WO2016001607A1 - Mat of mineral fibres and bituminated products incorporating said mat - Google Patents

Mat of mineral fibres and bituminated products incorporating said mat Download PDF

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Publication number
WO2016001607A1
WO2016001607A1 PCT/FR2015/051851 FR2015051851W WO2016001607A1 WO 2016001607 A1 WO2016001607 A1 WO 2016001607A1 FR 2015051851 W FR2015051851 W FR 2015051851W WO 2016001607 A1 WO2016001607 A1 WO 2016001607A1
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WO
WIPO (PCT)
Prior art keywords
mat
mat according
mineral
organic binder
formaldehyde
Prior art date
Application number
PCT/FR2015/051851
Other languages
French (fr)
Inventor
Alexandre Garcia
Agnès BEAUGENDRE
Original Assignee
Saint-Gobain Adfors
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 Adfors filed Critical Saint-Gobain Adfors
Publication of WO2016001607A1 publication Critical patent/WO2016001607A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/24Coatings containing organic materials
    • C03C25/26Macromolecular compounds or prepolymers
    • C03C25/32Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/34Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04DROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D1/00Roof covering by making use of tiles, slates, shingles, or other small roofing elements
    • E04D1/12Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface
    • E04D1/20Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface of plastics; of asphalt; of fibrous materials
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/24Coatings containing organic materials
    • C03C25/26Macromolecular compounds or prepolymers
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/24Coatings containing organic materials
    • C03C25/26Macromolecular compounds or prepolymers
    • C03C25/28Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209Inorganic fibres
    • D04H1/4218Glass fibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04DROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D5/00Roof covering by making use of flexible material, e.g. supplied in roll form
    • E04D5/02Roof covering by making use of flexible material, e.g. supplied in roll form of materials impregnated with sealing substances, e.g. roofing felt

Definitions

  • the present invention relates to the field of mineral fiber-based mats bound by an organic binder, in particular for the production of bituminous products for roofing.
  • the invention relates more particularly to asphalted membranes composed of said mat of mineral fibers provided with a coating based on bitumen.
  • bituminous membranes are intended in particular for the manufacture of shingles ("shingles" in English) by the application of an additional surface layer consisting of inorganic granules.
  • the mineral fiber mats may be manufactured by known methods operating dry or wet.
  • molten mineral matter contained in an oven is fed to a set of dies from which filaments flow by gravity and are drawn by a gaseous fluid.
  • the mineral filaments are harvested on a conveyor where they intermingle forming a mat.
  • an organic binder is applied using a suitable device, most often operating by curtain deposition, and the excess organic binder is removed by suction at the opposite side. .
  • the mat then enters a device containing hot air whose temperature, of the order of 200 to 250 ° C, is adapted to remove the water and crosslink the organic binder in a very short time, of the order from ten seconds to 1 minute, then the mat of mineral fibers is collected in the form of a coil.
  • the mat is obtained from an aqueous dispersion of cut mineral fibers which is deposited by means of a forming head on a conveyor provided with perforations and the water is extracted through the conveyor through to a suction box. Fibers cut mineral remaining on the conveyor form a mat that is treated under the same conditions as those described for the dry process.
  • the function of the organic binder is to bind the mineral fibers together and to give the mat which contains them mechanical properties suited to the desired use, in particular a rigidity sufficient to be easily handled without any risk, especially because it can be torn.
  • the organic binder to be applied to the mineral fibers is generally in the form of an aqueous solution containing at least one thermosetting resin and additives such as a crosslinking catalyst of the resin, a silane (coupling agent), a water repellent
  • thermosetting resins are urea-formaldehyde and melamine-formaldehyde resins, which have the advantage of being compatible with the bitumen thus making it possible to confer good mechanical properties on the final bituminous product, and in addition they are inexpensive.
  • bitumen comprising mineral stabilizers and optionally additives in the form of polymers is then deposited.
  • Deposition of the bitumen can be done by spraying on one side or on both sides, or by immersion in a bath of molten bitumen.
  • Mineral granules are then applied to the softened bitumen and embedded in it to obtain a shingle.
  • the mineral fiber mat has good tensile strength in the dry state, but also in the presence of hot bitumen.
  • the mat advantageously exhibits tensile strength under wet aging conditions, as well as good tear strength.
  • the object of the present invention is to improve the adhesion of hot bitumen to the mineral fiber mat, thus making it possible to improve the mechanical properties of the bitumen product, in particular its resistance to tensile failure.
  • an organic binder which comprises at least one melamine-formaldehyde or phenol-formaldehyde resin and at least one adhesion promoter selected from the group consisting of (meth) acrylic acid homopolymers and acid copolymers (meth) acrylic and at least one ethylenically unsaturated C 2 -C 8 monomer other than styrene.
  • the melamine-formaldehyde and phenol-formaldehyde resins are chosen from known resins having the properties which are suitable for application to the mat based on mineral fibers.
  • the resins according to the invention can be obtained conventionally by condensation of melamine or phenol and formaldehyde in the presence of a base, for example sodium hydroxide, in a formaldehyde / melamine or formaldehyde / higher phenol molar ratio. at 1, preferably less than 3.0.
  • the homopolymers according to the invention are preferably homopolymers of acrylic acid.
  • copolymers according to the invention are preferably copolymers of (meth) acrylic acid and ethylene, propene and / or butene, advantageously copolymers of acrylic acid and ethylene.
