EP1523456A1 - Sizing composition for glass staple fibres, method using said composition and resulting products - Google Patents

Sizing composition for glass staple fibres, method using said composition and resulting products

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Publication number
EP1523456A1
EP1523456A1 EP03765138A EP03765138A EP1523456A1 EP 1523456 A1 EP1523456 A1 EP 1523456A1 EP 03765138 A EP03765138 A EP 03765138A EP 03765138 A EP03765138 A EP 03765138A EP 1523456 A1 EP1523456 A1 EP 1523456A1
Authority
EP
European Patent Office
Prior art keywords
composition
verranne
glass
equal
glass strand
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03765138A
Other languages
German (de)
French (fr)
Inventor
Patrick Moireau
Anne Berthereau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Adfors SAS
Original Assignee
Saint Gobain Vetrotex France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Vetrotex France SA filed Critical Saint Gobain Vetrotex France SA
Publication of EP1523456A1 publication Critical patent/EP1523456A1/en
Withdrawn legal-status Critical Current

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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)

Abstract

The invention relates to a sizing composition for glass fibres, such as those in the form of glass staple fibres, comprising at least one fatty acid containing at least two ethylenic bonds. The invention also relates to a method of producing glass staple fibres using the inventive sizing composition and to glass staple fibres coated with said sizing composition.

Description

COMPOSITION D'ENSIMAGE POUR VERRANNE, PROCEDE UTILISANT CETTE COMPOSITION ET PRODUITS RESULTANTS SIZING COMPOSITION FOR VERRANNE, METHOD USING THE SAME AND RESULTING PRODUCTS
La présente invention se rapporte au domaine des fils de verre dénommés verranne entrant dans la constitution de tissus notamment destinés à former des revêtements muraux. Elle concerne une composition d'ensimage pour verranne, le procédé utilisant cette composition et la verranne obtenue.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.
On appelle « verranne » les fils de verre discontinus obtenus par fibrage de verre en fusion à travers les orifices d'une filière.The term "verranne" is used for discontinuous glass strands obtained by fiberizing molten glass through the orifices of a die.
La filière en question peut être alimentée indifféremment soit par des morceaux de verre, généralement sous forme de billes (procédé par « refusion »), soit par du verre fondu provenant d'un four (procédé « direct »). Le verre peut être du verre E, du verre C ou tout autre verre apte à subir l'opération de fibrage. La verranne peut se présenter sous la forme d'un ruban, improprement appelé « mèche », qui est un ensemble continu sans torsion de fils de verre sensiblement parallèles maintenus par leur adhérence réciproque. La mèche résulte de l'assemblage de filaments discontinus entremêlés à l'aide d'une fausse torsion. Généralement, ce ruban est soit utilisé tel quel pour former la trame de certains types de tissus, soit retordu pour en faire un fil textile, soit coupé en éléments de longueur déterminée.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. Generally, 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.
La fabrication de verranne peut être réalisée selon le procédé décrit par exemple dans la demande de brevet FR-A-2 817 548. Les filaments de verre fondu s'écoulant de la filière sont étirés et enroulés sous forme de nappe sur un cylindre situé sensiblement à la verticale de la filière. Après rotation du cylindre d'environ 270°, la nappe de filaments arrive au contact d'un racle qui la décolle de la surface du cylindre et coupe les filaments, puis ces filaments sont dirigés vers un dispositif oblong de forme conique comportant en son centre un fil d'âme qui se déplace d'une extrémité à l'autre du cône. Les filaments issus du cylindre s'enroulent autour du fil d'âme et forment une mèche qui, à la sortie du cône, est enroulée sur un bobinoir placé latéralement à l'élément oblong. Le fil d'âme donne de la résistance à la verranne lorsque cette dernière est sollicitée en traction : il peut être en verre ou mieux encore en matière plastique. Sauf lorsqu'ils sont destinés à former de la bourre, les filaments, avant leur rassemblement sous forme de fils, sont revêtus d'une composition d'ensimage destinée à les protéger de l'abrasion qui se produit lors du frottement avec les organes des différents dispositifs mis en œuvre pour leur formation. L'application de la composition d'ensimage est effectuée au moyen de dispositifs appropriés, tels que des buses de pulvérisation, des rouleaux enducteurs ou des pinceaux, généralement disposés en amont du dépôt des filaments sur le cylindre et en amont du racle.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. Except when they are intended to form a wad, 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.
Le rôle de l'ensimage est essentiel. En plus de sa fonction de protection contre l'abrasion, il permet d'associer la verranne avec des matières organiques et/ou inorganiques en facilitant notamment le mouillage et l'imprégnation de la mèche par ces matières. L'ensimage favorise aussi la liaison des filaments entre eux ce qui se traduit par une meilleure stabilité dimensionnelle du fil. Pouvoir disposer de tels fils présente un avantage lorsqu'on souhaite les utiliser dans conditions nécessitant des contraintes mécaniques fortes, par exemple pour des applications textiles.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.
On attend notamment d'un ensimage qu'il favorise le collage des filaments sur le cylindre d'étirement, permette d'obtenir une coupe franche par le racle et ne forme pas trop de « bourre », c'est-à-dire de filaments brisés qui en s'accumulant sur certains organes tels que les poulies en bloquent le fonctionnement. Une autre raison de vouloir limiter la bourre est qu'elle se disperse facilement dans l'air que les opérateurs sont susceptibles de respirer, ce qu'il est souhaitable d'éviter.In particular, 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.
De manière générale, les compositions d'ensimage doivent aussi pouvoir résister au cisaillement induit par le passage des fils sur les dispositifs d'étirage et mouiller la surface des filaments, et ce, à des vitesses d'étirage élevées, de l'ordre de plusieurs dizaines de mètres par seconde. Elles doivent aussi ne pas conférer un caractère « glissant » pas trop prononcé pour que les bobines de verranne gardent leur stabilité dimensionnelle pendant le transport et le stockage, à savoir que les spires ne s'effondrent pas. Les compositions doivent encore conserver leurs propriétés initiales dans le temps et leurs constituants doivent demeurer stables avant la dépose sur les filaments.In general, 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.
