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
  • C03C25/26—Macromolecular compounds or prepolymers
• • 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
  • C03C25/323—Polyesters, e.g. alkyd resins
• • 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
  • C03C25/48—Coating with two or more coatings having different compositions
  • C03C25/54—Combinations of one or more coatings containing organic materials only with one or more coatings containing inorganic materials only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
  • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
• • 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 invention relates to glass strands coated with a sizing composition intended for reinforcing organic materials of the polymer type. It also relates to the sizing composition used to coat said yarns, the composites incorporating these yarns and the use of sized yarns for the manufacture of articles by molding.
• the glass strands used for reinforcement in general are produced industrially from molten glass streaks flowing from the multiple orifices of a die. These threads are drawn mechanically in the form of continuous filaments, then are gathered into basic threads which are then collected, for example by winding on a rotating support. Before their gathering, the filaments are coated with a sizing composition by passing over a suitable device such as coating rollers.
• the sizing composition is essential for several reasons.
• the sizing composition protects the glass filaments from abrasion which occurs when the latter rub at high speed on the various members serving to guide and collect them. It also establishes connections between the filaments which makes it possible to give cohesion to the thread.
• the yarn being made more intact, its handling, especially during weaving operations, is improved and untimely breaks are avoided.
• the sizing composition promotes wetting and impregnation of the glass strands 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 glass strands in different forms: continuous or cut strands, mats of continuous or cut strands, fabrics ...
• Composites which incorporate cut glass strands can be obtained, inter alia, by the “contact molding” technique which consists in coating the interior of an open mold, without counter mold, with resin to be reinforced and glass wires of variable length.
• the resin and the cut wires are sprayed together on the internal walls of the mold by means of a “gun” comprising an incorporated cutter capable of cutting the wires extracted from one or more windings, generally in the form of rovings, and a device for spraying the resin, supplied for example by a pneumatic pump.
• thermosetting polymers belonging to the family of polyesters or epoxides The quality of the composites obtained by this process largely depends on the properties provided by the glass strands, and therefore on the size which covers them. In particular, it is sought to obtain compositions giving a size which can be easily wetted or impregnated on the surface with the resin in order to ensure close contact between the wires and the resin and thus obtain the expected mechanical reinforcement properties. It is also desired that these compositions are compatible with rapid processing, in particular that the son / resin mixture which is sprayed onto the mold in the form of overlapping strips can spread evenly.
• the subsequent rolling step intended to eliminate air bubbles and to ensure a better distribution of the wires in the resin must also be of short duration. Furthermore, it is necessary for the sizing composition to have a certain “incompatibility” with the resin so as to prevent the son / resin mixture from forming a compact mass which “collapses” by simple gravity. The impregnation of the wire with the resin must nevertheless be fast enough so that the wire / resin mixture can have a satisfactory "conformability", that is to say that it is able to perfectly match the shape of the mold.
• the sizing composition coating the glass strands combines at least one bis-silane and at least one unsaturated monosilane chosen from vinylsilanes and (meth) acrylosilanes.
• the present invention therefore aims to provide a sizing composition for reinforcing wires, in particular intended for open mold molding, and more particularly for molding by simultaneous projection of glass and resin wires, which allow to have a rapid resin impregnation of the strands and improved cutting ability with limited flock production.
• the subject of the invention is glass strands coated with an aqueous composition which combines as tackifying film-forming agents at least one polyester, at least one polyvinyl acetate and at least one polyurethane.
• glass strands coated with a sizing composition glass strands "which have been coated with a sizing composition which comprises ", that is to say not only the glass strands coated with the composition in question as obtained at the immediate exit from the sizing member or bodies, but also these same strands 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 rovings.
• Such assemblies can be obtained by simultaneously unwinding several windings of basic wires, then by assembling them into wicks which are wound on a rotating support. It can also be “direct” rovings with a title (or linear density) equivalent to that of the assembled rovings, obtained by gathering filaments directly under the die, and winding on a rotating support.
• the term "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 remainder consisting, where appropriate, of one or more essentially organic solvents which can help to dissolve certain constituents of the sizing composition.
• the sizing composition comprises as tackifying film-forming agents the mixture of at least one polyester, at least one polyvinyl acetate and at least one polyurethane. The polyester allows rapid impregnation with the resin and good conformability of the son / resin mixture in the mold. It also gives stiffness to the glass strands.
• the polyester is obtained by reaction of polycarboxylic acid (s) and / or anhydride (s) of these acids and polyol (s).
