WO2019158866A1 - Method for depositing an organic intumescent coating on a glass sheet - Google Patents

Method for depositing an organic intumescent coating on a glass sheet Download PDF

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Publication number
WO2019158866A1
WO2019158866A1 PCT/FR2019/050331 FR2019050331W WO2019158866A1 WO 2019158866 A1 WO2019158866 A1 WO 2019158866A1 FR 2019050331 W FR2019050331 W FR 2019050331W WO 2019158866 A1 WO2019158866 A1 WO 2019158866A1
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WO
WIPO (PCT)
Prior art keywords
acid
intumescent
coating
organic
vinyl
Prior art date
Application number
PCT/FR2019/050331
Other languages
French (fr)
Inventor
Marine BRUNET
François COMPOINT
François POTIER
Samuel KRON
Original Assignee
Saint-Gobain Glass France
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
Priority claimed from FR1851336A external-priority patent/FR3078014A1/en
Application filed by Saint-Gobain Glass France filed Critical Saint-Gobain Glass France
Priority to EP19710053.0A priority Critical patent/EP3752359A1/en
Priority to US16/968,008 priority patent/US20210363362A1/en
Publication of WO2019158866A1 publication Critical patent/WO2019158866A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/069—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of intumescent material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the present invention relates to the field of fireproof glazing. It relates in particular to a method of depositing an organic intumescent coating on a glass sheet, and a glazing comprising a glass sheet coated with an intumescent organic coating obtainable by this method.
  • the fire-resistant glazings are conventionally formed of a highly viscous aqueous solution based on hydrated alkali silicates sealed between two glass sheets (EP 3023245, WO 2007/118886, WO 2007/053248, EP 2072247, EP 2282889, WO 2008 / 053 248).
  • Other fireproof glazings are formed of a solid hydrogel layer between two sheets of glass, obtained by crosslinking a solution of water-soluble monomers (US 2016/2000077, EP 2330174).
  • the protection against fire is provided by the opaque mineral foam formed by the expansion of the layer of silicates due to the evaporation of the water it contains under the effect of heat.
  • hydrogel layer unlike the alkali silicate layer, there is no foaming.
  • the spread of fire is retarded by the evaporation of water and the inorganic additives contained in the hydrogel layer.
  • intumescent organic coatings such as paints or varnishes, developed to improve the fire resistance of building materials.
  • Such coatings comprise a polymeric binder and an intumescent system generally formed of an acid source such as phosphoric acid or a ammonium polyphosphate, a carbonaceous compound such as a polyol, and an expanding agent such as urea or melamine.
  • an acid source such as phosphoric acid or a ammonium polyphosphate
  • carbonaceous compound such as a polyol
  • an expanding agent such as urea or melamine
  • the object of the present invention is to provide an intumescent organic coating that is both suitable for application to a glass sheet, does not affect the optical properties thereof and has good intumescence.
  • one aspect of the present invention relates to a method of depositing an organic intumescent coating on a glass sheet comprising:
  • the latex has a pH of 4 to 6 and the intumescent agent is selected from thermodegradable polycarboxylic acids, preferably citric acid.
  • thermodegradable polycarboxylic acids preferably citric acid.
  • the Applicant has in fact demonstrated that the use of a latex having a pH of 4 to 6 in combination with a thermodegradable polycarboxylic acid, especially citric acid, as intumescent agent allowed to ensure good processability, especially for the deposition of thick layers (for example of the order of a millimeter or more), and to obtain a coating having a high transparency and little blur, while having good intumescent properties.
  • the latex is an aqueous dispersion of an organic binder.
  • the organic binder is preferably a thermoplastic polymer.
  • organic binders include homopolymers or copolymers derived from vinyl monomers or co-monomers.
  • the vinyl monomers include especially alkenes such as ethylene, propylene or isoprene, vinyl chloride, vinylidene chloride, styrene, vinyltoluene, acrylonitrile and vinyl esters.
  • vinyl esters include, for example, vinyl Cl-Cl 2 carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, sodium hexanoate and the like.