Les compositions d'ensimage usuelles qui conviennent à la production de verranne sont essentiellement à base d'huile(s) minérale(s), éventuellement en combinaison avec des agents tensioactifs. Si l'huile permet de protéger efficacement de l'abrasion et participe à former une mèche ayant du gonflant (on parle aussi de « voluminisation »), elle apporte aussi du « glissant » aux filaments qui rend la mèche insuffisamment cohésive pour lui permettre d'être tissée dans de bonnes conditions, notamment parce qu'il y a formation de nœuds. Pour satisfaire aux conditions du tissage, il est en effet impératif que la mèche ait de la tenue, c'est-à-dire que les filaments qui la constituent puissent en quelque sorte s'accrocher les uns aux autres. La liaison des filaments doit demeurer souple afin que ceux ci restent libres dans une certaine mesure de se déplacer les uns par rapport aux autres lorsque des variations de tension importantes se produisent, et éviter ainsi une rupture brutale de la mèche. De manière générale, on peut considérer que plus la résistance à l'allongement d'une mèche est élevée, meilleure est l'aptitude au tissage.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. In general, it can be considered that the higher the resistance to elongation of a wick, the better the weaving ability.
La recherche d'une composition d'ensimage ayant de meilleures performances au tissage ne doit pas se faire au détriment des autres propriétés. Notamment, la composition doit rester apte à être appliquée par l'intermédiaire de buses de pulvérisation à air fonctionnant avec une pression d'environ 20 bars sans générer des gouttelettes trop fines susceptibles de former une sorte de brouillard. La présence de brouillard au voisinage des buses se traduit par une perte d'ensimage qui ne se dépose pas sur les filaments et une probabilité plus grande pour les opérateurs d'inhaler les produits en cause.The search for a sizing composition having better weaving performance should not be to the detriment of the other properties. In particular, 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.
La présente invention a pour objet une composition d'ensimage apte à revêtir des fils de verre, en particulier sous forme de verranne, qui améliore leur résistance à la rupture en traction, et permet ainsi un meilleur tissage. Un autre objet de l'invention concerne les fils de verre ensimés, en particulier sous forme de verranne, au moyen de la composition définie au paragraphe précédent, lesdits fils ayant, du fait d'un certain degré d'élasticité, une meilleure résistance à la rupture en traction ce qui autorise leur tissage à une vitesse plus élevée pour former notamment un revêtement mural du type toile à peindre.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.
La composition d'ensimage conforme à l'invention est constituée d'une solution qui se caractérise par le fait qu'elle contient au moins un acide gras renfermant au moins deux liaisons éthyléniques. Dans la présente invention, on entend par « composition d'ensimage » une composition apte à être déposée sur des filaments de verre et à les protéger lors de leur élaboration, en particulier en vue d'obtenir une verranne. De manière générale, une telle composition se présente sous la forme d'une solution de viscosité inférieure ou égale à 120 x 10"3 Pa.s (120 cP) et elle comprend au moins un agent lubrifiant et éventuellement d'autres additifs par exemple un agent de couplage avec le verre, un agent textile ou un tensioactif. Dans le contexte de l'invention, la composition d'ensimage est substantiellement exempte d'eau c'est- à-dire qu'elle contient moins de 5 % d'eau, de préférence moins de 1 % et mieux encore n'en contient pas. En revanche, la composition peut contenir un ou plusieurs solvants organiques susceptibles d'être mis en œuvre pour solubiliser tout ou partie des composants entrant dans la composition de l'ensimage.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. In the present invention, 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. In general, 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. In the context of the invention, 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.
L'acide gras est choisi parmi les acides gras insaturés renfermant 10 à 24 atomes de carbone, et de préférence 14 à 22 atomes de carbone. Les acides gras à chaîne linéaire sont préférés.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.
Les acides gras insaturés répondent avantageusement à la formule générale suivante :Unsaturated fatty acids advantageously correspond to the following general formula:
dans laquelle A et B représentent une chaîne hydrocarbonée, et le nombre total d'atomes de carbone dans les chaînes A et B varie de 2 à 16. in which 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.
Les acides gras particulièrement préférés renferment 18 à 22 atomes de carbone et satisfont à la formule ci-dessus dans laquelle :The particularly preferred fatty acids contain 18 to 22 carbon atoms and satisfy the above formula in which:
A = (CH2)X ; x étant un nombre entier variant de 0 à 6, de préférence égal à 0,3 ou 6, B = (CH2)y > y étant un nombre entier variant de 2 à 11.A = (CH2) X; x being an integer varying from 0 to 6, preferably equal to 0.3 or 6, B = (CH2) y> y being an integer varying from 2 to 11.
A titre d'exemples, on peut citer l'acide linoléique (acide cis,cis-9,12- octadécadiénoïque), l'acide linolélaïdique (acide trans,trans-9,12- octadécadiénoïque), l'acide γ-linolénique (acide 6,9,12-octadécatriénoïque), l'acide linolénique (acide trans,trans,trans-9,12,15-octadécatriénoïque), l'acide α-éléos- téarique (acide cis,trans,trans-9,12,15-octadécatriénoïque), l'acide β-éléostéarique (acide trans,trans,trans-9,12,15-octadécatriénoïque), l'acide cis,cis-11,14-éicosa- diénoïque, l'acide cis,cis,cis-5,8,11-éicosatriénoïque, l'acide cis,cis,cis-8,11, 14-éicosatriénoïque, l'acide cis,cis,cis-11,14,17-éicosatriénoïque, l'acide cis,cis,cis,cis-5,8,11,14,17-éicosapentaénoïque l'acide arachidonique (acide 5,8,11 ,14-éicosatétraénoïque), l'acide cis,cis-13,16-docosadiénoïque, l'acide cis,cis,cis-13,16,19-docosatriénoïque, l'acide cis,cis,cis,cis-7, 10,13,16-docosa- tétraénoïque, l'acide clupanodonique (acide 4,8,12,15,19-docosapentaénoïque) l'acide cis,cis,cis,cis,cis-7,10,13,16,19-docosapentaénoïque, l'acide cis,cis,cis,- cis,cis,cis-4,7,10,13,16,19-docosahexaénoïque et les mélanges de ces composés. A titre d'exemple de tels mélanges, on peut citer les acides gras naturels, en particulier l'acide linoléique et l'acide linolénique. On préfère l'acide linoléique. Sans être lié par une quelconque explication, on pense que les doubles liaisons de l'acide gras réagissent avec l'oxygène de l'air et forment des produits de masse moléculaire plus élevée dotés de propriétés collantes permettant de faire adhérer les filaments entre eux et donc de donner de la cohésion à la mèche.By way of examples, mention may be made of linoleic acid (cis acid, cis-9,12-octadecadienoic acid), linolelaidic acid (trans acid, trans-9,12-octadecadienoic acid), γ-linolenic acid ( 6,9,12-octadecatrienoic acid), linolenic acid (trans, trans, trans-9,12,15-octadecatrienoic acid), α-eleostearic acid (cis, trans, trans-9,12 acid , 15-octadecatrienoic acid), β-eleostearic acid (trans, trans, trans-9,12,15-octadecatrienoic acid), cis acid, cis-11,14-eicosa- dienoic acid, cis acid, cis , cis-5,8,11-eicosatrienoic acid, cis, cis, cis-8,11, 14-eicosatrienoic acid, cis, cis, cis-11,14,17-eicosatrienoic acid, cis, cis, cis, cis-5,8,11,14,17-eicosapentaenoic acid arachidonic acid (5 , 8,11,14-eicosatetraenoic acid), cis acid, cis-13,16-docosadienoic acid, cis, cis, cis-13,16,19-docosatrienoic acid, cis, cis, cis, cis -7,10,13,16-docosa- tetraenoic acid, clupanodonic acid (4,8,12,15,19-docosapentaenoic acid) cis, cis, cis, cis, cis, cis-7,10,13, 16,19-docosapentaenoic acid, cis, cis, cis, - cis, cis, cis-4,7,10,13,16,19-docosahexaenoic and mixtures of these compounds. By way of example of such mixtures, mention may be made of natural 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.