  • the adhesion promoter is used in an amount ranging from 0.5 to 30 parts by weight per 100 parts by weight of melamine-formaldehyde or phenol-formaldehyde resin and optional additives, preferably 5 to 15 parts.
  • the organic binder may further comprise conventional additives, for example, an extender such as starch, a plasticizer such as polyvinyl alcohol and polyvinyl acetate, an anti-blocking agent. such as colloidal silica, antifoaming agent, a biocide and pigments.
  • an extender such as starch
  • a plasticizer such as polyvinyl alcohol and polyvinyl acetate
  • an anti-blocking agent such as colloidal silica, antifoaming agent, a biocide and pigments.
  • the basic organic binder (excluding adhesion promoter) preferably comprises the constituents below in the following proportions (in mass%):
  • plasticizers 0 to 30% of plasticizers.
  • the organic binder is in the form of an aqueous solution, an emulsion or an aqueous dispersion.
  • the organic binder is applied to fiber mats made of glass or rock, especially basalt, and preferably glass.
  • the organic binder is deposited on the mat of mineral fibers (formed by the dry route or the wet route), then the mat is treated at a temperature permitting the crosslinking of the organic binder which then becomes infusible.
  • the crosslinking of the organic binder according to the invention is carried out at a temperature which generally varies from 180 to 250 ° C., preferably from 200 to 220 ° C., and for a very short time, of the order of a few seconds to 1 minute. .
  • the adhesion promoter is preferably incorporated into the organic binder applied to the mineral fiber mat. However, application of the adhesion promoter separately from that of the organic base binder can not be ruled out on the mineral fiber mat.
  • the mineral fibers are both filaments and yarns composed of a multitude of filaments bonded together, in particular by a sizing, and assemblies of such threads.
  • the mineral fiber mat is composed of discontinuous mineral filaments of length up to 150 mm, preferably ranging from 20 to 100 mm and advantageously from 50 to 70 mm, and having a diameter that can vary. to a large extent, for example from 5 to 30 ⁇ .
  • the mineral fiber mat is composed of mineral threads.
  • the mineral threads may be yarns composed of a multitude of mineral filaments (or base yarns) or assemblies of these basic yarns in rovings ("rovings").
  • the aforementioned son may be son without torsion or twisted son (or son textile), preferably without torsion.
  • the mineral threads, especially glass, are generally cut to a length of up to 100 mm, preferably ranging from 6 to 30 mm, advantageously from 8 to 20 mm and more preferably from 10 to 18 mm.
  • the diameter of the glass filaments constituting the son can vary to a large extent, for example 5 to 30 ⁇ . In the same way, variations can occur in the linear density of the yarn which can range from 34 to 1500 tex.
  • the glass entering the constitution of the filaments can be of any type, for example C, E, R, AR (alkali-resistant). C-glass and E-glass are preferred.
  • the mat may, if necessary, be reinforced by continuous fibers which are generally deposited on the mat conveying device in the direction of advancement of the mat and distributed over all or part of the width of the mat. These fibers are generally deposited in the thickness of the mat of fibers, in particular mineral, before the application of the organic binder.
  • Reinforcing fibers are usually made of glass.
  • the mineral fiber mat generally has a basis weight which varies from 10 to 1100 g / m 2 , preferably from 30 to 350 g / m 2 , advantageously from 35 to 80 g / m 2 .
  • the organic binder generally represents 5 to 40% by weight of the fiber mat, in particular mineral, preferably 10 to 30%.
  • bitumen composition which may contain additives such as oils and petroleum residues, polymers, especially styrene-butadiene-styrene, mineral stabilizing agents, antistatic agents and agents. anti-UV, especially an atactic polypropylene.
  • additives such as oils and petroleum residues, polymers, especially styrene-butadiene-styrene, mineral stabilizing agents, antistatic agents and agents. anti-UV, especially an atactic polypropylene.
  • additives can represent up to 15% of the bitumen mass.
  • bitumen The purpose of the bitumen is to render the mineral fiber mat watertight while giving great flexibility to the final material. It also plays the role of support for mineral granules in a shingle.
  • the bitumen can be oxidized.
  • the amount of bitumen applied to the mineral fiber mat can vary to a large extent, until a bitumen product having a basis weight of from 1000 to 10,000 g / m 2, and preferably from 1500 to 7500 g / m, is obtained. 2 .
  • bitumen composition may be carried out by any means known to those skilled in the art, for example by softening, spraying or dipping in one or more passes.
  • Another aspect of the invention is the mineral fiber mat coated with bitumen. It can be used in particular as a waterproofing membrane for roofing, including rooftop terrace, and for the manufacture of shingle by applying an additional layer of mineral granules on at least one of its faces.
  • the tensile tensile strength is measured on the mat of glass fibers and on the matte mat under the conditions of the NF EN ISO 13934-1 standard. The measurement is performed on 10 samples 25 cm long and 5 cm wide. For example 2, the measurement is made in the transverse direction, the reinforcing son being located in the length of the sample.
  • a fiberglass mat is made wet.
  • cut glass yarn (diameter of the filaments: 13 ⁇ , length: 18 mm) are dispersed in 25 liters of water containing 3.75 g of a surfactant (1) , 62.5 g of a thickener ' 2 ' and 0.87 g of an antifoaming agent (3) .
  • the dispersion is poured into a container whose bottom is provided with a sieve and the water is removed by gravity through the sieve.
  • the glass filaments uniformly distributed on the sieve are recovered in the form of a mat.
  • the mat is immersed in an aqueous organic binder bath of the following composition (in% solids):
  • the organic binder contains 7.5% solids.