  • organic binders include copolymers based on ⁇ -alkenes, especially ethylene, and one or more vinyl and / or vinyl chloride esters, such as ethylene / vinyl acetate copolymers, ethylene terpolymers, and the like. / vinyl acetate / vinyl chloride and terpolymers ethylene / vinyl acetate / vinyl ester including C9-C1 vinyl loveratate.
  • the latex has a pH of 4 to 6, preferably 4.5 to 5.5, in particular to ensure a homogeneous dispersion of the thermodegradable polycarboxylic acid in the coating composition while maintaining good processability.
  • the thermodegradable polycarboxylic acid is a compound comprising at least two carboxylic acid functions, and which degrades and releases a gaseous compound under the effect of the rise in temperature (for example greater than 100 ° C. or even 150 ° C.) which allows the expansion of the organic coating.
  • the thermodegradable polycarboxylic acid preferably has a solubility in water at 20 ° C of greater than 50 g / l.
  • thermodegradable polycarboxylic acid may be a dicarboxylic acid, such as oxalic acid, malonic acid, malic acid, tartaric acid, tartronic acid or maleic acid, a tricarboxylic acid such as citric acid or tricarballylic acid, or a tetracarboxylic acid such as 1,2,3,4-butanetetracarboxylic acid.
  • a thermodegradable polycarboxylic acid in particular citric acid, as an intumescent agent is advantageous because, while providing a good intumescence, it does not affect or slightly affect the total light transmission of the coating formed and does not induce no or little blur.
  • the coating composition typically has a solids content of 30 to 70%, preferably 40 to 60%, by weight. It typically comprises from 5 to 50%, preferably from 10 to 40%, or even from 15 to 30% by dry weight of intumescent agent.
  • the coating composition may also comprise fillers, in particular inorganic or organometallic fillers, such as silica particles (in particular colloidal silica), silicates, precursors of sol-gel metal oxides or coupling based on silanes.
  • fillers selected from precursors of sol-gel metal oxides, in particular silicon and / or titanium, are preferred. It may comprise from 0.5%, or even 1% to 60%, or even 50%, 40%, 20% or even 15% by weight of fillers. Levels below 5% or
  • the coating composition does not include fillers.
  • the coating composition may also comprise from 0.5 to 15%, preferably 1 to 10%, by dry weight of a flame retardant.
  • the flame retardant is preferably selected from organophosphorus compounds, especially phosphonates such as diethyl ethylphosphonate or dimethyl methylphosphonate.
  • the glass sheet may have a thickness ranging from 1 to 8 mm, preferably 2 to 6 mm.
  • the glass may be a silico-soda-lime glass obtained by floating on a tin bath (according to the "float" method), a borosilicate glass or any other type of transparent glass. It can be a clear or colored glass according to the desired aesthetic rendering.
  • the glass sheet is a non-tempered glass sheet.
  • it is a sheet of tempered glass.
  • the coating composition may be applied to the surface of the glass sheet by any technique known to those skilled in the art, such as for example wet deposition techniques such as spray coating, curtain application ( curtain coating), by spraying (flow coating), by application to the roll (voiler coating) or by casting. It may optionally be applied in several times to obtain the desired final coating thickness. After In this application, the deposit is dried, typically at temperatures of 20 to 80 ° C for 5 minutes to 24 hours, preferably for 5 to 20 minutes, to obtain an intumescent organic coating.
  • wet deposition techniques such as spray coating, curtain application ( curtain coating), by spraying (flow coating), by application to the roll (voiler coating) or by casting. It may optionally be applied in several times to obtain the desired final coating thickness.
  • the deposit is dried, typically at temperatures of 20 to 80 ° C for 5 minutes to 24 hours, preferably for 5 to 20 minutes, to obtain an intumescent organic coating.
  • a glazing unit comprising a glass sheet coated with an intumescent organic coating, in particular capable of being obtained by the process according to the above method, characterized in that the organic coating comprises an organic binder. and an intumescent agent, said intumescent agent being selected from thermodegradable polycarboxylic acids, preferably citric acid.
