulus are measured under the conditions defined by ISO standard 178, before and after aging by immersion in water at 100 ° C for 24 hours (composites with polyester resin) and 72 hours (composites with epoxy resin). It is expressed in MPa.
• composition A triisocyanate (1)
• 35 gamma-methacryloxypropyl trimethoxysilane (2)
• compositions A and B have a viscosity equal to 49 mPa.s (at 21 ° C) and 58 mPa.s (at 22.5 ° C), respectively.
• compositions A and B are mixed in equal parts.
• the mixture has a viscosity equal to 1000 Pa.s after 1 hour and a gel time of 21 minutes.
• the ratios r and r 'of the sizing composition have identical values equal to 0.487.
• the filaments are brought together to form a thread which is wound on a rotating support in order to obtain a direct roving of 14 kg.
• the wire has a linear density of 297 tex and a loss on ignition of 0.65%.
• This yarn has a tensile strength equal to 38.7 g / tex, a stiffness equal to 162 mm (122 mm) and an amount of flock equal to 8 mg.
• the first resin is an epoxy resin consisting of 100 parts by weight of epoxy resin (5) , 90 parts by weight of phthalic anhydride (6) and 0.5 parts by weight of tertiary amine (7) .
• the second resin is an unsaturated polyester resin made up of 100 parts by weight of isophthalic polyester (8) and 1.5 parts by weight of peroxide (9) .
• composition A Composition A
• the mixture A and B are made in equal parts.
• the mixture has a viscosity equal to 2000 Pa.s after 1 hour and a gel time of 20 minutes.
• Compositions A and B have a viscosity of 49 cP (at 21 ° C) and 68 cP (at 22.5 ° C), respectively.
• the ratios r and r 'of the sizing composition have identical values equal to 0.998.
• the filaments are brought together to form a thread which is wound on a rotating support in order to obtain a direct roving of 14 kg.
• the wire has a linear density of 286 tex and a loss on ignition of 0.76%.
• This yarn has a tensile strength equal to 34.5 g / tex, a stiffness equal to 157 mm (110 mm) and an amount of flock equal to 5 mg.
• composition A triisocyanate (1) 35 gamma-methacryloxypropyl trimethoxysilane (2) 15 gamma-glycidoxypropyl trimethoxysilane (3) 5 isopropyl palmitate 5
• composition B • 1,5-pentanediol 18
• Compositions A and B have a viscosity equal to 49 cP (at 21 ° C) and 58 cP (at 22.5 ° C), respectively.
• the ratios r and r 'of the sizing composition have identical values equal to 0.375.
• the mixture A and B are made in equal parts.
• the mixture has a viscosity equal to 60 Pa.s after 1 hour and a gel time of 26 minutes.
• a wire with a linear mass equal to 287 tex is formed which is collected on a series of coils.
• This wire undergoes a "voluminization" treatment under the following conditions: the wires extracted from two coils are collected and they are passed successively over a first drawing cup (speed: 220 m / min), in a nozzle (diameter d '' inlet and outlet equal to 0.7 and 2.2 mm respectively; air pressure: 6-6.5 bars), on a second drawing cup (speed: 183.5 m / min) and finally on winding device (pressure: 2.5 bars).
• the wire obtained has a linear mass of 640 tex, a stiffness before embarrassment equal to 110 mm, a loss on ignition equal to 0.21% and does not reveal any sticky deposit.
• the yarn obtained has sufficient breaking strength to be able to be woven.
• the fabric formed has a good “covering” (is “closed"), is highly hydrophobic and has a good ability to impregnate with polyvinyl acetate (loss on ignition about 17%). It can be used as a painting canvas.
• composition A triisocyanate (11) 35 gamma-methacryloxypropyl trimethoxysilane (2) 10 gamma-glycidoxypropyl trimethoxysilane (3) 10 • isopropyl palmitate 5
• composition B polyethylene glycol isostearate (4) 9
• the ratios r and r 'of the sizing composition have identical values equal to 0.589.
• the mixture A and B are made in equal parts.
• the mixture has a viscosity equal to 2800 Pa.s after 1 hour and a gel time of 32 minutes.
• the filaments are gathered into 51 tex threads which are wound into cakes. From the yarns extracted from 24 cakes, a 1400 tex yarn is formed which has a loss on ignition of 1.28%.
• the wire has medium integrity and stiffness and can be easily cut. Its ability to be impregnated with a polyester resin is evaluated at 1, measured visually on a scale going from 0 (bad; absence of wetting) to 5 (excellent; invisible thread in the resin).
• the wire can be used as reinforcement in materials of the SMC type ("Sheet Molding Compound").
• composition A triisocyanate (1) 35 gamma-methacryloxypropyl trimethoxysilane (2) 15 isopropyl palmitate 7
• the ratios r and r 'of the sizing composition are equal to 4.71 and 3.01 respectively.
• the mixture A and B are made in equal parts.
• the mixture has a viscosity equal to 716 Pa.s after 1 hour and a gel time of 10.5 minutes.
• the filaments are brought together to form a thread which is wound on a rotating support in order to obtain a direct roving of 20 kg.
• the wire has a linear mass of 315 tex, a loss on ignition of 0.57%. It has a tensile strength equal to 31.1 g / tex, a stiffness equal to 170 mm (80 mm) and an amount of fill equal to 1.6 mg.
• the yarn thus obtained is woven and the fabric is used for the reinforcement of epoxy, polyester and phenolic matrices.

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• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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• 2002
  • 2002-05-22 FR FR0206197A patent/FR2839968B1/fr not_active Expired - Fee Related
• 2003
  • 2003-05-21 EP EP03752846A patent/EP1506144A1/fr not_active Withdrawn
  • 2003-05-21 CN CNB038115646A patent/CN100436357C/zh not_active Expired - Fee Related
  • 2003-05-21 AU AU2003258770A patent/AU2003258770A1/en not_active Abandoned
  • 2003-05-21 CA CA002486479A patent/CA2486479A1/fr not_active Abandoned
  • 2003-05-21 RU RU2004137495/04A patent/RU2314374C2/ru not_active IP Right Cessation
  • 2003-05-21 US US10/512,864 patent/US20060099417A1/en not_active Abandoned
  • 2003-05-21 MX MXPA04011511A patent/MXPA04011511A/es unknown
  • 2003-05-21 WO PCT/FR2003/001537 patent/WO2003097551A1/fr active Application Filing
  • 2003-05-21 JP JP2004505287A patent/JP2005530668A/ja active Pending
  • 2003-05-21 BR BR0310070-7A patent/BR0310070A/pt active Search and Examination
  • 2003-05-21 PL PL03372750A patent/PL372750A1/xx not_active Application Discontinuation
• 2004
  • 2004-11-19 ZA ZA200409327A patent/ZA200409327B/en unknown
  • 2004-12-10 NO NO20045406A patent/NO20045406D0/no not_active Application Discontinuation

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