EP0388338A1 - Coating complex for fibrous supports for use in coating processes with a compressed foam - Google Patents

Coating complex for fibrous supports for use in coating processes with a compressed foam Download PDF

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Publication number
EP0388338A1
EP0388338A1 EP90440026A EP90440026A EP0388338A1 EP 0388338 A1 EP0388338 A1 EP 0388338A1 EP 90440026 A EP90440026 A EP 90440026A EP 90440026 A EP90440026 A EP 90440026A EP 0388338 A1 EP0388338 A1 EP 0388338A1
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EP
European Patent Office
Prior art keywords
complex
coating
flame retardant
fillers
fibrous support
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Granted
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EP90440026A
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German (de)
French (fr)
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EP0388338B1 (en
Inventor
Claude Bibler
Jean-Jacques Schirm
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Senfa SAS
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Senfa SAS
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0045—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by applying a ready-made foam layer; obtained by compressing, crinkling or crushing a foam layer, e.g. Kaschierverfahren für Schaumschicht
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes

Definitions

  • the present invention relates to a flame retardant coating complex for fibrous support and coated support thus obtained.
  • This complex is intended for so-called crushed foam coating processes.
  • these walls are formed of a fibrous support made more or less opaque by a sheet or sheet glued against one of the faces of the support or by an appropriate surface treatment consisting in coating one of the faces with a compound. likely to form a non-transparent continuous layer.
  • the supports used must have, in addition to the opaque nature, real and sufficient fire resistance properties due to their main use in the building sector.
  • this product proves to be ill-suited for commercial use in decoration or protection of habitable interiors due not only to the deterioration of its qualities over time but also to their notable reduction with each washing or each dry cleaning. .
  • the coating of fibrous supports, woven or not, consists of depositing in different ways on the web or strip in continuous movement of scrolling a complex intended to completely cover one of its faces and to be fixed on this support by hot pressure .
  • the coating complex used is emulsified into foam and then deposited on the support, dried and calendered by hot pressure. These are coating processes using the crushed foam technique.
  • the object of the present invention is to simultaneously confer on any coated support properties of high fire resistance and, if necessary, to obtain the exceptional properties. joint and apparently contradictory total and permanent opacity and fire resistance up to the self-extinguishing character sufficient to meet the standards currently in force, and this even on a textile support not naturally flame retardant in the raw state.
  • the coating complex enabling the coated support to be given a permanent flame retardant character and, when necessary, total opacity for fibrous supports, characterized in that the coating foam consists, for at least the half by weight, of a composition of binders from polyurethane dispersions, then in variable proportions of flame retardant fillers including the synergetic association of antimony oxide with organobromo compounds, as well as substitution fillers including opacifying fillers and dyes or pigments, composition supplemented with surfactants and rheology aids.
  • the flame retardant nature of the coating is permanent regardless of the nature and frequency of cleaning and maintenance treatments; . the coating complex, suitably completed, additionally provides total and permanent opacity properties without reducing the flame retardancy; . the flame retardant coating according to the invention in no way modifies the main qualities of the support while giving it the desired properties; . the coating complex is applied to various materials without distinction of quality; . the properties conferred prove to be durable; . the solidity of the support is thereby improved; . the result is obtained whatever the nature and the properties of the support; . the flame retardancy lost with conventional coating complexes from woven supports of flame retardant fibers is recovered by coating with the coating complex according to the invention.
  • the present invention consists in using in a crushed foam coating process a coating foam in which the binders for at least half by weight are binders based on polyurethane dispersions, to be supplemented by various fillers including flame retardant fillers for about a quarter by weight by the synergistic pair of antimony oxide and organobromo compounds, to add substitution charges for 5 to 15% by weight and conventionally a complement of surfactants and rheology auxiliaries.
  • the coating complex according to the invention can be used for all the conventional coating processes using the crushed foam technique.
  • a paste is prepared by incorporating into a binder based on dispersions or polyurethane emulsions for at least half by weight of the total mass, various fillers including at least about a quarter by weight, antimony oxide associated with organobromo compounds, as well as substitution fillers and dyes or pigments in the proportions indicated. Surfactants and rheology aids are then added to control or ensure the quality of the coating.
  • paste used to prepare the coating foam consists in detail of the following products according to the main variants described below.
  • compositions of the coating complex for which the proportions are given by weight will be indicated below by way of example.
  • Flame retardant composition binders: 50 to 60%. binders based on polyurethane dispersions . flame retardant fillers: 25 to 35% . antimony oxide . organobromo compounds . substitution charges: 5 to 15% . dyes or pigments: 4 to 6% . surfactants: 4 to 5% . rheology auxiliaries: 2 to 4% Fireproof and opaque composition: .
  • binders 50 to 60%. binders based on polyurethane dispersions . flame retardant fillers: 25 to 35% . antimony oxide . organobromo compounds . opacifying fillers: 5 to 10% .
  • rheology auxiliaries 2 to 4% Variant of fireproof and opaque composition: . binders: 50 to 60%. binders based on polyurethane dispersions . flame retardant fillers: 25 to 35% . antimony oxide . organobromo compounds . opacifying fillers: 5 to 10% . carbon black . titanium oxide . substitution secondary charges: 2 to 10% . dyes or pigments: 4 to 6% . surfactants: 4 to 5% . rheology auxiliaries: 2 to 4%
  • substitution charges will be chosen from the list of the following products: alumina trihydrate, barium sulfate, kaolin, talc, zinc sulfide.
  • Ammonium stearate or sodium sulfosuccinamate or sodium lauryl sulfate may be used as surfactants.
  • synthetic thickeners can be chosen such as polyacrylic acids or polyethylene oxides.
  • binders based on polyurethane dispersions are dispersions or emulsions of linear polyurethane with a single component and more particularly anionic or cationic dispersions.
  • the dough thus prepared is aerated in a mixer 1 for example of the type known under the name "mixer”, to form a fluid foam 2 stable at room temperature of use, fluidity degree determined by rheology auxiliaries.
  • This foam 2 is poured in the pasty state in front of a blade-shaped part 3 used as a doctor blade arranged transversely to a fibrous support 4 to be coated in continuous movement of movement.
  • This doctor blade allows the uniform application of the coating foam on the support 4 in a single layer 5.
  • the coated support then passes through an oven or drying enclosure 7 at increasing temperature between the inlet and the outlet, for example from 100 ° C. to 180 ° C. along which the coating layer 5, optionally loaded with cotton or other particles is dried while remaining flexible or semi-flexible.
  • the support On leaving the drying chamber 7, the support is subjected to calendering under hot pressure by passing through a calendering assembly 8 in which the coating complex is hot pressed against the fibrous support.
  • the coated support then passes through a crosslinking chamber 9 at constant temperature around 200 ° C or increasing to 200 ° C to be then cooled for example by blowing in 10 and then wound on a reel such as 11 in the commercial format of the fibrous support. .
  • the coating layer fixed by heat is immobile and stable.
  • An opacity check carried out at 12 makes it possible to monitor the quality of the coating, for example in the form of a light emitter 13 illuminating one of the faces and a photoelectric detector 14 facing the other side of the support. .
  • one or more other coating layers are deposited on top of the first in the same way by as many additional passes by recycling in a loop 15.
  • the categories of supports targeted by the invention fall into two main families: conventional flammable supports such as conventional textile supports made of cotton or based on cotton or in cotton-polyester or full polyester blends or fabrics based on viscose on the one hand and the supports produced from special fibers with characteristic flame retardant properties, such as the woven supports with from polyethylene terephthalate fibers modified with a permanent flame retardant, on the other hand.
  • conventional flammable supports such as conventional textile supports made of cotton or based on cotton or in cotton-polyester or full polyester blends or fabrics based on viscose on the one hand
  • the supports produced from special fibers with characteristic flame retardant properties such as the woven supports with from polyethylene terephthalate fibers modified with a permanent flame retardant, on the other hand.
  • the flame-retardant nature of the coating obtained by the process according to the invention is total and permanent in the same way as opacity when this property is necessary.
  • a self-extinguishing property could also be highlighted as satisfying the standards currently in force.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Coating complex for fibrous supports for use in so-called compressed-foam coating processes, characterised in that it is composed in an amount of at least 50% by weight of a basic composition coming from binders obtained from polyurethane dispersions, then, in variable proportions, of fire-resistant fillers and substitution fillers and of dyes or pigments, surface-active agents and rheological auxiliaries to give the support a permanent fire-resistant quality, if necessary lined with complete opacity. <IMAGE>

