Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
  • C03B37/01—Manufacture of glass fibres or filaments
• • 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
• • 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
  • C03C25/12—General methods of coating; Devices therefor
  • C03C25/14—Spraying
• • 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
• • 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
  • Y10T428/2904—Staple length fiber
  • Y10T428/2907—Staple length fiber with coating or impregnation

Definitions

• the present invention relates to the field of glass yarns called verranne used in the constitution of fabrics, in particular intended to form wall coverings. It relates to a sizing composition for verranne, the process using this composition and the verranne obtained.
• the term "verranne” is used for discontinuous glass strands obtained by fiberizing molten glass through the orifices of a die.
• the sector in question can be fed either by pieces of glass, generally in the form of beads ("reflow” process), or by molten glass from an oven (“direct” process).
• the glass may be glass E, glass C or any other glass capable of undergoing the fiberizing operation.
• the verranne may be in the form of a ribbon, improperly called a "wick", which is a continuous assembly without twist of substantially parallel glass strands held together by their mutual adhesion. The wick results from the assembly of intermittent discontinuous filaments using a false twist.
• this ribbon is either used as it is to form the weft of certain types of fabric, or twisted to make a textile thread, or cut into elements of determined length.
• the production of verranne can be carried out according to the method described for example in patent application FR-A-2 817 548.
• the filaments of molten glass flowing from the die are drawn and wound in the form of a sheet on a cylinder located substantially vertical to the die. After rotation of the cylinder by approximately 270 °, the layer of filaments comes into contact with a doctor blade which detaches it from the surface of the cylinder and cuts the filaments, then these filaments are directed towards an oblong device of conical shape comprising in its center a core wire which moves from one end to the other of the cone.
• the filaments coming from the cylinder are wound around the core wire and form a wick which, at the exit of the cone, is wound on a winder placed laterally to the oblong element.
• the core wire gives resistance to the verranne when the latter is stressed in tension: it can be made of glass or better still plastic.
• the filaments, before their gathering in the form of threads are coated with a sizing composition intended to protect them from the abrasion which occurs during friction with the organs of the different systems implemented for their training.
• the application of the sizing composition is carried out by means of suitable devices, such as spray nozzles, coating rollers or brushes, generally arranged upstream of the deposit of the filaments on the cylinder and upstream of the doctor blade.
• the role of the sizing is essential. In addition to its function of protection against abrasion, it makes it possible to associate the verranne with organic and / or inorganic matters by facilitating in particular the wetting and the impregnation of the wick by these matters.
• the size also promotes the bonding of the filaments with each other, which results in better dimensional stability of the yarn. Being able to have such threads has an advantage when it is desired to use them under conditions requiring high mechanical stresses, for example for textile applications.
• a size is expected to promote the bonding of the filaments on the stretching cylinder, to allow a clean cut by the doctor blade and not to form too much "stuffing", that is to say of Broken filaments which by accumulating on certain organs such as pulleys block their functioning.
• Another reason for wanting to limit the flock is that it disperses easily in the air that operators are likely to breathe, which it is desirable to avoid.
• the sizing compositions must also be able to withstand the shear induced by the passage of the wires on the drawing devices and to wet the surface of the filaments, and this, at high drawing speeds, of the order of several tens of meters per second. They must also not confer a “slippery” character which is not too pronounced for the coils of verranne to keep their dimensional stability during transport and storage, namely that the turns do not collapse.
• the compositions must still retain their initial properties over time and their constituents must remain stable before being deposited on the filaments.
• the usual sizing compositions which are suitable for the production of verranne are essentially based on mineral oil (s), possibly in combination with surfactants. If the oil provides effective protection from abrasion and participates in forming a wicking having bulk (it is also called “volumization"), it also brings "slippery" to the filaments which makes the wicking insufficiently cohesive to allow it to be woven in good conditions, especially because there is knot formation. To satisfy the conditions of weaving, it is indeed imperative that the wick has hold, that is to say that the filaments which constitute it can somehow cling to each other.