  • the mat After immersion, the mat is dried in an oven at 210 ° C for 1 minute.
  • step b) manufacture of asphalt mat
  • the mat obtained in step a) is immersed in a bath of molten bitumen (180 ° C.) and then cooled to room temperature.
  • bituminous mat is prepared under the same conditions from a mat of glass fibers and an organic binder containing no adhesion promoter.
  • a mat consisting of glass filaments C reinforced with glass yarns (68 Tex) is formed by the dry route.
  • the reinforcing threads are deposited on a conveyor in the machine direction (warp) with a spacing of 16 mm, after the deposition of a portion of the filaments on the conveyor, so that the reinforcement threads are embedded in the web. thickness of the mat, then a binder is applied by curtain on the mat.
  • the conveyor then enters a 50 m long oven heated to a temperature ranging from 240 ° C (inlet) to 200 ° C (outlet) at a speed of 125 m / min.
  • the mat is wound in the form of a winding.
  • the organic binder has the composition of Example 1 modified in that the adhesion promoter is an ethylene-acrylic acid copolymer ( 11) .
  • the fiberglass mat obtained in step a) is immersed in a bath of molten bitumen (200 ° C.) by the dip coating method. The mat is then cooled to room temperature and coiled under the shape of a coil.
  • an organic binder containing no ethylene-acrylic acid copolymer is used to produce a mat of glass fibers and a matt mat under the conditions described above.

Abstract

The present invention relates to a mat made from mineral fibres, in particular glass, bound by an organic binder which comprises at least one melamine formaldehyde resin or phenol formaldehyde resin and at least one adhesion promoter selected from the group consisting of the homopolymers of methacrylic acid and the copolymers of methacrylic acid and of at least one ethylenic monomer unsaturated in C2-C8 excluding styrene. The invention also relates to bituminated products incorporating said mat made from mineral fibres, in particular a bituminated membrane and a shingle.

Description

MAT DE FIBRES MINERALES ET PRODUITS BITUMES INCORPORANT  MATERIAL OF MINERAL FIBERS AND BITUMEN PRODUCTS INCORPORATING
LEDIT MAT  LEDIT MAT
La présente invention se rapporte au domaine des mats à base de fibres minérales liées par un liant organique en particulier destinés à la réalisation de produits bitumés pour toiture. The present invention relates to the field of mineral fiber-based mats bound by an organic binder, in particular for the production of bituminous products for roofing.
L'invention concerne plus particulièrement des membranes bitumées composées dudit mat de fibres minérales pourvu d'un revêtement à base de bitume. De telles membranes bitumées sont destinées notamment à la fabrication de bardeaux (« shingles » en anglais) par l'application d'une couche de surface supplémentaire constituée de granules minéraux.  The invention relates more particularly to asphalted membranes composed of said mat of mineral fibers provided with a coating based on bitumen. Such bituminous membranes are intended in particular for the manufacture of shingles ("shingles" in English) by the application of an additional surface layer consisting of inorganic granules.
Les mats de fibres minérales (aussi appelés « intissés » ou « voiles ») peuvent être fabriqués selon les procédés connus opérant par voie sèche ou par voie humide.  The mineral fiber mats (also referred to as "non-woven" or "sails") may be manufactured by known methods operating dry or wet.
Dans le procédé par voie sèche, de la matière minérale fondue contenue dans un four est acheminée vers un ensemble de filières à partir desquelles des filaments s'écoulent par gravité et sont étirés par un fluide gazeux. Les filaments minéraux sont récoltés sur un convoyeur où ils s'entremêlent en formant un mat.  In the dry process, molten mineral matter contained in an oven is fed to a set of dies from which filaments flow by gravity and are drawn by a gaseous fluid. The mineral filaments are harvested on a conveyor where they intermingle forming a mat.
Sur la face supérieure du mat ainsi formé, on applique un liant organique à l'aide d'un dispositif adapté, le plus souvent opérant par dépôt par rideau, et on élimine l'excès de liant organique par aspiration au niveau de la face opposée. Le mat entre ensuite dans un dispositif contenant de l'air chaud dont la température, de l'ordre de 200 à 250°C, est adaptée pour éliminer l'eau et réticuler le liant organique en un temps très court, de l'ordre d'une dizaine de secondes à 1 minute, puis le mat de fibres minérales est collecté sous la forme d'un enroulement.  On the upper face of the mat thus formed, an organic binder is applied using a suitable device, most often operating by curtain deposition, and the excess organic binder is removed by suction at the opposite side. . The mat then enters a device containing hot air whose temperature, of the order of 200 to 250 ° C, is adapted to remove the water and crosslink the organic binder in a very short time, of the order from ten seconds to 1 minute, then the mat of mineral fibers is collected in the form of a coil.
Dans le procédé par voie humide, le mat est obtenu à partir d'une dispersion aqueuse de fibres minérales coupées qui est déposée au moyen d'une tête de formage sur un convoyeur muni de perforations et l'eau est extraite à travers le convoyeur grâce à un caisson d'aspiration. Les fibres minérales coupées restant sur le convoyeur forment un mat qui est traité dans les mêmes conditions que celles décrites pour le procédé par voie sèche. In the wet process, the mat is obtained from an aqueous dispersion of cut mineral fibers which is deposited by means of a forming head on a conveyor provided with perforations and the water is extracted through the conveyor through to a suction box. Fibers cut mineral remaining on the conveyor form a mat that is treated under the same conditions as those described for the dry process.