Description

La présente invention se rapporte à un complexe d'enduction ignifuge pour support fibreux et support enduit ainsi obtenu.The present invention relates to a flame retardant coating complex for fibrous support and coated support thus obtained.

Ce complexe est destiné aux procédés d'enduc­tion dits à mousse écrasée.This complex is intended for so-called crushed foam coating processes.

On cherche actuellement dans le domaine du bâtiment à remplacer les volets par un moyen satisfai­sant, pratique et peu cher, permettant d'assombrir facilement et rapidement une pièce un bureau ou une salle de projection. Ce moyen consiste à pourvoir les fenêtres de parois textiles ou de rideaux amovibles présentant une opacité suffisante pour remplacer avantageusement le cas échéant les volets. Ces parois ou rideaux sont dits d'occultation.We are currently seeking in the building sector to replace the shutters by a satisfactory, practical and inexpensive means, making it possible to easily and quickly darken a room, an office or a projection room. This means consists in providing the windows with removable textile walls or curtains having sufficient opacity to advantageously replace the shutters if necessary. These walls or curtains are called blackout.

Ils doivent présenter les propriétés requises pour tous les matériaux employés dans le bâtiment dont au moins des propriétés ignifuges suffisantes et permanentes.They must have the properties required for all materials used in the building, including at least sufficient and permanent flame retardant properties.

Dans d'autres domaines, on procède de la même façon pour former un écran obscur amovible sur les fenê­tres ou hublots (trains, avions) ou pour créer l'isola­tion visuelle ou à la lumière temporaire dont on a be­soin : cabinets de soins, hôpitaux.....Ici également, le caractère ignifuge s'avère d'une grande importance.In other fields, we proceed in the same way to form a removable dark screen on windows or portholes (trains, planes) or to create the visual or temporary light insulation that we need: medical offices, hospitals ..... Here too, the flame retardancy is of great importance.

Selon les fabrications connues, ces parois sont formées d'un support fibreux rendu plus ou moins opaque par une nappe ou feuille collée contre une des faces du support ou par un traitement approprié de surface consistant en une enduction d'une des faces par un composé susceptible de former une couche continue non transparente.According to known fabrications, these walls are formed of a fibrous support made more or less opaque by a sheet or sheet glued against one of the faces of the support or by an appropriate surface treatment consisting in coating one of the faces with a compound. likely to form a non-transparent continuous layer.

Comme déjà indiqué, les supports utilisés doivent présenter en plus du caractère opaque, des propriétés réelles et suffisantes de résistance au feu en raison de leur utilisation principale dans le domaine du bâtiment.As already indicated, the supports used must have, in addition to the opaque nature, real and sufficient fire resistance properties due to their main use in the building sector.

On connaît tout d'abord le procédé qui consis­ te à créer un rideau ou une doublure de rideau à partir d'une feuille mince et souple par exemple en caoutchouc, en chlorure de polyvinyle ou en métal par exemple en aluminium, adhérant sur toute sa surface sur une feuille mince et souple de matière synthétique cellulaire en vue d'obtenir une opacité et de bonnes qualités d'isolation thermique et acoustique sans accroissement notable de la densité du produit.We first know the process that consis te to create a curtain or a curtain lining from a thin and flexible sheet for example of rubber, polyvinyl chloride or metal for example of aluminum, adhering over its entire surface on a thin and flexible sheet of synthetic material cell in order to obtain opacity and good qualities of thermal and acoustic insulation without significant increase in the density of the product.