• the bonding of the filaments must remain flexible so that they remain free to a certain extent to move relative to each other when significant variations in tension occur, and thus avoid sudden rupture of the wick.
• the search for a sizing composition having better weaving performance should not be to the detriment of the other properties.
• the composition must remain suitable for application by means of air spray nozzles operating with a pressure of approximately 20 bars without generating too fine droplets capable of forming a kind of mist.
• the presence of fog in the vicinity of the nozzles results in a loss of size which does not deposit on the filaments and a greater probability for operators to inhale the products in question.
• the subject of the present invention is a sizing composition capable of coating glass strands, in particular in the form of verranne, which improves their tensile strength, and thus allows better weaving.
• Another object of the invention relates to sized glass strands, in particular in the form of verranne, by means of the composition defined in the preceding paragraph, said strands having, due to a certain degree of elasticity, better resistance to rupture in traction, which allows them to be woven at a higher speed, in particular to form a wall covering of the type of canvas to be painted.
• the sizing composition according to the invention consists of a solution which is characterized by the fact that it contains at least one fatty acid containing at least two ethylenic bonds.
• the term "sizing composition” means a composition capable of being deposited on glass filaments and of protecting them during their preparation, in particular with a view to obtaining a verranne.
• such a composition is in the form of a solution with a viscosity less than or equal to 120 ⁇ 10 ⁇ 3 Pa.s (120 cP) and it comprises at least one lubricating agent and possibly other additives for example a coupling agent with glass, a textile agent or a surfactant.
• the sizing composition is substantially free of water, that is to say that it contains less than 5% d water, preferably less than 1% and better still does not contain it, on the other hand, the composition may contain one or more organic solvents capable of being used to dissolve all or part of the components used in the composition of sizing.
• the fatty acid is chosen from unsaturated fatty acids containing 10 to 24 carbon atoms, and preferably 14 to 22 carbon atoms. Straight chain fatty acids are preferred.
• a and B represent a hydrocarbon chain, and the total number of carbon atoms in the chains A and B varies from 2 to 16.
• the particularly preferred fatty acids contain 18 to 22 carbon atoms and satisfy the above formula in which:
• linoleic acid cis acid, cis-9,12-octadecadienoic acid
• linolelaidic acid trans acid, trans-9,12-octadecadienoic acid
• ⁇ -linolenic acid 6,9,12-octadecatrienoic acid
• linolenic acid trans, trans, trans-9,12,15-octadecatrienoic acid
• ⁇ -eleostearic acid cis, trans, trans-9,12 acid , 15-octadecatrienoic acid
• ⁇ -eleostearic acid trans, trans, trans-9,12,15-octadecatrienoic acid
• cis acid cis-11,14-eicosa- dienoic acid
• cis acid cis acid, cis , cis-5,8,11-eicosatrienoic acid
• fatty acids in particular linoleic acid and linolenic acid.
• Linoleic acid is preferred. Without being bound by any explanation, it is believed that the double bonds of the fatty acid react with the oxygen in the air and form products of higher molecular mass endowed with sticky properties making it possible to adhere the filaments to each other and therefore to give cohesion to the wick.
• the content of unsaturated fatty acid in the sizing composition is greater than or equal to 5%, preferably greater than or equal to 8%.
• it does not exceed 60% by weight and preferably 40%.
• the fatty acid content is between 10 and 30%.
• the sizing composition further comprises at least one polymer carrying one or more hydroxy, epoxy and / or amine reactive functions, and more particularly having a molecular mass at least equal to 300 and preferably less at 3000.
• the aforementioned polymers also contain one or more double bonds.
• unsaturations brings the elastomeric character which allows the verranne to have a certain elasticity and therefore to have a better tensile strength.
• the polymers containing one or more hydroxy or epoxy-reactive functional groups is used, preferably at the terminal position, such as poly Bd ® hydroxyl-terminated marketed by Atofina, and polymers containing one or more amine reactive functional groups, preferably in the terminal position, for example the poly Bd "diamine marketed by Atofina.
