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
  • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
  • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C09D131/04—Homopolymers or copolymers of vinyl acetate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/06—Fibrous reinforcements only
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
  • B29C70/305—Spray-up of reinforcing fibres with or without matrix to form a non-coherent mat in or on a mould
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
  • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
  • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones

Definitions

• the invention relates to glass son coated with a sizing composition for reinforcing organic materials of the polymer type, the sizing composition used to coat said son and the composites thus obtained, in particular by molding.
• the glass threads used for reinforcement in general are industrially produced from molten glass threads flowing from the multiple orifices of a die. These nets are drawn mechanically in the form of continuous filaments, and are then combined into base wires which are then collected, for example by winding on a rotating support. Before their assembly, the filaments are coated with a sizing composition by passing on a suitable device such as coating rolls.
• the sizing composition proves essential for several reasons.
• the sizing composition protects the glass filaments from the abrasion that occurs when they rub at high speed on the various organs used to guide and collect them. It also establishes bonds between the filaments which makes it possible to give cohesion to the thread. As the yarn is made more upright, its handling, especially during weaving operations, is improved and untimely breaks are avoided.
• the sizing composition promotes the wetting and impregnation of the glass son by the matrix to be reinforced, which matrix is generally implemented in the form of a more or less fluid resin.
• the mechanical properties of the final composite are therefore significantly improved.
• the materials to be reinforced can integrate the glass threads in different forms: continuous or cut threads, mats of continuous or cut threads, fabrics, ...
• Composites that incorporate cut glass yarns can be obtained, inter alia, by the technique of "simultaneous projection molding” which consists in projecting inside a mold a resin to be reinforced and glass threads of variable length. .
• the threads and the resin are projected together on the inner walls of the mold by means of a "gun” comprising an incorporated cutter capable of cutting the son extracted from one or more windings and a device for spraying the resin.
• This process simple and flexible, is particularly suitable for the production of single or small series of parts based on thermosetting polymers belonging to the family of polyesters or epoxies.
• LFI Long Fiber Injection
• the quality of the composites obtained by these processes largely depends on the properties provided by the glass strands, and therefore on the size which coats them and the conditions of use.
• it seeks sizing compositions for obtaining a wire that can be extracted from a winding, for example a cake or a roving ("roving" in English), forming the least possible loop and retaining its integrity after cutting.
• loops are not desired for the following reasons: in the first place, the loops impede the passage of the wire inside the flexible arm which serves to cut and project said wire into the mold. It follows a malfunction of the cutter that does not deliver a constant amount of cut glass in the mold,
• the strong stress of the wire at the start of each cutting cycle causes the "filamentization" of the wire at the loops, ie a rupture of the filaments constituting the wire and the joint production of "wad” which s accumulates in various parts of the process.
• the flock forms clusters in the resin which adversely affect the quality of the molded part. In either case, the production is diminished because of the stops necessary to clean the soiled organs.
• the integrity of the wire remains at a high level so that it does not "open” by separating the filaments that constitute it during the start of each cutting cycle where the tension on the wire is important.
• the wire should not be to the detriment of other properties.
• the cut wire can be rapidly impregnated with the precursor monomers of the resin and that the mixture obtained be homogeneous and be distributed uniformly in the mold, without "collapsing" by gravity.
• Measured glass wires adapted to these projection molding techniques are already known.
• EP-A-0 869 927 there are described glass threads coated with a sizing composition comprising, as sticky film-forming agents, the combination of at least one low molecular weight polyvinyl acetate A and at least one vinyl acetate copolymer B self-crosslinkable thermally in a weight ratio A / B greater than or equal to 1. These son have a high rate of impregnation with the resin.
• the glass strands are coated with a substantially aqueous size composition which comprises at least one bis-silane A and at least one unsaturated monosilane (B) selected from vinylsilanes and methyl ( acrylosilanes). Sizing increases the life of the cutter blades. The speed of impregnation of the threads is important.
• the glass strands are coated with a lubricant comprising an aqueous mixture based on polyvinyl acetate, a fatty acid lubricant, methacrylato chromic chloride and gamma (ethylene diamine) propyltrimethoxysilane. If the performance level of these wires is generally satisfactory, the number of loops per unit length of wire remains high and the integrity is insufficient.
• the object of the present invention is to propose a glass reinforcement yarn, in particular intended for simultaneous projection molding, in particular for LFI molding, which forms few loops when it is extracted from the winding and which has a better integrity than the known son adapted to this type of molding.
• the invention relates to a glass wire coated with an aqueous sizing composition which comprises, as sticky film-forming agents, the mixture of at least one polyvinyl acetate and at least one polyvinylpyrrolidone.
• glass threads coated with a sizing composition which comprises " means not only glass threads coated with the composition in question as obtained at the immediate exit of the composition. organ or sizing organs, but also these same son after they have undergone one or more other treatments.