Habillée de cette feuille mince et souple, éventuellement doublée, la matière synthétique semble moins vulnérable au feu et constitue un écran dense pour la lumière. Néanmoins, dans la pratique, ce produit ne présente pas une opacité totale et on note une dégrada­tion de ses propriétés initiales essentielles dans le temps.Dressed in this thin and flexible sheet, possibly lined, the synthetic material seems less vulnerable to fire and constitutes a dense screen for light. However, in practice, this product does not have total opacity and there is a degradation of its essential initial properties over time.

Par ailleurs, ce produit s'avère mal adapté à un usage commercial en décoration ou protection d'inté­rieurs habitables en raison non seulement de la détério­ration de ses qualités dans le temps mais aussi à leur diminution notable à chaque lavage ou à chaque nettoyage à sec.Furthermore, this product proves to be ill-suited for commercial use in decoration or protection of habitable interiors due not only to the deterioration of its qualities over time but also to their notable reduction with each washing or each dry cleaning. .

L'enduction des supports fibreux, tissés ou non, consiste à déposer de différentes manières sur la nappe ou bande en mouvement continu de défilement un complexe destiné à recouvrir totalement l'une de ses faces et à être fixé sur ce support par pression à chaud.The coating of fibrous supports, woven or not, consists of depositing in different ways on the web or strip in continuous movement of scrolling a complex intended to completely cover one of its faces and to be fixed on this support by hot pressure .

Le complexe d'enduction utilisé est émulsionné en mousse puis déposée sur le support, sèché et calandré par pression à chaud. Il s'agit des procédés d'enduction utilisant la technique de la mousse écrasée.The coating complex used is emulsified into foam and then deposited on the support, dried and calendered by hot pressure. These are coating processes using the crushed foam technique.

Ces procédés classiques d'enduction permettent de conférer dans une certaine mesure à un support fibreux des propriétés d'opacité et de résistance au feu.These conventional coating processes make it possible to confer to a certain extent on a fibrous support properties of opacity and fire resistance.

Il s'agit, par exemple, du procédé d'enduction dit " à la râcle " qui consiste à enduire une des faces par application purement mécanique à la râcle du complexe émulsionné de manière à former sur la bande fibreuse ou textile en défilement continu, une couche uniforme d'une certine opacité qui sera ultérieurement séchée.This is, for example, the coating process known as "scraper" which consists in coating one of the faces by purely mechanical application to the doctor blade of the emulsified complex so as to form on the fibrous or textile strip in continuous movement, a uniform layer of a certain opacity which will be subsequently dried.

Il existe d'autres procédés d'enduction connus utilisant la technique de la mousse écrasée tels que ceux à cadre rotatif ou ceux connus sous la dénomination commerciale " VARIOPRINT ".There are other known coating processes using the crushed foam technique such as those with a rotating frame or those known under the trade name "VARIOPRINT".

En raison des faibles épaisseurs nécessaires pour la bonne application de la couche et en raison de la fluidité de la pâte employée, ce procédé ne permet d'obtenir ni une opacité totale, ni un caractère ignifuge suffisant. Par ailleurs, comme précédemment, le maintien de ces qualités et propriétés dans le temps n'est pas garanti, constituant un véritable handicap à la diffusion commerciale du produit dans le domaine du bâtiment.Because of the small thicknesses necessary for the correct application of the layer and because of the fluidity of the paste used, this process does not allow either total opacity or sufficient flame retardancy. Furthermore, as before, the maintenance of these qualities and properties over time is not guaranteed, constituting a real handicap to the commercial dissemination of the product in the building sector.

Ainsi, si ces procédés, avec les complexes d'enduction employés, permettent d'obtenir certains résultats simultanés en opacité et en propriétés ignifuges, des inconvénients d'insuffisance de degré dans le résultat et de non constance et maintien de celui-ci dans le temps tels que principalement la disparition des propriétés ignifuges au lavage et au nettoyage à sec, ne permettent pas de donner une garantie commerciale suffisante au produit pour l'application visée.Thus, if these processes, with the coating complexes used, make it possible to obtain certain simultaneous results in opacity and in flame-retardant properties, disadvantages of insufficient degree in the result and of non-consistency and maintenance of the latter in the times such as mainly the disappearance of the flame retardant properties in washing and dry cleaning, do not give a sufficient commercial guarantee to the product for the intended application.

Par ailleurs, l'obtention de ces résultats ne s'avère pas répétitive et, plus particulièrement et de façon surprenante, ne se produit pas sur certains tissus à base de fibres spéciales synthétiques possédant déjà avant tissage des propriétés ignifuges importantes.Furthermore, obtaining these results does not prove to be repetitive and, more particularly and surprisingly, does not occur on certain fabrics based on special synthetic fibers which already have significant flame retardant properties before weaving.

La présente invention a pour but de conférer simultanément à un support enduit quelconque des propriétés d'importante résistance au feu et, en cas de besoin d'obtenir les propriétés exceptionnelles conjointes et apparemment contradictoires d'opacité totale et permanente et de résistance au feu allant jusqu'au caractère auto-extinguible suffisant pour satisfaire aux normes actuellement en vigueur, et ceci même sur un support textile non naturellement ignifuge à l'état brut.The object of the present invention is to simultaneously confer on any coated support properties of high fire resistance and, if necessary, to obtain the exceptional properties. joint and apparently contradictory total and permanent opacity and fire resistance up to the self-extinguishing character sufficient to meet the standards currently in force, and this even on a textile support not naturally flame retardant in the raw state.