• the latter polymer gives a slight yellow coloring to the verranne and that it is also more difficult to handle since it is more sensitive to carbon dioxide gas. air than other polymers.
• the abovementioned polymer content can represent up to 40% by weight of the sizing composition, and preferably it varies from 5 to 30%, and better still from 8 to 25%.
• the sizing composition comprises the combination of linoleic acid and polybutadiene containing hydroxy reactive functions, preferably in the terminal position.
• the sizing composition may comprise one or more components (hereinafter referred to as additives) which give the sizing particular properties.
• composition according to the invention can thus comprise a solvent whose role consists in adapting the viscosity to the application conditions.
• This solvent does not react with the constituents of the sizing composition and neither does it function to dissolve them.
• the aforementioned esters are preferred in particular because they have a good ability to "wet" the glass without exhibiting any harmful character.
• the amount of solvent that can be used can represent up to 30% by weight of the sizing composition. However, it is preferred to limit the solvent content in order to avoid the risk of variation in the concentration of the various constituents of the sizing composition due to the evaporation induced by the high temperature necessary to produce the glass filaments.
• the presence of solvent (s) in limited quantity does not require any special treatment to remove them.
• the sizing composition can also comprise, as an additive, a coupling agent making it possible to hang the sizing on the glass.
• the coupling agent is generally chosen from silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-acryloxypropyltrimethoxy-silane, gamma-methacryloxypropyltrimethoxysilane, poly (oxyethylene / oxypropylene) trimethoxysilane, gamma-aminopropyltriethyl phenyl aminopropyltrimethoxysilane, styrylamino- ethylaminopropyltrimethoxy-silane or terbutylcarbamoylpropyl-trimethoxysilane, siloxanes, titanates, zirconates and mixtures of these compounds.
• the silanes are preferably chosen.
• the proportion of coupling agent (s) is generally between 0 and 20% by weight of the sizing composition and preferably between 0 and 15%. In general, the sizing composition does not contain any coupling agent.
• the composition may also comprise, as an additive, at least one textile processing agent essentially playing a role of lubricant and / or surfactant, 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 40% by weight of the composition, and preferably 5 and 25%.
• the textile processing agent is generally chosen from fatty esters such as decyl laurate, isopropyl palmitate, cetyl palmitate, isopropyl stearate, isobutyl stearate, trimethylolpropane trioctanoate and mixtures based on mineral oils.
• ком ⁇ онентs of ethylene glycol adipate, alkylphenol derivatives such as ethoxylated nonylphenol and glycol derivatives such as polyethylene glycols or polypropylene glycols of molecular mass less than 2000.
• the composition according to the invention is generally deposited on the glass filaments in a single step, for example under the conditions of the process described in FR-A-2 817 548.
• the sizing composition is applied to the filaments immediately before they come into contact with the cylinder, and possibly also after.
• the application can be done in different ways, the most used being spraying by means of a nozzle or more generally of two nozzles moving in opposite directions to each other along the generatrix of the cylinder in order to obtain a homogeneous distribution on the whole of the tablecloth.
• a sizing composition having a viscosity less than or equal to 120 ⁇ 10 ⁇ 3 Pa.s (120 cP), and advantageously between 50 and 100 ⁇ 10 ⁇ 3 Pa.s ( 50 and 100 cP).
• the sized filaments are detached from the cylinder and cut by the doctor blade, then they form a wick which is either collected in the form of windings by means of rotating supports, for example rollers, or deposited on a support in translation for form a tablecloth or "mat", either cut into segments of appropriate length.
• the verranne obtained according to the invention can thus be in different forms after collection, for example in the form of reels of ribbons, assembled locks or braids, "mats" or cut threads.
• the verranne coated with the sizing composition has a good unwinding ability and is easy to handle, the filaments remaining perfectly cohesive. In particular, the windings with straight edges retain their dimensional characteristics and are not deformed.
• the verranne is coated with a quantity of size such that it has a loss on ignition of less than 2%, preferably less than 1%, better still less than 0.85%. Preferably, the loss on ignition is greater than 0.3%, and advantageously greater than 0.6%.