De manière générale, la teneur en acide gras insaturé dans la composition d'ensimage est supérieure ou égale à 5 %, de préférence supérieure ou égale à 8 %. Avantageusement, elle n'excède pas 60 % en poids et de préférence 40 %. De manière particulièrement préférée, la teneur en acide gras est comprise entre 10 et 30 %.In general, the content of unsaturated fatty acid in the sizing composition is greater than or equal to 5%, preferably greater than or equal to 8%. Advantageously, it does not exceed 60% by weight and preferably 40%. In a particularly preferred manner, the fatty acid content is between 10 and 30%.
Selon une réalisation de l'invention, la composition d'ensimage comprend en outre au moins un polymère portant une ou plusieurs fonctions réactives hydroxy, époxy et/ou aminé, et plus particulièrement ayant une masse moléculaire au moins égale à 300 et de préférence inférieure à 3000.According to one embodiment of the invention, 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.
De préférence, les polymères précités renferment également une ou plusieurs doubles liaisons. La présence d' insaturations apporte le caractère élastomérique qui permet à la verranne d'avoir une certaine élasticité et donc d'avoir une meilleure résistance à la rupture en traction.Preferably, the aforementioned polymers also contain one or more double bonds. The presence of unsaturations brings the elastomeric character which allows the verranne to have a certain elasticity and therefore to have a better tensile strength.
De manière avantageuse, on utilise les polymères renfermant une ou plusieurs fonctions réactives hydroxy ou époxy, de préférence en position terminale, par exemple les poly Bd® à terminaisons hydroxyles commercialisé par Atofina, et les polymères renfermant une ou plusieurs fonctions réactives aminé, de préférence en position terminale, par exemple le poly Bd" diamine commercialisé par Atofina. Toutefois, il est à noter que ce dernier polymère donne une légère coloration jaune à la verranne et qu'il est aussi plus délicat à manipuler car plus sensible au gaz carbonique de l'air que les autres polymères. Conformément à l'invention, la teneur en polymère précité peut représenter jusqu'à 40 % en poids de la composition d'ensimage, et de préférence elle varie de 5 à 30 %, et mieux encore de 8 à 25 %.Advantageously, 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. However, it should be noted that 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. In accordance with the invention, 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%.
Selon le mode de réalisation préféré de l'invention, la composition d'ensimage comprend l'association d'acide linoléique et de polybutadiene renfermant des fonctions réactives hydroxy, de préférence en position terminale. Cette association permet d'obtenir des résultats particulièrement intéressants, notamment elle permet d'augmenter sensiblement la ténacité de la verranne, cette augmentation se faisant au cours du stockage des enroulements, sans étape de séchage comme cela est indiqué plus loin.According to the preferred embodiment of the invention, the sizing composition comprises the combination of linoleic acid and polybutadiene containing hydroxy reactive functions, preferably in the terminal position. This association makes it possible to obtain particularly interesting results, in particular it makes it possible to significantly increase the toughness of the verranne, this increase being made during the storage of the windings, without a drying step as indicated below.
En plus des composés précités, la composition d'ensimage peut comprendre un ou plusieurs composants (ci-après désignés par additifs) qui confèrent à l'ensimage des propriétés particulières.In addition to the above-mentioned compounds, the sizing composition may comprise one or more components (hereinafter referred to as additives) which give the sizing particular properties.
La composition selon l'invention peut ainsi comprendre un solvant dont le rôle consiste à adapter la viscosité aux conditions d'application. Ce solvant ne réagit pas avec les constituants de la composition d'ensimage et n'a pas non plus pour fonction de les solubiliser. A titre d'exemple, on peut citer la NMP (1-méthyl- 2-pyrrolidinone) et les diesters méthyliques ou éthyliques d'acide adipique ou d'acide succinique. On préfère les esters précités notamment parce qu'ils ont bonne aptitude à « mouiller » le verre sans présenter de caractère nocif.The 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. By way of example, mention may be made of NMP (1-methyl-2-pyrrolidinone) and the methyl or ethyl diesters of adipic acid or succinic acid. The aforementioned esters are preferred in particular because they have a good ability to "wet" the glass without exhibiting any harmful character.
La quantité de solvant pouvant être utilisée peut représenter jusqu'à 30 % en poids de la composition d'ensimage. Cependant, on préfère limiter la teneur en solvant afin de s'affranchir du risque de variation de la concentration des différents constituants de la composition d'ensimage dû à l'évaporation induite par la température élevée nécessaire pour produire les filaments de verre. La présence de solvant(s) en quantité limitée ne nécessite pas de traitement particulier pour les éliminer.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.
La composition d'ensimage peut aussi comprendre à titre d'additif un agent de couplage permettant d'accrocher l'ensimage sur le verre. L'agent de couplage est généralement choisi parmi les silanes tels que le gamma-glycidoxypropyltriméthoxysilane, le gamma-acryloxypropyltriméthoxy- silane, le gamma-méthacryloxypropyltriméthoxysilane, le poly(oxyéthylène/ oxypropylène) triméthoxysilane, le gamma-aminopropyltriéthoxysilane, le vinyltriméthoxysilane, le phényl-aminopropyltriméthoxysilane, le styrylamino- éthylaminopropyltriméthoxy-silane ou le terbutylcarbamoylpropyl-triméthoxysilane, les siloxanes, les titanates, les zirconates et les mélanges de ces composés. On choisit de préférence les silanes.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.