• the acid is chosen from saturated, unsaturated or aromatic diacids such as fumaric acid, isophthalic acid and terephthalic acid, anhydride from phthalic anhydride and maleic anhydride, and polyol among polyallene glycols such as ethylene glycol and propylene glycol, aromatic polyols such as bisphenol A or F, and novolaks.
• the polyesters obtained by reaction of phthalic or maleic anhydride and bis-phenol A or F, and phthalic and maleic anhydrides and propylene glycol are preferred.
• the polyester has a molecular weight which varies from 4000 to 17000 g / mol.
• the amount of polyester generally represents 50 to 80% by weight of the solids of the composition, preferably 50 to 70%.
• Polyvinyl acetate is important for achieving the required level of cut.
• the molecular weight of the polyvinyl acetate is generally less than 80,000 g / mol, preferably less than 70,000 g / mol and better still is between 40,000 and 65,000 g / mol.
• the amount of polyvinyl acetate used generally represents 10 to
• polyurethane makes the wire more integral and improves its cutting ability. It also plays the role of lubricant.
• the polyurethane is chosen from polyurethanes resulting from the reaction of at least one polyisocyanate and at least one polyol with an aliphatic and / or cycloaliphatic chain.
• the polyurethane has a molecular weight of less than 20,000 g / mol, preferably between 4,000 and 15,000 g / mol.
• the amount of polyurethane used generally represents 8 to 15% by weight of the solids of the sizing composition, preferably 8 to 10%.
• the sum of the weight contents of polyester, polyvinyl acetate and polyurethane represents at least 90%, preferably at least 95% of the solids of the sizing composition.
• the sizing composition may advantageously comprise one or more other components (hereinafter called "additives").
• the sizing composition can thus comprise a lubricating agent in an amount which can represent up to 5% by weight of the solid matters of the sizing composition.
• the lubricant helps to limit the formation of fluff, to increase the stiffness of the wire and to avoid sticking of the turns on the windings of base wires.
• this agent is chosen from cationic compounds of the polyalkylene imide type, and nonionic compounds of the ester type of fatty acids and of poly (alkylene glycols) / poly (oxyalkylene) such as polyethylene glycol monolaurate, or of the amides type. fatty acids and poly (oxyalkylene) such as hydrogenated tallow and polyethylene amides.
• the sizing composition can also comprise at least one coupling agent making it possible to hang the sizing on the surface of the glass filaments.
• the coupling agent is generally chosen from silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-acryloxypropyl-trimethoxysilane, gamma-methacryloxyprapyltrimethoxysilane, poly (oxyethylene / oxypropylene) trimethoxysilane, gamma-aminopropyl-triethyl phenylaminopropyltrimethoxysilane or styrylaminoethylaminopropyltrimethoxysilane, siloxanes, titanates, zirconates, in particular aluminum, and mixtures of these compounds.
• the silanes are chosen.
• the composition comprises at least two coupling agents, at least one of which is an unsaturated silane and the other is an aminosilane.
• a particularly advantageous combination comprises at least one silane containing an acrylic or methacrylic function and an aminosilane chosen from bis- (gamma-trimethoxysilylpropyl) silane and bis- (gamma-triethoxysilylpropyl) silane.
• the ratio generally ranges from 1: 1.5 to 1: 6, preferably from 1: 2 to 1: 5. The higher the ratio, the less the amount of oversize to deposit.
• the amount of coupling agent generally varies from 1 to 6% by weight of the solids of the sizing composition, preferably is greater than 1.5% and most often is of the order of 2%. It is also possible to introduce as an additive an anti-static agent such as lithium chloride, in an amount representing less than 5% by weight of the solids of the sizing composition.
• the glass strands coated with the sizing composition in accordance with the invention have a loss on ignition of less than 2.2%, preferably more than 1% and better still between 1.0 and 1.45%. Most often, the glass strands according to the invention are in the form of windings of basic strands which are subjected to a heat treatment.
• This treatment is intended essentially to remove the water provided by the sizing composition and, where appropriate, makes it possible to accelerate the crosslinking of the sticky film-forming agents.
• Treatment conditions may vary depending on the mass of the coil. 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 basic threads obtained are generally extracted from the winding and joined with several other basic threads in a wick which is then wound on a rotary support to form a roving.
• the application in “oversize” of a composition containing an anti- cationic static of the quaternary ammonium salt type on the wires makes it possible to reinforce the ability of the wires to be cut.
• the deposition of the above composition on the base threads, after extraction from the winding and assembly to form the wick, contributes to improving the cutting ability and consequently increases the life of the blades.