A cet effet, elle se rapporte à un complexe d'enduction permettant de conférer au support enduit un caractère ignifuge permanent et en cas de besoin une opacité totale pour supports fibreux caractérisé en ce que la mousse d'enduction se compose, pour au moins la moitié en poids, d'une composition de liants à partir de de dispersions de polyuréthane, puis en proportions variables de charges ignifugeantes dont l'association synergétique de l'oxyde d'antimoine avec des composés organobromés, ainsi que des charges de substitution dont des charges opacifiantes et des colorants ou pigments, composition complétée par des agents tensioactifs et des auxiliaires de rhéologie.To this end, it relates to a coating complex enabling the coated support to be given a permanent flame retardant character and, when necessary, total opacity for fibrous supports, characterized in that the coating foam consists, for at least the half by weight, of a composition of binders from polyurethane dispersions, then in variable proportions of flame retardant fillers including the synergetic association of antimony oxide with organobromo compounds, as well as substitution fillers including opacifying fillers and dyes or pigments, composition supplemented with surfactants and rheology aids.

De nombreux avantages résultent de la mise en oeuvre de la présente invention et du produit en résultant tels que :
. le caractère ignifuge de l'enduction est permanent quelles que soient la nature et la fréquence des traitements de nettoyage et d'entretien ;
. le complexe d'enduction, convenablement complété, confère en plus des propriétés d'opacité totale et permanentes sans amoindrir le caractère ignifuge ;
. l'enduction ignifuge selon l'invention ne modifie en rien les qualités principales du support tout en lui conférant les propriétés recherchées ;
. le complexe d'enduction s'applique sur des matières variées sans distinction de qualité ;
. les propriétés conférées s'avèrent durables ;
. la solidité du support s'en trouve améliorée ;
. le résultat est obtenu quelles que soient la nature et les propriétés du support ;
. le caractère ignifuge perdu avec les complexes d'enduction classiques à partir de supports tissés de fibres ignifuges est retrouvé grâce à l'enduction à l'aide du complexe d'enduction selon l'invention.Many advantages result from the implementation of the present invention and the resulting product such as:
. the flame retardant nature of the coating is permanent regardless of the nature and frequency of cleaning and maintenance treatments;
. the coating complex, suitably completed, additionally provides total and permanent opacity properties without reducing the flame retardancy;
. the flame retardant coating according to the invention in no way modifies the main qualities of the support while giving it the desired properties;
. the coating complex is applied to various materials without distinction of quality;
. the properties conferred prove to be durable;
. the solidity of the support is thereby improved;
. the result is obtained whatever the nature and the properties of the support;
. the flame retardancy lost with conventional coating complexes from woven supports of flame retardant fibers is recovered by coating with the coating complex according to the invention.

La description ci-après a pour but de mieux faire comprendre l'invention, elle est effectuée à l'aide de plusieurs exemples de complexes d'enduction et de supports fibreux.The description below is intended to better understand the invention, it is carried out using several examples of coating complexes and fibrous supports.

Pour plus de clarté, on décrira également ci-après un procédé d'enduction utilisant la technique de la mousse écrasée en référence au dessin accompagnant qui est un schéma de l'installation mettant en oeuvre le procédé choisi comme exemple .For clarity, a coating process will also be described below using the crushed foam technique with reference to the accompanying drawing which is a diagram of the installation implementing the method chosen as an example.

La présente invention consiste à utiliser dans un procédé d'enduction à mousse écrasée une mousse d'enduction dont les liants pour au moins la moitié en poids sont des liants à base de dispersions de polyuréthane, à compléter par des charges diverses dont des charges ignifugeantes pour environ un quart en poids par le couple synergétique oxyde d'antimoine et composés organobromés, à ajouter des charges de substitution pour 5 à 15 % en poids et classiquement un complément d'agents tensio actifs et des auxiliaires de rhéologie.The present invention consists in using in a crushed foam coating process a coating foam in which the binders for at least half by weight are binders based on polyurethane dispersions, to be supplemented by various fillers including flame retardant fillers for about a quarter by weight by the synergistic pair of antimony oxide and organobromo compounds, to add substitution charges for 5 to 15% by weight and conventionally a complement of surfactants and rheology auxiliaries.

Comme indiqué, le complexe d'enduction selon l'invention peut être utilisé pour tous les procédés classiques d'enduction mettant en oeuvre la technique de la mousse écrasée.As indicated, the coating complex according to the invention can be used for all the conventional coating processes using the crushed foam technique.

A titre illustratif et pour mieux faire comprendre l'invention, on décrira ci-après un des procédés d'enduction possibles, choisis parmi ceux indi­qués, par exemple celui dit "à la râcle". Ce procédé apporte d'excellents résultats avec le complexe d'enduc­tion selon l'invention. Il en est de même pour les autres procédés d'enduction connus, par exemple à cadre rotatif ou celui appelé "VARIOPRINT".By way of illustration and to better understand the invention, one of the possible coating methods will be described below, chosen from those indicated, for example that known as "scraper". This process provides excellent results with the coating complex according to the invention. It is the same for the other known coating methods, for example with a rotary frame or that called "VARIOPRINT".

Selon l'invention, on prépare une pâte en incorporant dans un liant à base de dispersions ou d'émulsions de polyuréthane pour au moins la moitié en poids de la masse totale, des charges diverses dont au moins pour environ un quart en poids, de l'oxyde d'antimoine associé avec des composés organobromés, ainsi que des charges de substitution et des colorants ou pigments dans les proportions indiquées. Des agents tensioactifs et des auxiliaires de rhéologie sont ensuite ajoutés pour maîtriser ou assurer la qualité de l'enduction.According to the invention, a paste is prepared by incorporating into a binder based on dispersions or polyurethane emulsions for at least half by weight of the total mass, various fillers including at least about a quarter by weight, antimony oxide associated with organobromo compounds, as well as substitution fillers and dyes or pigments in the proportions indicated. Surfactants and rheology aids are then added to control or ensure the quality of the coating.