La proportion d'agent(s) de couplage est généralement comprise entre 0 et 20 % en poids de la composition d'ensimage et de préférence entre 0 et 15 %. De manière générale, la composition d'ensimage ne contient aucun agent de couplage.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.
La composition peut encore comprendre, à titre d'additif, au moins un agent de mise en oeuvre textile jouant essentiellement un rôle de lubrifiant et/ou de tensioactif, et il est dans de nombreux cas nécessaire pour que la composition présente les fonctions d'un ensimage.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.
La proportion d'agent de mise en oeuvre textile est généralement comprise entre 0 et 40 % en poids de la composition, et de préférence 5 et 25 %.The proportion of textile processing agent is generally between 0 and 40% by weight of the composition, and preferably 5 and 25%.
L'agent de mise en oeuvre textile est généralement choisi parmi les esters gras tels que le laurate de décyle, le palmitate d'isopropyle, le palmitate de cétyle, le stéarate d'isopropyle, le stéarate d'isobutyle, le trioctanoate de triméthylolpropane et les mélanges à base d'huiles minérales.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.
A titre d'exemples de tensioactifs, on peut citer l'adipate d'éthylèneglycol, les dérivés d'alkylphénols tels que le nonylphénol éthoxylé et les dérivés de glycols tels que les polyéthyleneglycols ou les polypropyleneglycols de masse moléculaire inférieure à 2000.Mention may be made, as examples of surfactants, 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.
La composition selon l'invention est généralement déposée sur les filaments de verre en une seule étape, par exemple dans les conditions du procédé décrit dans FR-A-2 817 548. Dans ce procédé, on applique la composition d'ensimage sur les filaments immédiatement avant qu'ils n'entrent en contact avec le cylindre, et éventuellement aussi après. L'application peut se faire de différentes manières, la plus utilisée étant la pulvérisation au moyen d'une buse ou plus généralement de deux buses se déplaçant en sens inverse l'une de l'autre suivant la génératrice du cylindre afin d'obtenir une répartition homogène sur l'ensemble de la nappe. De manière générale, il est préférable d'utiliser une composition d'ensimage ayant une viscosité inférieure ou égale à 120 x 10"3 Pa.s (120 cP), et avantageusement comprise entre 50 et 100 x 10"3 Pa.s (50 et 100 cP). Lorsque l'application se fait par pulvérisation, il est recommandé d'avoir une viscosité de l'ordre de 60 à 100 x 10"3 Pa.s (60 à 100 cP). Une viscosité supérieure n'est cependant pas rédhibitoire, la pulvérisation restant possible si l'introduction d'air dans la buse se fait avec un débit plus élevé.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. In this process, 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. In general, it is preferable to use 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). When applying by spraying, it is recommended to have a viscosity of the order of 60 to 100 x 10 "3 Pa.s (60 to 100 cP). higher is however not prohibitive, spraying remaining possible if the introduction of air into the nozzle is done with a higher flow rate.
Les filaments ensimés sont décollés du cylindre et coupés par le racle, puis ils forment une mèche qui est soit collectée sous la forme d'enroulements par l'intermédiaire de supports en rotation, par exemple des roulettes, soit déposée sur un support en translation pour former une nappe ou « mat », soit coupée en segments de longueur appropriée.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.
La verranne obtenue selon l'invention peut ainsi se trouver sous différentes formes après la collecte, par exemple sous la forme de bobines de rubans, de mèches assemblées ou de tresses, de « mats » ou de fils coupés.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.
La verranne revêtue de la composition d'ensimage présente une bonne aptitude au dévidage et elle est facilement manipulable, les filaments restant parfaitement cohésifs. Notamment, les enroulements à bords droits conservent leurs caractéristiques dimensionnelles et ne sont pas déformés. En règle générale, la verranne est revêtue d'une quantité d'ensimage telle qu'elle présente une perte au feu inférieure à 2 %, de préférence inférieure à 1 %, mieux encore inférieure à 0,85 %. De préférence, la perte au feu est supérieure à 0,3 %, et avantageusement supérieure à 0,6 %.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. As a general rule, 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%.
Les filaments de verre constituant la verranne ont un diamètre qui peut varier dans une large mesure, le plus souvent de 5 à 30, de préférence de 6 à 14 //m. Ils peuvent être constitués de n'importe quel verre, le plus connu dans le domaine étant le verre E et le verre C.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 µm. They can be made of any glass, the best known in the field being E glass and C glass.
Les enroulements obtenus sont ensuite disposés sur des palettes pour être expédiés vers les différents lieux où l'on tisse la verranne pour en faire notamment du revêtement mural, par exemple de la toile à peindre. La composition d'ensimage conforme à l'invention ne nécessite aucun séchage préalable des enroulements avant de procéder à l'emballage. Eviter le passage dans une étuve permet à la fois de réduire la consommation d'énergie et de limiter la manipulation des enroulements, et par conséquent de diminuer le coût de production. Pour former la toile à peindre, on dispose les bobines de verranne sur des machines de tissage qui fonctionnent généralement à une cadence élevée, de l'ordre de 450 à 470 coups/minute. Avec la verranne revêtue de l'ensimage selon l'invention, il est possible d'utiliser des métiers à jet d'air qui fonctionnent avec une vitesse élevée (500 à 550 coups/minute voire davantage) et donc d'augmenter la productivité tout en conservant un nombre de « casse » relativement faible. En outre, la verranne présente a un gonflant amélioré qui lui confère un meilleur pouvoir « couvrant » et permet d'obtenir un tissu homogène (sans « trous »).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. To form the canvas to be painted, 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. With 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”. In addition, the verranne present has an improved swelling which gives it better “covering” power and makes it possible to obtain a homogeneous fabric (without “holes”).
La verranne présente généralement une ténacité supérieure à 4 cN/tex, de préférence supérieure à 7,5 cN/tex, permettant ainsi de former des tissus qui résistent bien aux traitements de peinture.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.
Après tissage, la toile est enduite d'un apprêt de « finissage » destiné à lui donner une rigidité suffisante pour permettre la pose sur le support final. Il s'agit généralement d'une solution d'amidon ou d'une émulsion acrylique ou de PVA qui est appliquée sur la toile par imprégnation dans un bain. Il est nécessaire d'avoir une grande compatibilité entre l'ensimage et l'apprêt afin que la toile garde ses propriétés jusqu'à l'utilisation finale. La verranne selon l'invention présente un très bon niveau de compatibilité avec l'apprêt notamment du fait que la composition d'ensimage est apte à contenir une quantité d'agents tensioactifs élevée (jusqu'à 40 % en poids).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. 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).