• the strands are coated with an aqueous composition containing 20 to 35% by weight of cetyltrimethylammonium chloride, preferably of the order of 25% by weight.
• the amount of “oversize” deposited generally represents 0.02 to 0.2% by weight of the wire, preferably 0.05 to 0.10%.
• the yarns coated with the sizing composition according to the invention may consist of glass of any kind as long as it is suitable for being fiber, for example glass E, C, AR (alkali-resistant), or low boron level (less than 5%).
• E glass and low boron glass are preferred.
• These same threads consist of filaments whose diameter can vary to a large extent, for example 9 to 17 ⁇ m, preferably 11 to 13 ⁇ m.
• the threads have a count of between 30 and 160 tex, preferably 40 and 60 tex.
• Such cut glass strands are distributed regularly and homogeneously within the resin, which makes it possible to have excellent quality reinforcement.
• Another subject of the invention relates to the sizing composition capable of coating said glass strands, which composition is characterized in that it comprises an aqueous mixture of at least one polyester, at least one polyvinyl acetate and at least one polyurethane as defined above.
• the sizing composition is an aqueous mixture comprising the following constituents, in the following weight contents expressed as percentages of solids:
• the sizing composition comprises between 5 and 15% by weight of solid matter, preferably between 6 and 11%.
• the liquid phase consists of 100% water.
• Another subject of the invention also relates to composites comprising glass strands coated with the sizing composition.
• Such composites comprise at least one thermosetting material, preferably a polyester, a vinylester, an acrylic, a phenolic or epoxy resin, and glass strands made up, in whole or in part, of glass strands in accordance with the invention.
• the content of glass in the composite is generally between 20 and 45% by weight, and preferably between 25 and 35%.
• the glass strands give the composites which contain them better resistance to aging, especially in a humid environment.
• Another subject of the invention is the use of glass strands coated with the sizing composition for the production of parts by the open mold molding technique, in particular by simultaneous spraying of said strands and of resin. It also relates to the use of said glass strands for the production of pipes by the centrifugation technique which consists in simultaneously projecting the strands and a resin in a rotary mold, the impregnation of the strands being carried out by centrifugal force. .
• the following examples illustrate the invention without, however, limiting it.
• sticky film-forming agents polyvinyl acetate (1) ; molecular weight 50,000 60.1 - vinyl acetate-N-methylolacrylamide copolymer (2) 21, 9
• plasticizer mixture of diethylene glycol dibenzoate and propylene glycol dibenzoate (5) (weight ratio 50: 50) 9.8 • lubricants - polyethylene glycol monolaurate 400 (6) 4.1 - polyethylene imide with free amide functions ( 7) 0.7
• the preparation of the sizing composition is carried out in the following manner: The alkoxy groups of the silanes (3) and (4) are hydrolyzed by adding acid to an aqueous solution of this silane which is kept under 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 sizing composition is used to coat, in a known manner, glass filaments E of approximately 12 ⁇ m in diameter drawn from glass filaments flowing from the orifices of a die, the filaments then being collected in the form of base wire windings with a title equal to 60 tex. The winding is dried at 130 ° C for 12 hours.
• the basic yarns extracted from 7 windings are coated with an aqueous solution at 25% by weight of cetyltrimethylammonium chloride (dry content: 0.05%).
• the wire unwound from the roving is inserted into a cutting device comprising two blades, one made of hard steel and the other made of “soft” quick-wear steel (heat treatment at 550 ° C), and equipped with strength and temperature.
• the cut carried out at 20 ° C under 50% relative humidity, is adjusted to form cut wires 50 mm in length.
• the ability to cut is measured by the mass of glass strands that can be cut until the appearance of strands of double length (2 x 50 mm).
• the mass of cut son obtained is assigned the value 1 which is used here as a reference value to measure the ability to cut.
• EXAMPLE 2 The process is carried out under the conditions of Example 1, modified in that the sizing composition comprises, in% by weight of the solid materials:
• the flock is measured by scrolling the thread on a device consisting of 6 tie-ins, at a speed of 93 m / min.
• the device is placed in a room conditioned at 20 ° C and 50% relative humidity.
• the flock is defined by the quantity of fibrils, in mg, obtained after passing through a mass of thread of 1 kg.
• the values of the loss on ignition, of the flock and of the ability to cut are shown in Table 1.
• EXAMPLE 3 The procedure is as in Example 2, modified in that the content of cetyltrimethylammonium chloride deposited on the basic wires is equal to 0.10%.