Plus particulièrement la pâte utilisée pour préparer la mousse d'enduction se compose en détail des produits suivants selon les principales variantes décrites ci-après.More particularly the paste used to prepare the coating foam consists in detail of the following products according to the main variants described below.

On indiquera ci-après à titre d'exemple quel­ques variantes de compositions du complexe d'enduction pour lesquelles les proportions sont données en poids.
Composition ignifuge : . liants : 50 à 60 % . liants à base de dispersions de polyuréthane
. charges ignifugeantes : 25 à 35 %
. oxyde d'antimoine
. composés organobromés
. charges de substitution : 5 à 15 %
. colorants ou pigments : 4 à 6 %
. agents tensioactifs : 4 à 5 %
. auxiliaires de rhéologie : 2 à 4 %
Composition ignifuge et opaque :
. liants : 50 à 60 % . liants à base de dispersions de polyuréthane
. charges ignifugeantes : 25 à 35 %
. oxyde d'antimoine
. composés organobromés
. charges opacifiantes : 5 à 10 %
. poudre d'aluminium
. oxyde de titane
. charges secondaires de substitution : 2 à 10 %
. colorants ou pigments : 4 à 6
. agents tensioactifs : 4 à 5 %
. auxiliaires de rhéologie : 2 à 4 %
Variante de composition ignifuge :
. liants : 50 à 60 % . liants à base de dispersions de polyuréthane
. charges ignifugeantes : 25 à 35 %
. oxyde d'antimoine
. composés organobromés
. charges de substitution : 5 à 15 %
. trihydrate d'alumine
. sulfate de baryum
. kaolin
. talc
. sulfure de zinc
. colorants ou pigments : 4 à 6 %
. agents tensioactifs : 4 à 5 %
. auxiliaires de rhéologie : 2 à 4 %
Variante de composition ignifuge et opaque :
. liants : 50 à 60 % . liants à base de dispersions de polyuréthane
. charges ignifugeantes : 25 à 35 %
. oxyde d'antimoine
. composés organobromés
. charges opacifiantes : 5 à 10 %
. noir de carbone
. oxyde de titane
. charges secondaires de substitution : 2 à 10 %
. colorants ou pigments : 4 à 6 %
. agents tensioactifs : 4 à 5 %
. auxiliaires de rhéologie : 2 à 4 %Some examples of compositions of the coating complex for which the proportions are given by weight will be indicated below by way of example.
Flame retardant composition:. binders: 50 to 60%. binders based on polyurethane dispersions
. flame retardant fillers: 25 to 35%
. antimony oxide
. organobromo compounds
. substitution charges: 5 to 15%
. dyes or pigments: 4 to 6%
. surfactants: 4 to 5%
. rheology auxiliaries: 2 to 4%
Fireproof and opaque composition:
. binders: 50 to 60%. binders based on polyurethane dispersions
. flame retardant fillers: 25 to 35%
. antimony oxide
. organobromo compounds
. opacifying fillers: 5 to 10%
. aluminum powder
. titanium oxide
. substitution secondary charges: 2 to 10%
. dyes or pigments: 4 to 6
. surfactants: 4 to 5%
. rheology auxiliaries: 2 to 4%
Variant of flame retardant composition:
. binders: 50 to 60%. binders based on polyurethane dispersions
. flame retardant fillers: 25 to 35%
. antimony oxide
. organobromo compounds
. substitution charges: 5 to 15%
. alumina trihydrate
. barium sulfate
. kaolin
. talc
. zinc sulfide
. dyes or pigments: 4 to 6%
. surfactants: 4 to 5%
. rheology auxiliaries: 2 to 4%
Variant of fireproof and opaque composition:
. binders: 50 to 60%. binders based on polyurethane dispersions
. flame retardant fillers: 25 to 35%
. antimony oxide
. organobromo compounds
. opacifying fillers: 5 to 10%
. carbon black
. titanium oxide
. substitution secondary charges: 2 to 10%
. dyes or pigments: 4 to 6%
. surfactants: 4 to 5%
. rheology auxiliaries: 2 to 4%

On citera ci-après de façon non limitative quelques exemples de produits annexes et de fonction particulière utilisés dans la composition ci-dessus et mentionnés de façon générale par des termes génériques.A few non-limiting examples will be given below of additional products and of particular function used in the above composition and generally mentioned by generic terms.

Selon l'application visée, les charges de substitution seront choisies parmi la liste des produits suivants : trihydrate d'alumine, sulfate de baryum, kaolin, talc, sulfure de zinc.Depending on the intended application, the substitution charges will be chosen from the list of the following products: alumina trihydrate, barium sulfate, kaolin, talc, zinc sulfide.

On peut citer comme exemple typique de composés organobromés le décabromodiphényle ou le décabromodiphényle oxyde.Mention may be made, as a typical example of organobromo compounds, of decabromodiphenyl or decabromodiphenyl oxide.

On pourra prendre à titre d'agents tensioactifs du stéarate d'ammonium ou du sulfosuccina­mate de sodium ou encore du laurylsulfate de sodium.Ammonium stearate or sodium sulfosuccinamate or sodium lauryl sulfate may be used as surfactants.

A titre d'auxiliaires de rhéologie, on pourra choisir des épaississants synthétiques tels que des acides polyacryliques ou des oxydes de polyéthylène.As rheology auxiliaries, synthetic thickeners can be chosen such as polyacrylic acids or polyethylene oxides.

Concernant les liants à base de dispersions de polyuréthane, on précise ici qu'il s'agit de dispersions ou d'émulsions de polyuréthane linéaire à un seul cons­tituant et plus particulièrement des dispersions anioni­ques ou cationiques.As regards the binders based on polyurethane dispersions, it is specified here that these are dispersions or emulsions of linear polyurethane with a single component and more particularly anionic or cationic dispersions.