  • an intumescent agent being selected from thermodegradable polycarboxylic acids, preferably citric acid.
  • the intumescent organic coating typically has a thickness of 0.01 to 3 mm, preferably 0.05 to 2 mm. It typically has a total light transmittance greater than 85%, preferably greater than 87%, and a blur of less than 15%, preferably less than 10%, measured by Hazemeter according to standard
  • the intumescent organic coating may be in direct contact with the glass sheet.
  • an element A "in direct contact" with an element B means that no other element is disposed between said elements A and B.
  • an element A "in contact" with an element B does not exclude the presence of another element between said elements A and B.
  • a bonding layer in particular based on silanes, can be placed between the intumescent organic coating and glass sheet to enhance its adhesion to the glass sheet.
  • the intumescent organic coating has the property of foaming under the effect of temperature, typically at temperatures above 100 ° C, or even above 180 ° C, for example between 200 and 400 ° C, to reach at least eight times, preferably at least 10 times their initial thickness.
  • the glazing may be single glazing or multiple glazing (for example double or triple). It can include several intumescent organic coatings.
  • the glass sheet may be coated with an intumescent organic coating on each of its faces.
  • several glass sheets or even each glass sheet may be coated on at least one of their faces with an intumescent organic coating.
  • the glazing may also comprise functional coatings, especially solar control, low-e, photocatalytic, etc.
  • the glazing according to the invention is a fireproof glazing comprising two sheets of glass separated by an intumescent organic coating according to the invention or a stack of layers comprising the intumescent organic coating according to the invention, this fireproof glazing can also be integrated in a multiple glazing optionally comprising functional coatings.
  • Example 1 The compositions of Examples 1 (according to the invention) and 2 to 6 (comparative) were prepared by mixing various latexes and 20% by dry weight of intumescent agents. These compositions were then cast onto the surface of a 2.5 mm thick glass sheet and dried to obtain an intumescent organic coating of about 2 mm.
  • the total light transmission (TL) and the blur of the coatings Hazemeter measured according to ASTM D 1003-00 with Illuminant C.
  • the coated glass sheets were then subjected to temperatures of 300 ° C for 10 minutes.
  • the intumescence quality of the organic coating during this heat treatment was quantified by comparing the thickness of the foam obtained with respect to the initial thickness of the intumescent coating.
  • compositions of Examples 7 to 9 were not prepared from latex but from a crosslinkable resin based on acrylates (polyester acrylate and polyethylene glycol (PEG 400) acrylate - ratio 10: 90 by weight).
  • the resin is mixed with a photoinitiator, then the intumescent agents (20% by dry weight) are introduced into the mixture.
  • the formulation is then deposited on a substrate and crosslinked under a UV lamp.
  • Table 1 summarizes the nature of the coating compositions and the properties of intumescent coatings obtained.
  • the processability taking into account the ease of implementation of the composition and the quality of the coating obtained, is noted as follows: ® impossible application; ⁇ S> possible application but poor quality coating; O possible application and good quality coating.
  • Example 1 Only the composition of Example 1 exhibits good processability and makes it possible to obtain a coating having both satisfactory optical and intumescent properties. On the contrary, the coating compositions of Examples 2 and 3 do not make it possible to obtain a coating that does not have a blur and / or intumescent sufficient for application to glass.
  • the compositions of Examples 4 to 9 However, they do not exhibit sufficient processability: for Examples 4 to 6, the composition gels rapidly, preventing any application; for Examples 7 to 9, the coating obtained cracks and / or delaminates after drying and crosslinking.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention concerns a method for depositing an organic intumescent coating on a glass sheet that comprises preparing an organic intumescent coating composition by mixing a latex having a pH of between 4 and 6 and an intumescent agent chosen from the thermodegradable polycarboxylic acids; and applying the organic intumescent coating composition to the glass sheet, and a glazing comprising a glass sheet coated with an organic intumescent coating likely to be obtained by this method.