Dans les procédés précités, le liant organique a pour fonction de lier les fibres minérales entre-elles et de conférer au mat qui les contient des propriétés mécaniques adaptées à l'usage désiré, notamment une rigidité suffisante pour pouvoir être manipulé facilement sans risque notamment qu'il puisse être déchiré.  In the abovementioned processes, the function of the organic binder is to bind the mineral fibers together and to give the mat which contains them mechanical properties suited to the desired use, in particular a rigidity sufficient to be easily handled without any risk, especially because it can be torn.
Le liant organique à appliquer sur les fibres minérales se présente généralement sous la forme d'une solution aqueuse renfermant au moins une résine thermodurcissable et des additifs tels qu'un catalyseur de réticulation de la résine, un silane (agent de couplage), un hydrofugeant, ... Les résines thermodurcissables les plus couramment utilisées sont des résines urée- formaldéhyde et mélamine-formaldéhyde qui présentent l'avantage d'être compatibles avec le bitume permettant ainsi de conférer de bonnes propriétés mécaniques au produit bitumé final, et de surcroit sont peu coûteuses.  The organic binder to be applied to the mineral fibers is generally in the form of an aqueous solution containing at least one thermosetting resin and additives such as a crosslinking catalyst of the resin, a silane (coupling agent), a water repellent The most commonly used thermosetting resins are urea-formaldehyde and melamine-formaldehyde resins, which have the advantage of being compatible with the bitumen thus making it possible to confer good mechanical properties on the final bituminous product, and in addition they are inexpensive.
Sur le mat de fibres de verre ainsi obtenu, on dépose ensuite une couche de bitume comprenant des stabilisants minéraux et éventuellement des additifs sous forme de polymères. Le dépôt du bitume peut se faire par pulvérisation sur une seule face ou sur les deux faces, ou par immersion dans un bain de bitume fondu. Des granules minéraux sont ensuite appliqués sur le bitume ramolli et incrustés dans ce dernier afin d'obtenir un bardeau.  On the fiberglass mat thus obtained, a layer of bitumen comprising mineral stabilizers and optionally additives in the form of polymers is then deposited. Deposition of the bitumen can be done by spraying on one side or on both sides, or by immersion in a bath of molten bitumen. Mineral granules are then applied to the softened bitumen and embedded in it to obtain a shingle.
Il est important que le mat à base de fibres minérales ait une bonne résistance à la traction à l'état sec, mais aussi en présence de bitume chaud. Le mat présente avantageusement une résistance à la traction dans des conditions de vieillissement en milieu humide, ainsi qu'une bonne résistance à la déchirure.  It is important that the mineral fiber mat has good tensile strength in the dry state, but also in the presence of hot bitumen. The mat advantageously exhibits tensile strength under wet aging conditions, as well as good tear strength.
La présente invention a pour but d'améliorer l'adhésion du bitume chaud au mat de fibres minérales, permettant ainsi d'améliorer les propriétés mécaniques du produit bitumé, notamment sa résistance à la rupture en traction.  The object of the present invention is to improve the adhesion of hot bitumen to the mineral fiber mat, thus making it possible to improve the mechanical properties of the bitumen product, in particular its resistance to tensile failure.
Ce but est atteint grâce à l'utilisation d'un liant organique qui comprend au moins une résine mélamine-formaldéhyde ou phénol-formaldéhyde et au moins un promoteur d'adhésion choisi dans le groupe constitué par les homopolymères d'acide (méth)acrylique et les copolymères d'acide (méth)acrylique et d'au moins un monomère éthyléniquement insaturé en C2-C8 différent du styrène. This object is achieved through the use of an organic binder which comprises at least one melamine-formaldehyde or phenol-formaldehyde resin and at least one adhesion promoter selected from the group consisting of (meth) acrylic acid homopolymers and acid copolymers (meth) acrylic and at least one ethylenically unsaturated C 2 -C 8 monomer other than styrene.
Les résines mélamine-formaldéhyde et phénol-formaldéhyde sont choisies parmi les résines connues présentant les propriétés qui conviennent pour l'application sur le mat à base de fibres minérales. Les résines conformes à l'invention peuvent être obtenues de manière classique par condensation de mélamine ou de phénol et de formaldéhyde en présence d'une base, par exemple l'hydroxyde de sodium, dans un rapport molaire formaldéhyde/mélamine ou formaldéhyde/phénol supérieur à 1 , de préférence inférieur à 3,0.  The melamine-formaldehyde and phenol-formaldehyde resins are chosen from known resins having the properties which are suitable for application to the mat based on mineral fibers. The resins according to the invention can be obtained conventionally by condensation of melamine or phenol and formaldehyde in the presence of a base, for example sodium hydroxide, in a formaldehyde / melamine or formaldehyde / higher phenol molar ratio. at 1, preferably less than 3.0.
Les homopolymères conformes à l'invention sont de préférence des homopolymères d'acide acrylique.  The homopolymers according to the invention are preferably homopolymers of acrylic acid.
Les copolymères conformes à l'invention sont de préférence des copolymères d'acide (méth)acrylique et d'éthylène, de propène et/ou de butène, avantageusement des copolymères d'acide acrylique et d'éthylène.  The copolymers according to the invention are preferably copolymers of (meth) acrylic acid and ethylene, propene and / or butene, advantageously copolymers of acrylic acid and ethylene.