Les exemples qui suivent permettent d'illustrer l'invention sans toutefois la limiter.The following examples illustrate the invention without, however, limiting it.
Dans ces exemples, on utilise les méthodes suivantes pour la mesure des propriétés physiques et mécaniques de la verranne revêtue de la composition d'ensimage selon l'invention.In these examples, the following methods are used for measuring the physical and mechanical properties of the verranne coated with the sizing composition according to the invention.
- La viscosité est mesurée sur un appareil BROOKFIELD RVT M2, à 20 ± 2°C et elle est exprimée en Pa.s.- The viscosity is measured on a BROOKFIELD RVT M2 device, at 20 ± 2 ° C and it is expressed in Pa.s.
- La tension de surface est mesurée à l'aide d'un tensiomètre à lame M3 commercialisé par PROLABO. Elle est exprimée en mN/m. - La ténacité est évaluée par mesure de la force de rupture en traction dans les conditions suivantes. On utilise un dispositif constitué de deux poulies, d'un dynamomètre et d'un fil de traction relié à un moteur. La poulie supérieure (diamètre : 205 mm) et la poulie inférieure de plus faible diamètre sont distantes de 355 mm , les poulies étant disposées verticalement. La poulie inférieure est reliée à un dynamomètre, lui- même relié au fil de traction mû par le moteur (vitesse : 350 mm/min.). La verranne est enroulée deux fois autour des poulies et le moteur est mis en marche. La mesure de la ténacité correspond à la valeur mesurée sur le dynamomètre lorsqu'il y a rupture de la verranne. La ténacité est exprimée en cN/tex. - La perte au feu est mesurée selon la norme ISO 1887 et elle est exprimée en % en poids. EXEMPLE 1 (comparatif)- 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. EXAMPLE 1 (comparative)
On forme une verranne constituée de 400 filaments de verre C de 11 μm de diamètre en utilisant le dispositif décrit dans FR-A-2 817 548. Sur les filaments, immédiatement après qu'ils arrivent au contact du cylindre, on pulvérise une composition d'ensimage comprenant un mélange d'huiles minérales et de tensioactifs (1) ayant une viscosité égale à 80 x 10"3 Pa.s (80 cP) et une tension de surface égale à 31 ,4 mN/m.A verranne formed from 400 glass filaments C of 11 μm in diameter is formed using the device described in FR-A-2 817 548. On the filaments, immediately after they come into contact with the cylinder, 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.
La nappe de filaments est décollée du cylindre et les filaments coupés sont rassemblés en verranne pour former une bobine.The layer of filaments is detached from the cylinder and the cut filaments are gathered together in verranne to form a coil.
L'évolution de la ténacité de la verranne extraite de la bobine en fonction du temps est donnée dans la figure 1. La ténacité initiale est égale à 2,6 cN/tex et à 3 cN/tex après 10 jours.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.
La perte au feu est égale à 0,5 %. EXEMPLE 2The loss on ignition is equal to 0.5%. EXAMPLE 2
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) :The procedure of example 1 is carried out, the sizing composition comprising (in percentage by weight):
• mélange d'huiles minérales et de tensioactifs (1) 42• mixture of mineral oils and surfactants (1) 42
• acide linoléique 42• linoleic acid 42
• alcool laurique éthoxylé (4 OE) (2) 16 La viscosité de la composition est égale à 70 x 10"3 Pa.s (70 cP). La verranne extraite de la bobine présente une ténacité initiale égale à 2,6 cN/tex et égale à 3,9 cN/tex après 10 jours. EXEMPLE 3• lauric ethoxylated alcohol (4 EO) (2) 16 The viscosity of the composition is equal to 70 x 10 "3 Pa.s (70 cP). The verranne extracted from the reel has an initial toughness equal to 2.6 cN / tex and equal to 3.9 cN / tex after 10 days EXAMPLE 3
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) : • acide linoléique 60The process is carried out under the conditions of Example 1, the sizing composition comprising (in percentage by weight): • linoleic acid 60
• palmitate d'isopropyle 40 La viscosité de la composition est égale à 44 x 10"3 Pa.s (44 cP).• isopropyl palmitate 40 The viscosity of the composition is equal to 44 × 10 −3 Pa.s (44 cP).
La verranne extraite de la bobine présente une ténacité initiale égale à 2,7 cN/tex et égale à 5,4 cN/tex après 10 jours. EXEMPLE 4The 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. EXAMPLE 4
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) : mélange d'huiles minérales et de tensioactifs (1) 15 acide linoléique 20 palmitate d'isopropyle 15 polyuréthane aromatique hexaacrylate (masse moléculaire : 1000)(3) 20 alcool laurique éthoxylé (4 OE) ( ) 15The procedure of example 1 is carried out, 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 La viscosité de la composition est égale à 105 x 10"3 Pa.s (105 cP).NMP 15 The viscosity of the composition is equal to 105 × 10 −3 Pa.s (105 cP).
La verranne extraite de la bobine présente une ténacité initiale égale à 2,7 cN/tex et égale à 8,1 cN/tex après 10 jours. EXEMPLE 5The 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. EXAMPLE 5
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) :The procedure of example 1 is carried out, the sizing composition comprising (in percentage by weight):
• acide linoléique 25• linoleic acid 25
• polybutadiene à terminaisons hydroxyles (4) 25 (masse moléculaire : 2800)• polybutadiene with hydroxyl endings (4) 25 (molecular weight: 2800)
• palmitate d'isopropyle 12,5 • alcool laurique éthoxylé (4 OE) (2) 12,5• isopropyl palmitate 12.5 • ethoxylated lauric alcohol (4 EO) (2) 12.5
• NMP 25• NMP 25
La viscosité de la composition est égale à 120 x 10"3 Pa.s (120 cP) et une tension de surface égale à 34,7 mN/m.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.
La verranne extraite de la bobine présente une ténacité initiale égale à 1 ,6 cN/tex et égale à 7,5 cN/tex après 10 jours, et une perte au feu de 0,72 %.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%.