Description

PROCEDE DE DEPOT D’UN REVETEMENT INTUMESCENT ORGANIQUE METHOD FOR DEPOSITING AN INTUMESCENT ORGANIC COATING
SUR FEUILLE DE VERRE ON GLASS SHEET
La présente invention concerne le domaine des vitrages anti-feu. Elle concerne notamment une méthode de dépôt d’un revêtement intumescent organique sur une feuille de verre, ainsi qu’un vitrage comprenant une feuille de verre revêtue d’un revêtement organique intumescent susceptible d’être obtenue par ce procédé. The present invention relates to the field of fireproof glazing. It relates in particular to a method of depositing an organic intumescent coating on a glass sheet, and a glazing comprising a glass sheet coated with an intumescent organic coating obtainable by this method.
Les vitrages anti-feu sont classiquement formés d’une solution aqueuse très visqueuse à base de silicates alcalins hydratés scellée entre deux feuilles de verre (EP 3023245, WO 2007/118886, WO 2007/053248, EP 2072247, EP 2282889, WO 2008/053248). D’autres vitrages anti-feu sont formés d’une couche d’hydrogel solide entre deux feuilles de verre, obtenue par réticulation d’une solution de monomères hydrosolubles (US 2016/2000077, EP 2330174). Dans le premier cas, la protection contre le feu est assurée par la mousse minérale opaque formée par l’expansion de la couche de silicates due à l’évaporation de l’eau qu’elle renferme sous l’effet de la chaleur. Pour la couche d’hydrogel, contrairement à la couche de silicate alcalin, il n’y a pas formation de mousse. La propagation du feu est retardée par l’évaporation de l’eau et les additifs inorganiques contenus dans la couche d’hydrogel. Ces solutions, bien qu’efficaces, mettent en œuvre des procédés de fabrication qui peuvent s’avérer complexes du fait des contraintes liées à l’injection d’une solution entre deux feuilles de verre. The fire-resistant glazings are conventionally formed of a highly viscous aqueous solution based on hydrated alkali silicates sealed between two glass sheets (EP 3023245, WO 2007/118886, WO 2007/053248, EP 2072247, EP 2282889, WO 2008 / 053 248). Other fireproof glazings are formed of a solid hydrogel layer between two sheets of glass, obtained by crosslinking a solution of water-soluble monomers (US 2016/2000077, EP 2330174). In the first case, the protection against fire is provided by the opaque mineral foam formed by the expansion of the layer of silicates due to the evaporation of the water it contains under the effect of heat. For the hydrogel layer, unlike the alkali silicate layer, there is no foaming. The spread of fire is retarded by the evaporation of water and the inorganic additives contained in the hydrogel layer. These solutions, although effective, implement manufacturing processes that can be complex due to the constraints of injecting a solution between two sheets of glass.
Il existe des revêtements organiques intumescents, tels que des peintures ou des vernis, développés pour améliorer la résistance au feu des matériaux de construction. De tels revêtements comprennent un liant polymère et un système intumescent généralement formé d’une source acide tel que l’acide phosphorique ou un polyphosphate d’ammonium, d’un composé carboné tel qu’un polyol, et un agent d’expansion tel que l’urée ou la mélamine. Lorsqu’ils sont exposés au feu, ces revêtements moussent et produisent un résidu charbonneux protecteur. Le résidu charbonneux agit comme une barrière protégeant physiquement et thermiquement le matériau revêtu. Dans la plupart des cas, le revêtement joue également un rôle esthétique permettant de modifier l’apparence des surfaces des matériaux recouverts. Il existe également des vernis intumescents dits transparents, destinés à des applications sur des surfaces en bois ou en plastique, permettant de conserver l’apparence esthétique des surfaces recouvertes. Ce type de revêtements intumescents présente un intérêt pour améliorer la résistance au feu des vitrages. Cependant, les vernis intumescents dits transparents connus à ce jour n’apportent pas entière satisfaction. Appliqués en couche épaisse sur du verre, ils présentent un aspect laiteux qui n’est pas acceptable du point de vue esthétique. Il semblerait en effet que ces revêtements nécessitent en réalité d’être appliqués sur une surface suffisamment poreuse ou rugueuse pour être perçus comme transparent après application. There are intumescent organic coatings, such as paints or varnishes, developed to improve the fire resistance of building materials. Such coatings comprise a polymeric binder and an intumescent system generally formed of an acid source such as phosphoric acid or a ammonium polyphosphate, a carbonaceous compound such as a polyol, and an expanding agent such as urea or melamine. When exposed to fire, these coatings foam and produce a protective carbonaceous residue. The carbonaceous residue acts as a barrier physically and thermally protecting the coated material. In most cases, the coating also plays an aesthetic role in changing the appearance of the surfaces of the coated materials. There are also so-called transparent intumescent varnishes, intended for applications on wooden or plastic surfaces, making it possible to preserve the aesthetic appearance of the surfaces covered. This type of intumescent coating is of interest for improving the fire resistance of glazing. However, so-called transparent intumescent varnishes known to date do not provide complete satisfaction. Applied in a thick layer on glass, they have a milky appearance that is not acceptable from an aesthetic point of view. It would seem indeed that these coatings actually need to be applied on a sufficiently porous or rough surface to be perceived as transparent after application.