Le promoteur d'adhésion est mis en œuvre en une quantité variant de 0,5 à 30 parts en masse pour 100 parts en masse de résine mélamine- formaldéhyde ou phénol-formaldéhyde et d'éventuels additifs, de préférence 5 à 15 parts.  The adhesion promoter is used in an amount ranging from 0.5 to 30 parts by weight per 100 parts by weight of melamine-formaldehyde or phenol-formaldehyde resin and optional additives, preferably 5 to 15 parts.
Comme indiqué ci-dessus, le liant organique peut comprendre en outre des additifs conventionnels, par exemple un extendeur tel que l'amidon, un agent plastifiant tel que le poly(alcool vinylique) et le poly(acétate de vinyle), un agent anti-feu tel que de la silice colloïdale, un agent anti-mousse, un biocide et des pigments.  As indicated above, the organic binder may further comprise conventional additives, for example, an extender such as starch, a plasticizer such as polyvinyl alcohol and polyvinyl acetate, an anti-blocking agent. such as colloidal silica, antifoaming agent, a biocide and pigments.
Le liant organique de base (hors promoteur d'adhésion) comprend préférentiellement les constituants ci-après dans les proportions suivantes (en % massique) :  The basic organic binder (excluding adhesion promoter) preferably comprises the constituents below in the following proportions (in mass%):
- 5 à 100 % de résine mélamine-formaldéhyde ou phénol- formaldéhyde,  5 to 100% of melamine-formaldehyde or phenol-formaldehyde resin,
- 0 à 95 % d'amidon, et  0 to 95% of starch, and
- 0 à 30 % d'agents plastifiants.  0 to 30% of plasticizers.
Le liant organique se présente sous la forme d'une solution, d'une émulsion ou d'une dispersion aqueuse. Le liant organique est appliqué sur des mats de fibres constituées de verre ou d'une roche, en particulier le basalte, et de préférence de verre. The organic binder is in the form of an aqueous solution, an emulsion or an aqueous dispersion. The organic binder is applied to fiber mats made of glass or rock, especially basalt, and preferably glass.
De manière classique, on dépose le liant organique sur le mat de fibres minérales (formé par la voie sèche ou la voie humide), puis le mat est traité à une température permettant la réticulation du liant organique qui devient alors infusible. La réticulation du liant organique selon l'invention se fait à une température qui varie généralement de 180 à 250 °C, de préférence de 200 à 220 °C, et pendant une durée très courte, de l'ordre de quelques secondes à 1 minute.  Conventionally, the organic binder is deposited on the mat of mineral fibers (formed by the dry route or the wet route), then the mat is treated at a temperature permitting the crosslinking of the organic binder which then becomes infusible. The crosslinking of the organic binder according to the invention is carried out at a temperature which generally varies from 180 to 250 ° C., preferably from 200 to 220 ° C., and for a very short time, of the order of a few seconds to 1 minute. .
Le promoteur d'adhésion est préférentiellement incorporé dans le liant organique appliqué sur le mat de fibres minérales. Cependant, on ne saurait exclure l'application du promoteur d'adhésion séparément de celle du liant organique de base sur le mat de fibres minérales.  The adhesion promoter is preferably incorporated into the organic binder applied to the mineral fiber mat. However, application of the adhesion promoter separately from that of the organic base binder can not be ruled out on the mineral fiber mat.
Les fibres minérales sont aussi bien des filaments que des fils composés d'une multitude de filaments liés ensemble, notamment par un ensimage, et des assemblages de tels fils.  The mineral fibers are both filaments and yarns composed of a multitude of filaments bonded together, in particular by a sizing, and assemblies of such threads.
Ainsi, selon un premier mode de réalisation, le mat de fibres minérales est composé de filaments minéraux discontinus de longueur pouvant atteindre 150 mm, de préférence variant de 20 et 100 mm et avantageusement de 50 à 70 mm, et ayant un diamètre qui peut varier dans une large mesure, par exemple de 5 à 30 μιτι.  Thus, according to a first embodiment, the mineral fiber mat is composed of discontinuous mineral filaments of length up to 150 mm, preferably ranging from 20 to 100 mm and advantageously from 50 to 70 mm, and having a diameter that can vary. to a large extent, for example from 5 to 30 μιτι.
Selon un deuxième mode de réalisation, le mat de fibres minérales est composé de fils minéraux.  According to a second embodiment, the mineral fiber mat is composed of mineral threads.
Les fils minéraux peuvent être des fils composés d'une multitude de filaments minéraux (ou fils de base) ou des assemblages de ces fils de base en stratifils (« rovings » en anglais).  The mineral threads may be yarns composed of a multitude of mineral filaments (or base yarns) or assemblies of these basic yarns in rovings ("rovings").
Les fils précités peuvent être des fils sans torsion ou des fils retordus (ou fils textiles), de préférence sans torsion.  The aforementioned son may be son without torsion or twisted son (or son textile), preferably without torsion.
Les fils minéraux, notamment de verre, sont généralement coupés à une longueur pouvant aller jusqu'à 100 mm, de préférence variant de 6 à 30 mm, avantageusement de 8 à 20 mm et mieux encore de 10 à 18 mm.  The mineral threads, especially glass, are generally cut to a length of up to 100 mm, preferably ranging from 6 to 30 mm, advantageously from 8 to 20 mm and more preferably from 10 to 18 mm.