• the glass filaments constituting the verranne have a diameter which can vary to a large extent, most often from 5 to 30, preferably from 6 to 14 ⁇ m. They can be made of any glass, the best known in the field being E glass and C glass.
• the windings obtained are then placed on pallets to be shipped to the various places where the woven veneer is woven, in particular to make wall covering, for example canvas to paint.
• the sizing composition according to the invention does not require any prior drying of the windings before proceeding to packaging. Avoiding passage through an oven both reduces energy consumption and limits handling of the windings, and therefore reduces the cost of production.
• the spools of verranne are placed on weaving machines which generally operate at a high rate, of the order of 450 to 470 strokes / minute.
• the verranne coated with the size according to the invention it is possible to use air jet looms which operate at a high speed (500 to 550 strokes / minute or even more) and therefore to increase the productivity while maintaining a relatively low number of “breaks”.
• the verranne present has an improved swelling which gives it better “covering” power and makes it possible to obtain a homogeneous fabric (without “holes”).
• the verranne generally has a toughness greater than 4 cN / tex, preferably greater than 7.5 cN / tex, thus making it possible to form fabrics which are resistant to paint treatments.
• the canvas After weaving, the canvas is coated with a "finishing" primer intended to give it sufficient rigidity to allow it to be laid on the final support.
• a "finishing" primer intended to give it sufficient rigidity to allow it to be laid on the final support.
• It is generally a starch solution or an acrylic or PVA emulsion which is applied to the canvas by impregnation in a bath. It is necessary to have a great compatibility between the size and the primer so that the canvas keeps its properties until the final use.
• the verranne according to the invention has a very good level of compatibility with the primer, in particular because the sizing composition is capable of containing a high amount of surfactants (up to 40% by weight).
• the following methods are used for measuring the physical and mechanical properties of the verranne coated with the sizing composition according to the invention.
• the surface tension is measured using an M3 blade tensiometer marketed by PROLABO. It is expressed in mN / m.
• the toughness is evaluated by measuring the tensile breaking force under the following conditions.
• a device is used which consists of two pulleys, a dynamometer and a traction wire connected to a motor.
• the upper pulley (diameter: 205 mm) and the lower pulley of smaller diameter are 355 mm apart, the pulleys being arranged vertically.
• the lower pulley is connected to a dynamometer, itself connected to the traction wire driven by the motor (speed: 350 mm / min.).
• the verranne is wrapped twice around the pulleys and the engine is started.
• the toughness measurement corresponds to the value measured on the dynamometer when the verranne breaks.
• the toughness is expressed in cN / tex.
• the loss on ignition is measured according to ISO 1887 and is expressed in% by weight.
• a verranne formed from 400 glass filaments C of 11 ⁇ m in diameter is formed using the device described in FR-A-2 817 548.
• a composition of 'size comprising a mixture of mineral oils and surfactants (1) having a viscosity equal to 80 x 10 "3 Pa.s (80 cP) and a surface tension equal to 31.4 mN / m.
• the layer of filaments is detached from the cylinder and the cut filaments are gathered together in verranne to form a coil.
• the evolution of the tenacity of the verranne extracted from the coil as a function of time is given in FIG. 1.
• the initial tenacity is equal to 2.6 cN / tex and to 3 cN / tex after 10 days.
• Example 1 the sizing composition comprising (in percentage by weight): • linoleic acid 60
• the verranne extracted from the coil has an initial toughness equal to 2.7 cN / tex and equal to 5.4 cN / tex after 10 days.
• the sizing composition comprising (in percentage by weight): mixture of mineral oils and surfactants (1) 15 linoleic acid 20 isopropyl palmitate 15 aromatic polyurethane hexaacrylate (molecular weight: 1000) (3) 20 ethoxylated lauric alcohol (4 EO) () 15
• NMP 15 The viscosity of the composition is equal to 105 ⁇ 10 ⁇ 3 Pa.s (105 cP).
• the verranne extracted from the coil has an initial toughness equal to 2.7 cN / tex and equal to 8.1 cN / tex after 10 days.