• son means the basic son from the gathering under the die of a multitude of filaments, and products derived from these son, including the assemblies of these basic son in rovings. Such assemblies can be obtained by unwinding simultaneously several windings of basic son, and then gathering them in locks which are wound on a rotating support. It may also be “direct” rovings of a linear density (or linear density) equivalent to that of assembled rovings, obtained by the gathering of filaments directly under the die and the winding on a rotating support.
• aqueous sizing composition means a sizing composition in the form of a solution in which the liquid phase consists of 97% by weight of water, preferably 99% and better still 100%, the complement being constituted if necessary of one or more essentially organic solvents which can help solubilize certain constituents of the sizing composition.
• the sizing composition contains 85 to 95% by weight of water, preferably 89 to 94%.
• the sizing composition comprises, as sticky film-forming agents, the mixture of at least one polyvinyl acetate and at least one polyvinylpyrrolidone.
• Polyvinyl acetate is important to quickly reach a high level of impregnation of the son by the resin and get a good conformability of the son / resin mixture in the mold. Polyvinyl acetate also brings stiffness to the wire.
• the molecular weight of the polyvinyl acetate is generally less than or equal to 80,000 g / mol, preferably less than or equal to 70,000 g / mol and preferably is between 29,000 and 65,000 g / mol.
• the amount of polyvinyl acetate is generally 70 to 90% by weight of the solids of the size deposited on the wire, preferably 75 to 85%.
• the polyvinylpyrrolidone participates in bonding the glass filaments, thereby increasing the integrity of the yarn after cutting, and furthermore makes it possible to adjust the tackiness of the yarn and to reduce the ability of the yarn to form loops.
• the molecular weight of the polyvinylpyrrolidone is generally less than or equal to 4000 g / mol, preferably less than or equal to 3000 g / mol, and advantageously between 1000 and 2000 g / mol.
• the amount of polyvinylpyrrolidone is such that the weight ratio polyvinyl acetate / polyvinylpyrrolidone varies from 14 to 900, preferably 18.75 to 106.25.
• the sizing composition may comprise one or more other components (hereinafter referred to as "additives").
• the sizing composition may thus comprise at least one plasticizing agent whose function is to soften the polymer chains of the film-forming film-forming agents.
• the plasticizer makes it possible to obtain a better "conformability" of the cut son / resin mixture in a mold of complex shape.
• the plasticizing agent is chosen from glycols derivatives such as alkylene glycol dibenzoates, preferably dibenzoates of ethylene and / or propylene glycol.
• the amount of plasticizer in the size depends on the degree of flexibility that it is desired to give the wire, it being understood that the wire must be rigid enough to allow it to distribute itself properly within the resin. Generally, the plasticizer is 6 to 20% by weight of the solids of the size.
• the composition may further comprise at least one lubricating agent in an amount of 3 to 9% by weight of the solids of the sizing composition.
• the lubricant helps to limit the formation of flock and to avoid the gluing of the turns on the windings of basic threads.
• these agents are chosen from polyalkylene imide type cationic compounds and poly (oxyalkylene) poly (alkylene glycol) fatty acid esters and ionic compounds, such as polyethylene glycol monolaurate, or acid amide type.
• fatty and poly (oxyalkylene) such as hydrogenated tallow amides and polyethylene.
• the sizing composition may also comprise at least one coupling agent for hanging the size on the surface of the glass filaments.
• the coupling agent is generally chosen from silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, poly (oxyethylene / oxypropylene) -trimethoxysilane, gamma-aminopropyltriethoxysilane, vinyltrimethoxysilane, phenylaminopropyltrimethoxysilane or styrylaminoethylaminopropyltrimethoxysilane, siloxanes, titanates, zirconates and mixtures of these compounds.
• the silanes are selected.
• the amount of coupling agent generally represents less than 7% by weight of the solids of the sizing composition, preferably is greater than 2% and most often is of the order of 5%.
• the size may further comprise at least one antistatic agent which contributes to improving the cutting ability of the glass yarn.
• the antistatic agent is selected from metal salts such as lithium chloride.
• the amount antistatic agent generally represents at most 5% of the weight of the solids of the size.
• All these additives combine to obtain reinforcement yarns that can be easily manufactured, which can be extracted without difficulty from the windings with a reduced number of loops and which can be cut without any problem and projected into a mold while retaining a good integrity.
• the yarn according to the invention may undergo an additional step of coating it with an additional size ("over-image") in order to give it a better slipperiness and to reduce the level of electrostatic charges in order to give the yarn a better aptitude. the cutting.
• the application of a super-image is advantageous in the case where the sizing composition contains no anti-static agent.
• the oversteaming then comprises as antistatic agent at least one quaternary ammonium salt.
• the amount of overstocking is 0.02 to 0.2% of the weight of the yarn, preferably 0.05 to 0.10%.
• the glass wire coated with the sizing composition according to the invention has a loss on ignition of less than 3%, preferably less than or equal to 2%.
• the loss on ignition is greater than 1, 25% and better still is between 1, 3 and 1, 7%.
• the son of glass according to the invention are in the form of son son windings which is subjected to a heat treatment. This treatment is intended essentially to eliminate the water provided by the sizing composition and, where appropriate, to accelerate the crosslinking of film-forming agents.