Le diamètre des filaments de verre constituant les fils peut varier dans une large mesure, par exemple 5 à 30 μιτι. De la même manière, de larges variations peuvent survenir dans la masse linéique du fil qui peut aller de 34 à 1500 tex. The diameter of the glass filaments constituting the son can vary to a large extent, for example 5 to 30 μιτι. In the same way, variations can occur in the linear density of the yarn which can range from 34 to 1500 tex.
Le verre entrant dans la constitution des filaments peut être de tout type, par exemple C, E, R, AR (alcali-résistant). On préfère le verre C et le verre E.  The glass entering the constitution of the filaments can be of any type, for example C, E, R, AR (alkali-resistant). C-glass and E-glass are preferred.
Le mat peut, le cas échéant, être renforcé par des fibres continues qui sont généralement déposées sur le dispositif de convoyage du mat dans le sens d'avancement du mat et réparties sur tout ou partie de la largeur du mat. Ces fibres sont généralement déposées dans l'épaisseur du mat de fibres, notamment minérales, avant l'application du liant organique.  The mat may, if necessary, be reinforced by continuous fibers which are generally deposited on the mat conveying device in the direction of advancement of the mat and distributed over all or part of the width of the mat. These fibers are generally deposited in the thickness of the mat of fibers, in particular mineral, before the application of the organic binder.
Les fibres de renforcement sont généralement en verre.  Reinforcing fibers are usually made of glass.
Le mat de fibres minérales présente généralement une masse surfacique qui varie de 10 à 1 100 g/m2, de préférence de 30 à 350 g/m2, avantageusement de 35 à 80 g/m2. The mineral fiber mat generally has a basis weight which varies from 10 to 1100 g / m 2 , preferably from 30 to 350 g / m 2 , advantageously from 35 to 80 g / m 2 .
Le liant organique représente généralement 5 à 40 % en masse du mat de fibres, notamment minérales, de préférence 10 à 30 %.  The organic binder generally represents 5 to 40% by weight of the fiber mat, in particular mineral, preferably 10 to 30%.
Le mat de fibres minérales précité est ensuite traité avec une composition de bitume qui peut contenir des additifs tels que des huiles et résidus de pétrole, des polymères, notamment styrène-butadiène-styrène, des agents de stabilisation minéraux, des agents antistatiques et des agents anti- UV, notamment un polypropylène atactique. Ces additifs peuvent représenter jusqu'à 15 % de la masse du bitume.  The aforementioned mineral fiber mat is then treated with a bitumen composition which may contain additives such as oils and petroleum residues, polymers, especially styrene-butadiene-styrene, mineral stabilizing agents, antistatic agents and agents. anti-UV, especially an atactic polypropylene. These additives can represent up to 15% of the bitumen mass.
Le bitume a pour fonction de rendre le mat de fibres minérales étanche à l'eau tout en conférant une grande flexibilité au matériau final. Il joue également le rôle de support pour les granules minéraux dans un bardeau. Le bitume peut être oxydé.  The purpose of the bitumen is to render the mineral fiber mat watertight while giving great flexibility to the final material. It also plays the role of support for mineral granules in a shingle. The bitumen can be oxidized.
La quantité de bitume appliquée sur le mat de fibres minérales peut varier dans une large mesure, jusqu'à obtenir un produit bitumé présentant une masse surfacique qui varie de 1000 à 10 000 g/m, et de préférence de 1500 à 7500 g/m2. The amount of bitumen applied to the mineral fiber mat can vary to a large extent, until a bitumen product having a basis weight of from 1000 to 10,000 g / m 2, and preferably from 1500 to 7500 g / m, is obtained. 2 .
L'application de la composition de bitume peut être effectuée par tout moyen connu de l'homme du métier, par exemple par enduction à l'état ramolli, par pulvérisation ou au trempé, en une ou plusieurs passes. Le mat à base de fibres minérales revêtu de bitume constitue un autre objet de l'invention. Il peut être utilisé notamment en tant que membrane d'étanchéité pour toiture, notamment de toit-terrasse, et pour la fabrication de bardeau par application d'une couche supplémentaire de granules minéraux sur au moins une de ses faces. The application of the bitumen composition may be carried out by any means known to those skilled in the art, for example by softening, spraying or dipping in one or more passes. Another aspect of the invention is the mineral fiber mat coated with bitumen. It can be used in particular as a waterproofing membrane for roofing, including rooftop terrace, and for the manufacture of shingle by applying an additional layer of mineral granules on at least one of its faces.
Les exemples qui suivent permettent d'illustrer l'invention sans toutefois la limiter.  The following examples illustrate the invention without limiting it.
Dans ces exemples, on mesure la résistance à la rupture en traction sur le mat de fibres de verre et sur le mat bitumé dans les conditions de la norme NF EN ISO 13934-1 . La mesure est effectuée sur 10 échantillons de 25 cm de long et 5 cm de large. Pour l'exemple 2, la mesure est effectuée dans le sens transverse, les fils de renforcement étant situés dans la longueur de l'échantillon.  In these examples, the tensile tensile strength is measured on the mat of glass fibers and on the matte mat under the conditions of the NF EN ISO 13934-1 standard. The measurement is performed on 10 samples 25 cm long and 5 cm wide. For example 2, the measurement is made in the transverse direction, the reinforcing son being located in the length of the sample.
EXEMPLE 1  EXAMPLE 1
a) fabrication du mat de fibres minérales  a) manufacture of the mineral fiber mat
On fabrique un mat de fibres de verre par la voie humide.  A fiberglass mat is made wet.