EXEMPLE 6EXAMPLE 6
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) :The procedure of example 1 is carried out, the sizing composition comprising (in percentage by weight):
• acide linoléique 25 • polybutadiene à terminaisons hydroxyles (5) 20• linoleic acid 25 • polybutadiene with hydroxyl endings (5) 20
(masse moléculaire : 1220)(molecular weight: 1220)
• palmitate d'isopropyle 15• isopropyl palmitate 15
• alcool laurique éthoxylé (4 OE) (2) 15• lauric ethoxylated alcohol (4 EO) (2) 15
• mélange d'esters méthyliques d'acides adipique, succinique et glutarique (6) 25• mixture of methyl esters of acids adipic, succinic and glutaric (6) 25
La viscosité de la composition est égale à 64 x 10"3 Pa.s (64 cP) et une tension de surface égale à 32,8 mN/m.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.
La verranne extraite de la bobine présente une ténacité initiale égale à 2,5 cN/tex et égale à 8,0 cN/tex après 10 jours, et une perte au feu de 0,4 %. EXEMPLE 7The 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%. EXAMPLE 7
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) :The procedure of example 1 is carried out, the sizing composition comprising (in percentage by weight):
• acide linoléique 20 • polybutadiene à terminaisons hydroxyles (5) 20• linoleic acid 20 • polybutadiene with hydroxyl endings (5) 20
(masse moléculaire : 1220)(molecular weight: 1220)
• agent textile à base d'huiles minérales (7) 20• textile agent based on mineral oils (7) 20
• alcool laurique éthoxylé (4 OE) (2) 15• lauric ethoxylated alcohol (4 EO) (2) 15
• mélange d'esters méthyliques d'acides adipique, succinique et glutarique (6) 25• mixture of methyl esters of adipic, succinic and glutaric acids (6) 25
La viscosité de la composition est égale à 68 x 10"3 Pa.s (68 cP) et une tension de surface égale à 32,5 mN/m.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.
L'évolution de la ténacité de la verranne extraite de la bobine en fonction de la durée de stockage, sans séchage préalable, est donnée dans la figure 1. La ténacité initiale est égale à 3,2 cN/tex et à 9,5 cN/tex après 10 jours, et une perte au feu de 0,6 %.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%.
EXEMPLE 8EXAMPLE 8
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) : • acide linoléique 20The procedure of example 1 is carried out, the sizing composition comprising (in percentage by weight): • linoleic acid 20
• polybutadiene à terminaisons hydroxyles (5) 20 (masse moléculaire : 1220)• polybutadiene with hydroxyl endings (5) 20 (molecular weight: 1220)
• 2,2,4-triméthyl-1 ,3-pentanediol monoisobutyrate (8) 20• 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate (8) 20
• alcool laurique éthoxylé (4 OE) (2) 15 • mélange d'esters méthyliques d'acides adipique, succinique et glutarique (6) 25• ethoxylated lauric alcohol (4 EO) (2) 15 • mixture of methyl esters of adipic, succinic and glutaric acids (6) 25
La viscosité de la composition est égale à 68 x 10"3 Pa.s (68 cP) et une tension de surface égale à 32,7 mN/m. La verranne extraite de la bobine présente une ténacité initiale égale à 3,1 cN/tex et égale à 9,2 cN/tex après 10 jours, et une perte au feu de 0,81 %. EXEMPLE 9The 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%. EXAMPLE 9
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) :The procedure of example 1 is carried out, the sizing composition comprising (in percentage by weight):
• acide linoléique 12,5• linoleic acid 12.5
• polybutadiene à terminaisons hydroxyles (5) 20 (masse moléculaire : 1220)• polybutadiene with hydroxyl endings (5) 20 (molecular weight: 1220)
• 2,2,4-triméthyl-1 ,3-pentanediol monoisobutyrate (8) 27,5 • alcool laurique éthoxylé (4 OE) (2) 15• 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate (8) 27.5 • lauric ethoxylated alcohol (4 EO) (2) 15
• mélange d'esters méthyliques d'acides adipique, succinique et glutarique (6) 25• mixture of methyl esters of adipic, succinic and glutaric acids (6) 25
La viscosité de la composition est égale à 62 x 10"3 Pa.s (62 cP) et une tension de surface égale à 32,2 mN/m. La verranne extraite de la bobine présente une ténacité initiale égale à 3,2 cN/tex et égale à 8,5 cN/tex après 10 jours, et une perte au feu de 0,25 %. EXEMPLE 10The 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%.
On procède dans les conditions de l'exemple 1 , la composition d'ensimage comprenant (en pourcentage pondéral) : • acide linoléique 20 polybutadiene à terminaisons hydroxyles (5) 18The procedure of example 1 is carried out, the sizing composition comprising (in percentage by weight): • polyolefin linoleic acid 20 with hydroxyl endings (5) 18
(masse moléculaire : 1220)(molecular weight: 1220)
2,2,4-triméthyl-1 ,3-pentanediol monoisobutyrate (8) 17 alcool laurique éthoxylé (4 OE) (2) 15 • mélange d'esters méthyliques d'acides adipique, succinique et glutarique (6) 25 gamma-méthacryloxypropyl triméthoxysilane (9) 7 gamma-glycidoxypropyl triméthoxysilane (10) 32,2,4-trimethyl-1, 3-pentanediol monoisobutyrate (8) 17 ethoxylated lauric alcohol (4 EO) (2) 15 • mixture of methyl esters of adipic, succinic and glutaric acids (6) 25 gamma-methacryloxypropyl trimethoxysilane (9) 7 gamma-glycidoxypropyl trimethoxysilane (10) 3
La viscosité de la composition est égale à 59 x 10"3 Pa.s (59 cP) et une tension de surface égale à 32,7 mN/m.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.
La verranne extraite de la bobine présente une ténacité initiale égale à 2,7 cN/tex et égale à 10,0 cN/tex après 10 jours, et une perte au feu de 0,65 %.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%.
Les exemples qui précèdent montrent que l'ajout d'acide gras insaturé a pour effet d'améliorer la ténacité de la verranne, cet effet étant attribué à la transformation des liaisons éthyléniques. Si la ténacité initiale mesurée immédiatement après le bobinage de la verranne reste similaire à celle que l'on obtient avec un ensimage de référence (exemple 1), de l'ordre de 3 cN/tex, en revanche elle évolue au cours du temps. Après 10 jours, l'accroissement de la ténacité varie de 50 % (exemple 2) à 200 % (exemple 4) alors qu'il reste faible pour l'ensimage de référence (13 % pour l'exemple 1).The above examples show that the addition of unsaturated fatty acid has the effect of improving the tenacity of the verranne, this effect being attributed to the transformation of ethylenic bonds. If the initial toughness measured immediately after the winding of the verranne remains similar to that obtained with a reference size (example 1), of the order of 3 cN / tex, on the other hand it changes over time. After 10 days, the increase in toughness varies from 50% (example 2) to 200% (example 4) while it remains low for the reference size (13% for example 1).