Selon le procédé classique de la mousse écrasée appliquée à la râcle, la pâte ainsi préparée est aérée dans un mélangeur 1 par exemple du type connu sous la dénomination "mixer", pour former une mousse fluide 2 stable à la température ambiante d'utilisation, de degré de fluidité déterminé par les auxiliaires de rhéologie.According to the conventional process of crushed foam applied to the scraper, the dough thus prepared is aerated in a mixer 1 for example of the type known under the name "mixer", to form a fluid foam 2 stable at room temperature of use, fluidity degree determined by rheology auxiliaries.

On déverse cette mousse 2 à l'état pâteux devant une pièce 3 en forme de lame utilisée comme râcle disposée transversalement à un support fibreux 4 à enduire en mouvement continu de défilement. Cette râcle permet l'application uniforme de la mousse d'enduction sur le support 4 selon une seule couche 5.This foam 2 is poured in the pasty state in front of a blade-shaped part 3 used as a doctor blade arranged transversely to a fibrous support 4 to be coated in continuous movement of movement. This doctor blade allows the uniform application of the coating foam on the support 4 in a single layer 5.

Après application continue en une seule couche du complexe d'enduction à la râcle sur le support fibreux 4 à enduire, celui-ci subit éventuellement à un poste 6 dit de flockage une déposition de particules de coton ou une projection de coton finement divisé, ou d'autres fibres naturelles ou synthétiques.After continuous application in a single layer of the scraper coating complex on the fibrous support 4 to be coated, this optionally undergoes, at a so-called flocking station 6, deposition of cotton particles or a projection of finely divided cotton, or other natural or synthetic fibers.

Le support enduit passe ensuite dans un four ou enceinte de séchage 7 à température croissante entre l'entrée et la sortie par exemple de 100 °C à 180 °C le long duquel la couche 5 d'enduction éventuellement chargée en particules de coton ou autre est séchée tout en restant souple ou semi-souple.The coated support then passes through an oven or drying enclosure 7 at increasing temperature between the inlet and the outlet, for example from 100 ° C. to 180 ° C. along which the coating layer 5, optionally loaded with cotton or other particles is dried while remaining flexible or semi-flexible.

A la sortie de l'enceinte de séchage 7, le support subit un calandrage sous pression à chaud par passage dans un ensemble de calandrage 8 dans lequel le complexe d'enduction est pressé à chaud contre le support fibreux.On leaving the drying chamber 7, the support is subjected to calendering under hot pressure by passing through a calendering assembly 8 in which the coating complex is hot pressed against the fibrous support.

Le support enduit traverse ensuite une chambre de réticulation 9 à température constante autour de 200°C ou croissante jusqu'à 200 °C pour être refroidi ensuite par exemple par soufflage en 10 puis enroulé sur une bobine telle que 11 au format commercial du support fibreux.The coated support then passes through a crosslinking chamber 9 at constant temperature around 200 ° C or increasing to 200 ° C to be then cooled for example by blowing in 10 and then wound on a reel such as 11 in the commercial format of the fibrous support. .

A l'issue de ce traitement, la couche d'enduc­tion fixée par la chaleur, est immobile et stable.At the end of this treatment, the coating layer fixed by heat, is immobile and stable.

Un contrôle d'opacité effectué en 12 permet de suivre la qualité de l'enduction par exemple sous la forme d'un émetteur lumineux 13 éclairant l'une des faces et d'un détecteur photoélectrique 14 en regard de l'autre côté du support.An opacity check carried out at 12 makes it possible to monitor the quality of the coating, for example in the form of a light emitter 13 illuminating one of the faces and a photoelectric detector 14 facing the other side of the support. .

Si nécessaire, une ou plusieurs autres couches d'enduction sont déposées au-dessus de la première de la même façon par autant de passages supplémentaires par recyclage selon une boucle 15.If necessary, one or more other coating layers are deposited on top of the first in the same way by as many additional passes by recycling in a loop 15.

Une telle mousse, lorsqu'étendue, séchée et fixée par la chaleur, confère à la bande fibreuse qui la porte une résistance suffisante au feu qu'elle pouvait ne pas posséder d'origine de manière à résister à l'épreuve des tests officiels.Such foam, when extended, dried and fixed by heat, gives the fibrous strip which carries it sufficient resistance to fire which it could not have possessed of origin so as to withstand the test of official tests.

Les catégories de supports visés par l'inven­tion se partagent en deux familles principales : les supports classiques inflammables tels que les supports textiles classiques en coton ou à base de coton ou en mélanges coton-polyester ou en polyester intégral ou des tissus à base de viscose d'une part et les supports fabriqués à partir de fibres spéciales à propriétés ignifuges caractérisées, tels que les supports tissés à partir de fibres de polytéréphtalate d'éthylène modifiées par un agent permanent retardateur de flamme, d'autre part.The categories of supports targeted by the invention fall into two main families: conventional flammable supports such as conventional textile supports made of cotton or based on cotton or in cotton-polyester or full polyester blends or fabrics based on viscose on the one hand and the supports produced from special fibers with characteristic flame retardant properties, such as the woven supports with from polyethylene terephthalate fibers modified with a permanent flame retardant, on the other hand.

Comme déjà indiqué et de façon surprenante, dans ce dernier cas, le caractère ignifuge n'est pas conservé lors de l'application d'un complexe opacifiant classique.As already indicated and surprisingly, in the latter case, the flame retardancy is not retained during the application of a conventional opacifying complex.

Le caractère ignifuge de l'enduction obtenue par le procédé selon l'invention est total et permanent de la même façon que l'opacité lorsque cette propriété est nécessaire.The flame-retardant nature of the coating obtained by the process according to the invention is total and permanent in the same way as opacity when this property is necessary.