5,08 g de fils de verre coupés (diamètre des filaments : 13 μιτι; longueur : 18 mm) sont dispersés dans 25 litres d'eau contenant 3,75 g d'un tensioactif(1 ), 62,5 g d'un épaississant'2' et 0,87 g d'un agent antimousse(3). 5.08 g of cut glass yarn (diameter of the filaments: 13 μιτι, length: 18 mm) are dispersed in 25 liters of water containing 3.75 g of a surfactant (1) , 62.5 g of a thickener ' 2 ' and 0.87 g of an antifoaming agent (3) .
La dispersion est versée dans un récipient dont le fond est pourvu d'un tamis et l'eau est éliminée par gravité à travers le tamis. Les filaments de verre uniformément répartis sur le tamis sont récupérés sous la forme d'un mat.  The dispersion is poured into a container whose bottom is provided with a sieve and the water is removed by gravity through the sieve. The glass filaments uniformly distributed on the sieve are recovered in the form of a mat.
Le mat est immergé dans un bain de liant organique aqueux de composition suivante (en % de matières solides) :  The mat is immersed in an aqueous organic binder bath of the following composition (in% solids):
- Résine mélamine-formaldéhyde1 ' 24,5 - Melamine-formaldehyde resin 1 '24.5
- Homopolymère d'acide acrylique(5) 10,0 - Homopolymer of acrylic acid (5) 10.0
- Amidon(6) 68,6 - Starch (6) 68.6
- Poly(alcool polyvinylique)(7) 2,0 - Poly (polyvinyl alcohol) (7) 2.0
- Poly(acétate de vinyle)(8) 4,9 - Polyvinyl acetate (8) 4.9
Le liant organique contient 7,5 % de matières solides.  The organic binder contains 7.5% solids.
Après immersion, le mat est séché dans une étuve à 210°C pendant 1 minute.  After immersion, the mat is dried in an oven at 210 ° C for 1 minute.
b) fabrication du mat bitumé Le mat obtenu à l'étape a) est immergé dans un bain de bitume fondu (180°C), puis refroidi à la température ambiante. b) manufacture of asphalt mat The mat obtained in step a) is immersed in a bath of molten bitumen (180 ° C.) and then cooled to room temperature.
A titre de comparaison (exemple comparatif 1 ), un mat bitumé est préparé dans les mêmes conditions à partir d'un mat de fibres de verre et d'un liant organique ne contenant pas de promoteur d'adhésion.  For comparison (comparative example 1), a bituminous mat is prepared under the same conditions from a mat of glass fibers and an organic binder containing no adhesion promoter.
Les propriétés des mats obtenus sont données dans le tableau 1 .  The properties of the mats obtained are given in Table 1.
EXEMPLE 2  EXAMPLE 2
a) fabrication du mat de fibres minérales  a) manufacture of the mineral fiber mat
Dans une installation industrielle, on forme par la voie sèche un mat constitué de filaments de verre C renforcé par des fils de verre (68 Tex).  In an industrial installation, a mat consisting of glass filaments C reinforced with glass yarns (68 Tex) is formed by the dry route.
Les fils de renforcement sont déposés sur un convoyeur dans le sens machine (chaîne) avec un espacement de 16 mm, après le dépôt d'une partie des filaments sur le convoyeur, de manière à ce que les fils de renforcement se trouvent noyés dans l'épaisseur du mat, puis un liant est appliqué par rideau sur le mat. Le convoyeur entre ensuite dans une étuve de 50 m de long chauffée à une température qui varie de 240 °C (entrée) à 200 °C (sortie) à la vitesse de 125 m/min. Le mat est bobiné sous la forme d'un enroulement.  The reinforcing threads are deposited on a conveyor in the machine direction (warp) with a spacing of 16 mm, after the deposition of a portion of the filaments on the conveyor, so that the reinforcement threads are embedded in the web. thickness of the mat, then a binder is applied by curtain on the mat. The conveyor then enters a 50 m long oven heated to a temperature ranging from 240 ° C (inlet) to 200 ° C (outlet) at a speed of 125 m / min. The mat is wound in the form of a winding.
Le liant organique a la composition de l'exemple 1 modifiée en ce que le promoteur d'adhésion est un copolymère éthylène-acide acrylique'11 ). The organic binder has the composition of Example 1 modified in that the adhesion promoter is an ethylene-acrylic acid copolymer ( 11) .
b) Fabrication du mat bitumé  b) Manufacture of the asphalt mat
Le mat de fibre de verre obtenu dans l'étape a) est immergé dans un bain de bitume en fusion (200 °C) par la méthode au trempé (« dip coating » en anglais). Le mat est ensuite refroidi à la température ambiante et bobiné sous la fome d'un enroulement.  The fiberglass mat obtained in step a) is immersed in a bath of molten bitumen (200 ° C.) by the dip coating method. The mat is then cooled to room temperature and coiled under the shape of a coil.
A titre de comparaison, on utilise un liant organique ne contenant pas de copolymère éthylène-acide acrylique pour fabriquer un mat de fibres de verre et un mat bitumé dans les conditions décrites précédemment.  By way of comparison, an organic binder containing no ethylene-acrylic acid copolymer is used to produce a mat of glass fibers and a matt mat under the conditions described above.
Les propriétés des mats figurent dans le tableau 1 .  The properties of the mats are shown in Table 1.