Les exemples 5 à 10 montrent que l'effet de l'acide gras insaturé est renforcé lorsqu'on ajoute un polymère à terminaisons hydroxyles. Une valeur de la ténacité plus de 3 fois supérieure à celle de l'ensimage de l'exemple 1 est notamment obtenue dans les exemples 7, 8 et 10. En outre, il est intéressant de noter que le polymère contribue à rendre la composition d'ensimage plus stable. Cet effet est visible en particulier pour la composition de l'exemple 4 qui, bien que conférant à la verranne un bon niveau de résistance à la traction, est instable et nécessite d'être mise en œuvre rapidement. Par comparaison, la composition des exemples 7, 8 et 10 associant la même teneur en acide gras insaturé et un polymère reste stable, avec en outre une ténacité accrue.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. In addition, it is interesting to note that 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. By comparison, 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.
L'augmentation de la ténacité obtenue avec la composition d'ensimage conforme à l'invention ne se fait pas au détriment des autres propriétés que sont la tension de surface et la viscosité, ces dernières étant comparables à celles de la composition de référence.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.
Par ailleurs, on a constaté que la composition d'ensimage selon l'invention a pu être pulvérisée sans générer de brouillard et que la verranne obtenue est aisément manipulable : elle se dévide facilement et présente une amélioration de la ténacité pour une perte au feu relativement faible, c'est-à-dire inférieure à 0,85 %.Furthermore, it was found that 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%.
(1 commercialisé sous la référence « Smotilon VS 12 » par la société GOLDSCHMIDT(1 sold under the reference "Smotilon VS 12" by the company GOLDSCHMIDT
(2: commercialisé sous la référence « Simulsol P4 » par la société SEPPIC o; commercialisé sous la référence « Ebecryl 220 » par la société UNION CHIMIQUE BELGE (4: commercialisé sous la référence « PolyBd R 45 HT » par la société ATOFINA (s: commercialisé sous la référence « PolyBd R 20 M »> par la société ATOFINA (e: commercialisé sous la référence « Dibasic Ester » par la société Du Pont (7: commercialisé sous la référence « Torfil LA 4 » par la société LAMBERTI (s: commercialisé sous la référence « Texanol » par la société EASTMAN(2: marketed under the reference "Simulsol P4" by the company SEPPIC o; marketed under the reference "Ebecryl 220" by the company UNION CHIMIQUE BELGE (4: marketed under the reference "PolyBd R 45 HT" by the company ATOFINA (s : marketed under the reference "PolyBd R 20 M"> by the company ATOFINA (e: marketed under the reference "Dibasic Ester" by the company Du Pont (7: marketed under the reference "Torfil LA 4" by the company LAMBERTI (s : marketed under the reference "Texanol" by the company EASTMAN
(9 commercialisé sous la référence « Silquest Si A 174 » par la société WITCO OSI(9 marketed under the reference " Silquest Si A 174" by the company WITCO OSI
(10) commercialisé sous la référence « Silquest Si A 187 » par la société WITCO OSI (10) marketed under the reference “Silquest Si A 187” by the company WITCO OSI

Claims

REVENDICATIONS
1. Fil de verre, en particulier une verranne, revêtu d'une composition d'ensimage constituée d'une solution comprenant au moins un acide gras renfermant au moins deux liaisons éthyléniques.1. Glass strand, in particular a verranne, coated with a sizing composition consisting of a solution comprising at least one fatty acid containing at least two ethylenic bonds.
2. Fil de verre selon la revendication 1 , caractérisé en ce que l'acide gras renferme 10 à 24 atomes de carbone, de préférence 14 à 22.2. Glass strand according to claim 1, characterized in that the fatty acid contains 10 to 24 carbon atoms, preferably 14 to 22.
3. Fil de verre selon l'une des revendications 1 ou 2, caractérisé en ce que l'acide gras est choisi parmi les acides gras à chaîne linéaire. 3. Glass strand according to one of claims 1 or 2, characterized in that the fatty acid is chosen from straight chain fatty acids.
4. Fil de verre selon la revendication 3, caractérisé en ce que l'acide gras répond à la formule4. Glass strand according to claim 3, characterized in that the fatty acid corresponds to the formula
dans laquelle A et B représentent une chaîne hydrocarbonée, et le nombre total d'atomes de carbone dans les chaînes A et B varie de 2 à 16. in which 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.
5. Fil de verre selon la revendication 4, caractérisé en ce que l'acide renferme 18 à 22 atomes de carbone et satisfait à la formule ci-dessus dans laquelle5. Glass strand according to claim 4, characterized in that the acid contains 18 to 22 carbon atoms and satisfies the above formula in which
A = (CH2)χ > x étant un nombre entier variant de 0 à 6, de préférence égal à 0, 3 ou 6, B = (CH2)y ( y étant un nombre entier variant de 2 à 11.A = (CH2) χ > x being an integer varying from 0 to 6, preferably equal to 0, 3 or 6, B = (CH 2 ) y ( y being an integer varying from 2 to 11.
6. Fil de verre selon l'une des revendications 1 à 5, caractérisé en ce que la composition comprend en outre au moins un polymère portant une ou plusieurs fonctions réactives hydroxy, époxy et/ou aminé.6. Glass strand according to one of claims 1 to 5, characterized in that the composition also comprises at least one polymer carrying one or more reactive hydroxy, epoxy and / or amine functions.
7. Fil de verre selon la revendication 6, caractérisé en ce que le polymère a une masse moléculaire au moins égale à 300, et de préférence inférieure à 3000.7. Glass strand according to claim 6, characterized in that the polymer has a molecular mass at least equal to 300, and preferably less than 3000.
8. Fil de verre selon l'une des revendications 6 ou 7, caractérisé en ce que le polymère est un polybutadiene à terminaisons hydroxyles ou aminés.8. Glass strand according to one of claims 6 or 7, characterized in that the polymer is a polybutadiene with hydroxyl or amine endings.
9. Fil de verre selon l'une des revendications 1 à 8, caractérisé en ce que la teneur en acide gras est supérieure ou égale à 5 %, de préférence supérieure ou égale à 8 % en poids de la composition. 9. Glass strand according to one of claims 1 to 8, characterized in that the fatty acid content is greater than or equal to 5%, preferably greater than or equal to 8% by weight of the composition.