Une propriété d'auto-extinguibilité a pu éga­lement être mise en évidence telle que satisfaisant aux normes actuellement en vigueur.A self-extinguishing property could also be highlighted as satisfying the standards currently in force.

Ainsi, même sur des tissus réalisés avec des fibres inflammables, on arrive à un comportement au feu suffisamment satisfaisant pour permettre au produit en­duit d'être classé non-feu selon les normes internatio­nales.Thus, even on fabrics made with flammable fibers, we arrive at a sufficiently satisfactory fire behavior to allow the coated product to be classified fireproof according to international standards.

L'invention a été décrite ci-dessus en détail. Il est bien entendu cependant que diverses modifications simples, adjonctions, variantes directes, substitutions par des moyens équivalents entrent dans le cadre de la présente protection.The invention has been described above in detail. It is understood, however, that various simple modifications, additions, direct variants, substitutions by equivalent means fall within the scope of this protection.

Claims (12)

1. Complexe d'enduction pour support fibreux, mis en oeuvre dans un procédé d'enduction utilisant la technique de la mousse écrasée, caractérisé en ce qu'il se compose pour au moins la moitié en poids de la masse totale, de liants à base de dispersions ou d'émulsions de polyuréthane et, pour le reste de la masse, de char­ges diverses dont pour au moins un quart en poids, une composition ignifugeante d'oxyde d'antimoine et de composés organobromés complétée par des charges de substitution et dans les proportions suivantes des colorants ou pigments pour 4 à 6 %, des agents tensioactifs pour 4 à 5 % et des auxiliaires de rhéographie pour 2 à 4 %.1. Coating complex for fibrous support, used in a coating process using the crushed foam technique, characterized in that it is composed for at least half by weight of the total mass, of binders base of polyurethane dispersions or emulsions and, for the rest of the mass, of various fillers, of which for at least a quarter by weight, a flame retardant composition of antimony oxide and of organobromo compounds supplemented by substitution fillers and in the following proportions dyes or pigments for 4 to 6%, surfactants for 4 to 5% and rheography aids for 2 to 4%. 2. Complexe d'enduction pour support fibreux selon la revendication 1, caractérisé en ce qu'un des composés organobromés est le décabromodiphényle.2. Coating complex for fibrous support according to claim 1, characterized in that one of the organobrominated compounds is decabromodiphenyl. 3. Complexe d'enduction pour support fibreux selon la revendication 1, caractérisé en ce qu'un des composés organobromés est le décabromodiphényle oxyde.3. Coating complex for fibrous support according to claim 1, characterized in that one of the organobrominated compounds is decabromodiphenyl oxide. 4. Complexe d'enduction pour support fibreux selon la revendication 1, caractérisé en ce que les charges de substitution comportent des charges opaci­fiantes.4. Coating complex for fibrous support according to claim 1, characterized in that the substitution fillers include opacifying fillers. 5. Complexe d'enduction pour support fibreux selon la revendication 4, caractérisé en ce que les charges opacifiantes contiennent de la poudre d'alumi­nium ou du noir de carbone.5. Coating complex for fibrous support according to claim 4, characterized in that the opacifying fillers contain aluminum powder or carbon black. 6. Complexe selon la revendication 1, caracté­risé en ce que le support à enduire est un support fibreux non ignifuge.6. Complex according to claim 1, characterized in that the support to be coated is a non-flame retardant fibrous support. 7. Complexe selon la revendication 1, caracté­risé en ce que le support à enduire est un support fibreux ignifuge.7. Complex according to claim 1, characterized in that the support to be coated is a flame-retardant fibrous support. 8. Complexe selon la revendication 7 caracté­risé en ce que le support fibreux ignifuge à enduire est un tissu de fibres en polytéréphtalate d'éthylène modifiées par un agent permanent retardateur de flamme.8. Complex according to claim 7 characterized in that the flame retardant fibrous support to be coated is a fabric of polyethylene terephthalate fibers modified by a permanent flame retardant agent. 9. Procédé d'enduction utilisant un complexe d'enduction revendiqué dans l'une quelconque des revendications précédentes par application selon la technique dite de la mousse écrasée, caractérisé en ce que l'on utilise le complexe d'enduction suivant :
. liants : 50 à 60 % . liants à base de dispersions de polyuréthane
. charges ignifugeantes : 25 à 35 %
. oxyde d'antimoine
. composés organo-bromés
. charges de substitution : 5 à 15 %
. colorants ou pigments : 4 à 6 %
. agents tensioactifs : 4 à 5 %
. auxiliaires de rhéologie : 2 à 4 %9. Coating process using a coating complex claimed in any one of the preceding claims by application according to the so-called crushed foam technique, characterized in that the following coating complex is used:
. binders: 50 to 60%. binders based on polyurethane dispersions
. flame retardant fillers: 25 to 35%
. antimony oxide
. organo-brominated compounds
. substitution charges: 5 to 15%
. dyes or pigments: 4 to 6%
. surfactants: 4 to 5%
. rheology auxiliaries: 2 to 4% 10. Procédé d'enduction utilisant un complexe revendiqué dans l'une quelconque des revendications pré­cédentes, par application selon la technique dite de la mousse écrasée, caractérisé en ce que l'on utilise le complexe d'enduction suivant :
. liants : 50 à 60 % . liants à base de dispersions de polyuréthane
. charges ignifugeantes : 25 à 35 %
. oxyde d'antimoine
. composés organo-bromés
. charges opacifiantes : 5 à 10 %
. poudre d'aluminium ou noir de carbone
. oxyde de titane
. charges de substitution : 2 à 10 %
. colorants ou pigments : 4 à 6 %
. agents tensioactifs : 4 à 5 %
. auxiliaires de rhéologie : 2 à 4 %10. Coating process using a complex claimed in any one of the preceding claims, by application according to the so-called crushed foam technique, characterized in that the following coating complex is used:
. binders: 50 to 60%. binders based on polyurethane dispersions
. flame retardant fillers: 25 to 35%
. antimony oxide
. organo-brominated compounds
. opacifying fillers: 5 to 10%
. aluminum powder or carbon black
. titanium oxide
. substitution charges: 2 to 10%
. dyes or pigments: 4 to 6%
. surfactants: 4 to 5%
. rheology auxiliaries: 2 to 4% 11. Support fibreux enduit à caractère igni­fuge tel qu'obtenu par l'utilisation du complexe reven­diqué en revendications de 1 à 10 dans un procédé d'en­ duction mettant en oeuvre la technique de la mousse écrasée.11. Coated fibrous support with a flame retardant nature as obtained by the use of the complex claimed in claims from 1 to 10 in a process for duction using the crushed foam technique. 12. Support fibreux enduit à caractère ignifu­ge et d'opacité totale tel qu'obtenu par l'utilisation du complexe revendiqué dans l'une quelconque des reven­dications 1 à 8, dans le cadre d'un procédé d'enduction mettant en oeuvre la technique de la mousse écrasée.12. Coated fibrous support with a flame retardant nature and total opacity as obtained by the use of the complex claimed in any one of claims 1 to 8, within the framework of a coating process using the technique crushed foam.
EP90440026A 1989-03-17 1990-03-16 Coating complex for fibrous supports for use in coating processes with a compressed foam Expired - Lifetime EP0388338B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8903719A FR2644485B1 (en) 1989-03-17 1989-03-17 COATING COMPLEX FOR FIBROUS SUPPORTS FOR USE IN THE SAID CRUSHED COATING PROCESSES
FR8903719 1989-03-17