• the composition has a solids content of 6.6%.
• the values of the loss on ignition, the flock and the ability to cut are given in table 1.
• EXAMPLE 4 (COMPARATIVE) The process is carried out under the conditions of Example 2, modified in that the film-forming tackifiers consist solely of polyester® in a content equal to 93%.
• the sizing composition has a solids content of 6.5%.
• the values of the loss on ignition, of the flock and of the ability to cut are shown in Table 1.
• EXAMPLE 5 (COMPARATIVE) The procedure is as in Example 2, modified in that the sizing composition includes the following film-forming tackifiers, in% by weight of solids:
• the sizing composition has a solids content equal to 6.8%.
• the values of the loss on ignition, of the wadding and of the ability to cut are shown in table 1.
• EXAMPLE 7 (COMPARATIVE! Glass strands coated with a size suitable for making composite parts by molding are used These yarns are marketed by PPG under the reference 6313.
• the values of loss on ignition, wadding and cutting ability are given in Table 1.
• EXAMPLE 8 The procedure is carried out under Example 2, modified in that the sizing composition contains 0.2% of lubricating agent * 1) and is devoid of antistatic agent * 12) .
• the sizing composition has a solids content of 6.4%.
• the values of the loss on ignition, of the flock and of the ability to cut are shown in Table 1.
• EXAMPLE 9 The procedure is as in Example 3, modified in that the sizing composition contains 0, 2% lubricant (11) .
• the sizing composition has a solids content of 6.94%. The values of the loss on ignition, the flock and the ability to cut are given in table 1.
• EXAMPLE 10 The procedure is carried out under the conditions of Example 2, modified in that the sizing composition comprises, in% by weight of the solid materials: - polyester® 64.0 - polyvinyl acetate * 1) 24.0 - polyurethane® 10, 0 - silane (10) 1.7 - lubricating agent * 11) 0.3
• the sizing composition has a solids content of 8.4%.
• the values of the loss on ignition, of the flock and of the ability to cut are shown in Table 1.
• EXAMPLE 11 The procedure is carried out under example 2, modified in that the size composition, the polyester® is replaced by polyester * 13) .
• the sizing composition has a solids content of 8.3
• the sizing composition comprises the agents for following couplings, in% by weight of solids: - polyester® 61.8 - polyvinyl acetate (1) 23.0 - polyurethane® 10.2 - silane (10) unsaturated 0.8 - bis (triethoxysilyIpropyl) amine * 13) 4.0 - lubricating agent * 11) 0.2
• the sizing composition has a solids content of 8.6%.
• the values of the loss on ignition, of the flock and of the ability to cut are shown in Table 1.
• EXAMPLE 13 The procedure is carried out under the conditions of Example 12 modified in that the content of cetyltrimethylammonium chloride deposited on the base wires is equal to 0.10%. The cutting ability is given in Table 1.
• EXAMPLE 14 The procedure is carried out under the conditions of Example 12 modified in that no cetyltrimethylammonium chloride is deposited on the basic yarns. The values of the loss on ignition, of the flock and of the ability to cut are shown in table 1.
• the horizontal wall has two grooves 2 cm deep to assess the conformation of the cut son / resin mixture, - the mixture projected onto the mold contains 30% by weight of glass and has an average thickness of around 3 mm .
• the performance of the wires is collated in table 2 below: Table 2 Ex. 15 Ex. 16 Ex17 Ex. Wire 2 Ex. 10 Ex. 7
• the yarns having lower contents of lubricating agent (examples 8 and 9) and of coupling agent (example 10) have a high cutting ability and a moderate production of flock.
• the combination of an unsaturated silane and an aminosilane makes it possible to obtain yarns having a high cutting capacity without oversizing (example 14), the latter increasing considerably when the content of oversizing increases (examples 12 and 13).
• Table 2 shows that the threads according to the invention (examples 15 to 17) retain a high impregnation speed under the conditions of the spraying, equivalent to that of the threads of Comparative Example 7, with however a regularity of the carpet and improved vertical wall strength.
• the integrity of the cut wire is determined visually according to a scale of values ranging from 1 (poor; cottony appearance) to 5 (very good; no breakage of the wire).
• the cutting ability is measured under the conditions of Example 1.
• Example 19 Example 20 Integrity 4.5 4.5 Cutting ability 2.40 0.95
• the wire according to the invention has a cutting ability markedly improved compared to the known wire and identical integrity.

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• Inorganic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Reinforced Plastic Materials (AREA)
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• Adhesives Or Adhesive Processes (AREA)

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