• the conditions of the treatment may vary according to the mass of the winding. In general, the drying is carried out at a temperature of the order of 110 to 140 ° C. for several hours, preferably 12 to 18 hours.
• the son coated with the sizing composition according to the invention may be made of glass of any kind as long as it is suitable for being fiber, for example E, C, AR (alkali-resistant) glass, or at a low temperature. boron level (less than 5%).
• these same son consist of filaments whose diameter may vary to a large extent, for example 10 to 20 microns, preferably 11 to 16 microns.
• these threads have a titer of between 30 and 200 tex, preferably 50 and 160 tex.
• composition suitable for coating said glass yarns, which composition is characterized in that it comprises the constituents below, in the following weight contents expressed in percentages of the solids. :
• the sizing composition comprises between 5 and 15% by weight of solids, preferably between 6 and 14% and more preferably between 8 and 12%.
• the sizing composition is prepared by simple mixing of the above constituents and water.
• the coupling agent is a silane, it is subjected to a step of prior hydrolysis in the presence of an acid.
• Another object of the invention relates to composites comprising glass son coated with the sizing composition.
• Such composites comprise at least one thermosetting material, preferably a polyester, a vinylester, an acrylic polymer, a polyurethane, a phenolic or epoxy resin, and glass threads consisting, in whole or in part, of glass yarns in accordance with the invention. 'invention.
• the level of glass within the composite is generally between
• the invention also relates to the use of glass son coated with the sizing composition for the production of composite parts by the technique of simultaneous projection molding, in particular by the technique LFI.
• the following example illustrates the invention without limiting it.
• the properties relating to the glass strands coated with the sizing composition are measured as follows: - the loss on ignition, in percentage, of the sized glass wire is measured under the conditions of the ISO 1887 standard.
• the number of loops is measured by unwinding the wire from a roving over a length of 500 meters, and scrolling between two optical sensors that detect defects. The number of loops is given per kg of wire.
• the flock is measured by passing 0.5 kg of wire unwound from a roving on a docking, at a speed of 80 m / min, and determining the mass of fibrils generated during scrolling.
• the flock is given in mg / kg of yarn.
• the half-discharge time (in seconds) is calculated from the measurements of the electric field obtained by means of a static voltmeter, on the wire placed in a static enclosure at 20 ° C. and 20% relative humidity. - the integrity of the yarn is measured by unrolling the yarn in a cutter
• the integrity of the wire after the cut is measured in the following manner: the wire unwound from a roving is introduced into a cutter WOLFANGEL 500 which cuts it and projects it substantially horizontally on a vertical wall (speed of cutting: 1200 m / min, length: 12 mm).
• a sizing composition is prepared in the form of an aqueous solution comprising, as a weight percentage of solids: » film-forming film-forming agents
• the preparation of the sizing composition is carried out as follows:
• the methoxy groups of the silanes (3) (4) are hydrolysed by addition of acid to an aqueous solution of this silane maintained with stirring.
• the other constituents are then introduced, still with stirring, and the pH is adjusted to a value of 4 ⁇ 0.2, if necessary.
• the weight content of solids in the sizing composition is equal to 9.9%.
• the sizing composition is used to coat, in known manner, glass filaments E about 12 ⁇ m in diameter drawn from glass threads flowing from the orifices of a die, the filaments then being collected in the form of of basewires of title equal to 57 tex.
• the coil is then dried at 130 ° C for 12 hours.
• the base yarns extracted from 6 windings are brought together to form a roving.
• the wire thus obtained has a loss on ignition equal to 1, 4%.
• the yarn of the example according to the invention has better performances than the reference yarn with equivalent quantity of flock and half-discharge time, namely that it has a number of loops. lower and better integrity before and after cutting.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Wood Science & Technology (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)

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• 2006
  • 2006-04-12 FR FR0651333A patent/FR2899893B1/fr not_active Expired - Fee Related
• 2007
  • 2007-04-06 EP EP07731884A patent/EP2091885A1/fr not_active Withdrawn
  • 2007-04-06 BR BRPI0711543-1A patent/BRPI0711543A2/pt not_active IP Right Cessation
  • 2007-04-06 JP JP2009504793A patent/JP2009533307A/ja not_active Abandoned
  • 2007-04-06 CA CA002647974A patent/CA2647974A1/en not_active Abandoned
  • 2007-04-06 CN CNA2007800200881A patent/CN101460420A/zh active Pending
  • 2007-04-06 US US12/297,107 patent/US20100022698A1/en not_active Abandoned
  • 2007-04-06 KR KR1020087027035A patent/KR20090008322A/ko not_active Application Discontinuation
  • 2007-04-06 RU RU2008140363/03A patent/RU2458873C2/ru not_active IP Right Cessation
  • 2007-04-06 WO PCT/FR2007/051082 patent/WO2007116191A1/fr active Application Filing
  • 2007-04-06 MX MX2008013060A patent/MX2008013060A/es unknown

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