Publications (2)

Publication Number Publication Date
EP0388338A1 true EP0388338A1 (en) 1990-09-19
EP0388338B1 EP0388338B1 (en) 1994-11-09

Family

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Family Applications (1)

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EP90440026A Expired - Lifetime EP0388338B1 (en) 1989-03-17 1990-03-16 Coating complex for fibrous supports for use in coating processes with a compressed foam

Country Status (4)

Country Link
EP (1) EP0388338B1 (en)
AT (1) ATE114000T1 (en)
DE (1) DE69013949T2 (en)
FR (1) FR2644485B1 (en)

Cited By (12)

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WO2003064759A1 (en) * 2002-01-29 2003-08-07 Elk Premium Building Products, Inc. Fire resistant structural material and fabrics made therefrom
US7361617B2 (en) 2004-03-23 2008-04-22 Elkcorp Fire resistant composite material and fabrics therefrom
CN100406642C (en) * 2003-12-31 2008-07-30 上海洁润丝新材料股份有限公司 Flame Retardant Coating Process for Heavy Fabrics
US7521385B2 (en) 1999-11-30 2009-04-21 Building Materials Invest Corp Fire resistant structural material, fabrics made therefrom
US7563733B2 (en) 2002-01-29 2009-07-21 Elkcorp Composite material
US8017531B2 (en) 2001-09-18 2011-09-13 Elkcorp Composite material
US8030229B2 (en) 2002-01-29 2011-10-04 Elkcorp. Composite material
US8822356B2 (en) 2004-03-23 2014-09-02 Elkcorp Fire resistant composite material and fabrics made therefrom
US8822355B2 (en) 2004-03-23 2014-09-02 Elkcorp Fire resistant composite material and fabrics made therefrom
US8987149B2 (en) 2004-03-23 2015-03-24 Elkcorp Fire resistant composite material and fabrics made therefrom
US9435074B2 (en) 2004-03-23 2016-09-06 Elkcorp Fire resistant composite material and fabrics made therefrom
WO2018203017A1 (en) * 2017-05-04 2018-11-08 Senfa Composite support and uses

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7521385B2 (en) 1999-11-30 2009-04-21 Building Materials Invest Corp Fire resistant structural material, fabrics made therefrom
US8017531B2 (en) 2001-09-18 2011-09-13 Elkcorp Composite material
US8030229B2 (en) 2002-01-29 2011-10-04 Elkcorp. Composite material
US7563733B2 (en) 2002-01-29 2009-07-21 Elkcorp Composite material
WO2003064759A1 (en) * 2002-01-29 2003-08-07 Elk Premium Building Products, Inc. Fire resistant structural material and fabrics made therefrom
CN100406642C (en) * 2003-12-31 2008-07-30 上海洁润丝新材料股份有限公司 Flame Retardant Coating Process for Heavy Fabrics
US7361617B2 (en) 2004-03-23 2008-04-22 Elkcorp Fire resistant composite material and fabrics therefrom
US8822356B2 (en) 2004-03-23 2014-09-02 Elkcorp Fire resistant composite material and fabrics made therefrom
US8822355B2 (en) 2004-03-23 2014-09-02 Elkcorp Fire resistant composite material and fabrics made therefrom
US8987149B2 (en) 2004-03-23 2015-03-24 Elkcorp Fire resistant composite material and fabrics made therefrom
US9435074B2 (en) 2004-03-23 2016-09-06 Elkcorp Fire resistant composite material and fabrics made therefrom
WO2018203017A1 (en) * 2017-05-04 2018-11-08 Senfa Composite support and uses
FR3065906A1 (en) * 2017-05-04 2018-11-09 Senfa COMPOSITE SUPPORT AND USES
CN110573672A (en) * 2017-05-04 2019-12-13 塞恩法公司 Composite supports and applications

Also Published As

Publication number Publication date
FR2644485B1 (en) 1992-11-27
DE69013949T2 (en) 1995-04-27
EP0388338B1 (en) 1994-11-09
FR2644485A1 (en) 1990-09-21
ATE114000T1 (en) 1994-11-15
DE69013949D1 (en) 1994-12-15

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