Référence Aérosol G61 commercialisé par la société Cytec Reference Aerosol G61 marketed by Cytec
Référence Agitan® commercialisé par la société Munzing Reference Agitan ® marketed by Munzing
Référence Tylose® commercialisé par la société ShinEtsu Tylose ® reference marketed by ShinEtsu
Référence Préfère® 71 0463J commercialisé par la société Préfère ResinsReference Préfère ® 71 0463J marketed by Préfère Resins
Référence Plextol® BV595 commercialisé par la société Synthomer <6) Référence Tackidex® G076 commercialisé par la société Roquette <7) Référence Mowiol® 40-88 commercialisé par la société Clariant Reference Plextol ® BV595 sold by the company Synthomer <6) Reference Tackidex ® G076 marketed by the company Roquette <7) Reference Mowiol ® 40-88 marketed by the company Clariant
(8) Référence Winacet® DP commercialisé par la société Synthos ( 8) Winacet ® DP reference sold by the company Synthos
Référence Michem® Prime 4983R commercialisé par la société Synthomer Reference Michem ® Prime 4983R marketed by the company Synthomer
Tableau 1 Table 1
Figure imgf000010_0001
Figure imgf000010_0001

Claims

REVENDICATIONS
1. Mat de fibres minérales comprenant un liant organique, caractérisé en ce que le liant organique comprend au moins une résine mélamine- formaldéhyde ou phénol-formaldéhyde et au moins un promoteur d'adhésion choisi dans le groupe constitué par les homopolymères d'acide (méth)acrylique et les copolymères d'acide (méth)acrylique et d'au moins un monomère éthyléniquement insaturé en C2-C8 différent du styrène. A mineral fiber mat comprising an organic binder, characterized in that the organic binder comprises at least one melamine-formaldehyde or phenol-formaldehyde resin and at least one adhesion promoter selected from the group consisting of homopolymers of acid ( meth) acrylic and copolymers of (meth) acrylic acid and at least one ethylenically unsaturated C 2 -C 8 monomer other than styrene.
2. Mat selon la revendication 1 , caractérisé en ce que l'homopolymère est un homopolymère d'acide acrylique.  2. Mat according to claim 1, characterized in that the homopolymer is a homopolymer of acrylic acid.
3. Mat selon la revendication 1 , caractérisé en ce que le copolymère est un copolymère d'acide (méth)acrylique et d'éthylène, de propène et/ou de butène, de préférence un copolymère d'acide acrylique et d'éthylène.  3. Mat according to claim 1, characterized in that the copolymer is a copolymer of (meth) acrylic acid and ethylene, propene and / or butene, preferably a copolymer of acrylic acid and ethylene.
4. Mat selon l'une des revendications 1 à 3, caractérisé en ce que la quantité de promoteur d'adhésion varie de 0,5 à 30 parts en masse pour 100 parts en masse de résine mélamine-formaldéhyde ou phénol-formaldéhyde et d'éventuels additifs, de préférence 5 à 15 parts.  4. Mat according to one of claims 1 to 3, characterized in that the amount of adhesion promoter varies from 0.5 to 30 parts by weight per 100 parts by weight of melamine-formaldehyde resin or phenol-formaldehyde and optional additives, preferably 5 to 15 parts.
5. Mat selon l'une des revendications 1 à 4, caractérisé en ce que le liant organique de base (hors promoteur d'adhésion) comprend les constituants ci-après dans les proportions suivantes (en % massique) :  5. Mat according to one of claims 1 to 4, characterized in that the organic base binder (excluding adhesion promoter) comprises the following constituents in the following proportions (in mass%):
- 5 à 100 % de résine mélamine-formaldéhyde ou phénol- formaldéhyde,  5 to 100% of melamine-formaldehyde or phenol-formaldehyde resin,
- 0 à 95 % d'amidon, et  0 to 95% of starch, and
- 0 à 30 % d'agents plastifiants.  0 to 30% of plasticizers.
6. Mat selon l'une des revendications 1 à 5, caractérisé en ce qu'il présente une masse surfacique qui varie de 10 à 1 100 g/m2, de préférence de 30 à 350 g/m2 et avantageusement de 35 à 80 g/m2. 6. Mat according to one of claims 1 to 5, characterized in that it has a weight per unit area which varies from 10 to 1100 g / m 2 , preferably from 30 to 350 g / m 2 and preferably from 35 to 80 g / m 2 .
7. Mat selon l'une des revendications 1 à 6, caractérisé en ce que la quantité de liant organique représente 5 à 40 % en masse du mat de fibres, et de préférence 10 à 30 %.  7. Mat according to one of claims 1 to 6, characterized in that the amount of organic binder is 5 to 40% by weight of the fiber mat, and preferably 10 to 30%.
8. Mat bitumé, caractérisé en ce qu'il comprend un mat de verre selon l'une des revendications 1 à 7. 8. asphalt mat, characterized in that it comprises a glass mat according to one of claims 1 to 7.
9. Mat selon la revendication 8, caractérisé en ce qu'il présente une masse surfacique qui varie de 1000 à 10 000 g/m, et de préférence de 1500 à 7500 g/m2. 9. Mat according to claim 8, characterized in that it has a mass per unit area which varies from 1000 to 10 000 g / m, and preferably from 1500 to 7500 g / m 2 .
10. Bardeau comprenant un mat bitumé selon la revendication 8 ou 9 et une couche des granules minéraux sur au moins une de ses faces.  10. Shingle comprising a bitumen mat according to claim 8 or 9 and a layer of mineral granules on at least one of its faces.
PCT/FR2015/051851 2014-07-04 2015-07-03 Mat of mineral fibres and bituminated products incorporating said mat WO2016001607A1 (en)

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