10. Fil de verre selon l'une des revendications 6 à 8, caractérisé en ce que la teneur en polymère représente jusqu'à 40 % en poids de la composition, de préférence 5 à 30 %, et avantageusement 8 à 25 %.10. Glass strand according to one of claims 6 to 8, characterized in that the polymer content represents up to 40% by weight of the composition, preferably 5 to 30%, and advantageously 8 to 25%.
11. Fil de verre selon l'une des revendications 1 à 10, caractérisé en ce que la composition d'ensimage comprend en outre au moins un solvant dans une proportion comprise entre 0 et 30 % en poids de la composition.11. Glass strand according to one of claims 1 to 10, characterized in that the sizing composition also comprises at least one solvent in a proportion of between 0 and 30% by weight of the composition.
12. Fil de verre selon l'une des revendications 1 à 11 , caractérisé en ce que la composition comprend en outre au moins un agent de couplage dans une proportion comprise entre 0 et 20 % en poids. 12. Glass strand according to one of claims 1 to 11, characterized in that the composition also comprises at least one coupling agent in a proportion of between 0 and 20% by weight.
13. Fil de verre selon l'une des revendications 1 à 12, caractérisé en ce que la composition comprend au moins un agent de mise en oeuvre textile dans une proportion comprise entre 0 et 40 %.13. Glass strand according to one of claims 1 to 12, characterized in that the composition comprises at least one textile processing agent in a proportion of between 0 and 40%.
14. Composition d'ensimage pour fil de verre, en particulier une verranne, constituée d'une solution contenant moins de 5 % d'eau et comprenant au moins un acide gras renfermant au moins deux liaisons éthyléniques.14. Sizing composition for glass wire, in particular a verranne, consisting of a solution containing less than 5% of water and comprising at least one fatty acid containing at least two ethylenic bonds.
15. Composition selon la revendication 14, caractérisée en ce qu'elle présente une viscosité inférieure ou égale à 120 x 10"3 Pa.s, de préférence comprise entre 50 et 100 x 10"3 Pa.s.15. Composition according to claim 14, characterized in that it has a viscosity less than or equal to 120 x 10 "3 Pa.s, preferably between 50 and 100 x 10 " 3 Pa.s.
16. Composition selon l'une des revendications 14 ou 15, caractérisée en ce que la teneur en acide gras est supérieure ou égale à 5 %, de préférence supérieure ou égale à 8 % en poids de la composition.16. Composition according to one of claims 14 or 15, characterized in that the fatty acid content is greater than or equal to 5%, preferably greater than or equal to 8% by weight of the composition.
17. Composition selon l'une des revendications 14 à 16, caractérisée en ce qu'elle comprend en outre au moins un polymère portant une ou plusieurs fonctions réactives hydroxy, époxy et/ou aminé. 17. Composition according to one of claims 14 to 16, characterized in that it further comprises at least one polymer carrying one or more reactive hydroxy, epoxy and / or amine functions.
18. Composition selon la revendication 17, caractérisée en ce qu'elle comprend un mélange d'acide linoléique et de polybutadiene à terminaisons hydroxyles.18. Composition according to claim 17, characterized in that it comprises a mixture of linoleic acid and polybutadiene with hydroxyl endings.
19. Procédé de fabrication de fils de verre ensimés, notamment de verranne, selon lequel on étire une multiplicité de filets de verre fondu s'écoulant d'une multiplicité d'orifices et on les enroule sous forme de nappe sur un cylindre en rotation situé sensiblement à la verticale de la filière, on décolle la nappe et on coupe les filaments au moyen d'un racle et on rassemble lesdits filaments pour former une verranne, ledit procédé consistant à déposer à la surface des filaments, avant qu'ils n'entrent en contact avec le cylindre, une composition d'ensimage selon l'une des revendications 14 à 18.19. Method for manufacturing sized glass strands, in particular verranne, according to which a multiplicity of molten glass streaks flowing from a multiplicity of orifices is stretched and it is wound in the form of a sheet on a rotating cylinder located substantially vertical to the die, the sheet is peeled off and the filaments are cut by means of a doctor blade and the said filaments are brought together to form a verranne, said process consisting in depositing on the surface of the filaments, before they come into contact with the cylinder, a sizing composition according to one of claims 14 to 18.
20. Procédé selon la revendication 19, caractérisé en ce que le dépôt de la composition d'ensimage est effectué par pulvérisation. 20. Method according to claim 19, characterized in that the deposition of the sizing composition is carried out by spraying.
21. Utilisation du fil selon l'une des revendications 1 à 13 pour former un tissu, notamment une toile à peindre.21. Use of the wire according to one of claims 1 to 13 to form a fabric, in particular a canvas to paint.
22. Tissu en verre, caractérisé en ce qu'il comprend une verranne selon l'une des revendications 1 à 13 et en ce que ladite verranne a une ténacité supérieure à 4 cN/ tex, de préférence supérieure à 7,5 cN/tex. 22. Glass fabric, characterized in that it comprises a verranne according to one of claims 1 to 13 and in that said verranne has a toughness greater than 4 cN / tex, preferably greater than 7.5 cN / tex .
EP03765138A 2002-07-18 2003-07-09 Sizing composition for glass staple fibres, method using said composition and resulting products Withdrawn EP1523456A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0209368 2002-07-18
FR0209368A FR2842516B1 (en) 2002-07-18 2002-07-18 SIZING COMPOSITION FOR VERRANNE, METHOD USING THE SAME AND RESULTING PRODUCTS
PCT/FR2003/002137 WO2004009506A1 (en) 2002-07-18 2003-07-09 Sizing composition for glass staple fibres, method using said composition and resulting products

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AU (1) AU2003263276A1 (en)
BR (1) BR0312670A (en)
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JPWO2016009858A1 (en) * 2014-07-16 2017-04-27 Jsr株式会社 Manufacturing method of molded body
KR101814057B1 (en) * 2015-09-25 2018-01-03 지에스칼텍스 주식회사 Manufacturing method of fiber reinforced resin composite, fiber reinforced resin composite and molded article using the same

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CN1668546A (en) 2005-09-14
CN1308256C (en) 2007-04-04
US20060147706A1 (en) 2006-07-06
BR0312670A (en) 2005-04-26
EA200500226A1 (en) 2005-06-30
WO2004009506A1 (en) 2004-01-29
NO20050799L (en) 2005-02-15
KR20050021496A (en) 2005-03-07
PL372991A1 (en) 2005-08-08
FR2842516A1 (en) 2004-01-23
EA007255B1 (en) 2006-08-25
AU2003263276A1 (en) 2004-02-09
MXPA05000759A (en) 2005-04-19
FR2842516B1 (en) 2004-10-15

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