• the viscosity of the composition is equal to 120 x 10 ⁇ 3 Pa.s (120 cP) and a surface tension equal to 34.7 mN / m.
• the verranne extracted from the coil has an initial toughness equal to 1.6 cN / tex and equal to 7.5 cN / tex after 10 days, and a loss on ignition of 0.72%.
• the viscosity of the composition is equal to 64 x 10 -3 Pa.s (64 cP) and a surface tension equal to 32.8 mN / m.
• the verranne extracted from the coil has an initial toughness equal to 2.5 cN / tex and equal to 8.0 cN / tex after 10 days, and a loss on ignition of 0.4%.
• the viscosity of the composition is equal to 68 x 10 ⁇ 3 Pa.s (68 cP) and a surface tension equal to 32.5 mN / m.
• the evolution of the tenacity of the verranne extracted from the reel as a function of the storage time, without prior drying, is given in FIG. 1.
• the initial tenacity is equal to 3.2 cN / tex and to 9.5 cN / tex after 10 days, and a loss on ignition of 0.6%.
• the viscosity of the composition is equal to 68 ⁇ 10 -3 Pa.s (68 cP) and a surface tension equal to 32.7 mN / m.
• the verranne extracted from the coil has an initial toughness equal to 3.1 cN / tex and equal to 9.2 cN / tex after 10 days, and a loss on ignition of 0.81%.
• the viscosity of the composition is equal to 62 ⁇ 10 -3 Pa.s (62 cP) and a surface tension equal to 32.2 mN / m.
• the verranne extracted from the coil has an initial toughness equal to 3.2 cN / tex and equal to 8.5 cN / tex after 10 days, and a loss on ignition of 0.25%.
• the viscosity of the composition is equal to 59 ⁇ 10 ⁇ 3 Pa.s (59 cP) and a surface tension equal to 32.7 mN / m.
• the verranne extracted from the coil has an initial toughness equal to 2.7 cN / tex and equal to 10.0 cN / tex after 10 days, and a loss on ignition of 0.65%.
• Examples 5 to 10 show that the effect of the unsaturated fatty acid is enhanced when a hydroxyl-terminated polymer is added.
• a toughness value more than 3 times greater than that of the size of example 1 is notably obtained in examples 7, 8 and 10.
• the polymer contributes to making the composition d more stable size. This effect is visible in particular for the composition of Example 4 which, although giving verranne a good level of tensile strength, is unstable and needs to be implemented quickly.
• the composition of Examples 7, 8 and 10 combining the same content of unsaturated fatty acid and a polymer remains stable, with, in addition, increased toughness.
• the increase in toughness obtained with the sizing composition in accordance with the invention is not to the detriment of the other properties which are the surface tension and the viscosity, the latter being comparable to those of the reference composition.
• the sizing composition according to the invention could be sprayed without generating a mist and that the verranne obtained is easy to handle: it is easily unwound and has an improvement in toughness for a loss on ignition relatively low, i.e. less than 0.85%.

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

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• 2002
  • 2002-07-18 FR FR0209368A patent/FR2842516B1/fr not_active Expired - Fee Related
• 2003
  • 2003-07-09 MX MXPA05000759A patent/MXPA05000759A/es unknown
  • 2003-07-09 PL PL03372991A patent/PL372991A1/xx not_active Application Discontinuation
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  • 2003-07-09 JP JP2004522225A patent/JP2005538917A/ja active Pending
  • 2003-07-09 AU AU2003263276A patent/AU2003263276A1/en not_active Abandoned
  • 2003-07-09 EP EP03765138A patent/EP1523456A1/de not_active Withdrawn
  • 2003-07-09 KR KR10-2005-7000846A patent/KR20050021496A/ko not_active Application Discontinuation
  • 2003-07-09 US US10/519,848 patent/US20060147706A1/en not_active Abandoned
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  • 2003-07-09 WO PCT/FR2003/002137 patent/WO2004009506A1/fr active Application Filing
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