L’objectif de la présente invention est de proposer un revêtement organique intumescent qui soit à la fois adapté à une application sur une feuille de verre, n’affecte pas les propriétés optiques de celle-ci et présente une bonne intumescence. Ainsi, un aspect de la présente invention concerne un procédé de dépôt d’un revêtement intumescent organique sur une feuille de verre comprenant : The object of the present invention is to provide an intumescent organic coating that is both suitable for application to a glass sheet, does not affect the optical properties thereof and has good intumescence. Thus, one aspect of the present invention relates to a method of depositing an organic intumescent coating on a glass sheet comprising:
- la préparation d’une composition de revêtement intumescent organique par mélange d’un latex et d’un agent intumescent; et  the preparation of an organic intumescent coating composition by mixing a latex and an intumescent agent; and
- l’application de la composition de revêtement intumescent organique sur la feuille de verre ; the application of the organic intumescent coating composition to the sheet of glass ;
caractérisé en ce que le latex présente un pH de 4 à 6 et l’agent intumescent est choisi parmi les acides polycarboxylique thermodégradable, de préférence l’acide citrique. La Demanderesse a en effet mis en évidence que l’utilisation d’un latex présentant un pH de 4 à 6 en combinaison avec un acide polycarboxylique thermodégradable, notamment l’acide citrique, comme agent intumescent permettait d’assurer une bonne processabilité, notamment pour le dépôt de couches épaisses (par exemple de l’ordre du millimètre ou plus), et d’obtenir un revêtement présentant une transparence élevée et peu de flou, tout en présentant de bonnes propriétés intumescentes. Le latex est une dispersion aqueuse d’un liant organique. Le liant organique est de préférence un polymère thermoplastique. Des exemples de liants organiques comprennent les homopolymères ou copolymères dérivés de monomères ou co- monomères vinyliques. Les monomères vinyliques comprennent notamment les a- alcènes tels que l’éthylène, le propylène ou l’isoprène, le chlorure de vinyle, le chlorure de vinylidène, le styrène, le vinyltoluène, l’acrylonitrile et les esters de vinyle. Des exemples d’esters de vinyle comprennent notamment les Cl -Cl 2 carboxylates de vinyle tels que l'acétate de vinyle, le propionate de vinyle, le butyrate de vinyle, l'isobutyrate de vinyle, le valérate de vinyle, l’hexanoate de vinyle, le 2-méthylhexanoate de vinyle, le 2-éthylhexanoate de vinyle, l’iso-octanoate de vinyle, le nonanoate de vinyle, le décanoate de vinyle, le laurate de vinyle, le palmitate de vinyle, le stéarate de vinyle, le néodécanoate de vinyle et les C9-C11 versatates de vinyle (aussi appelés VeoVa pour vinyl ester of versatic acid). Des liants organiques préférés comprennent les copolymères à base d’a-alcènes, notamment l’éthylène, et d’un ou plusieurs esters de vinyle et/ou de chlorure de vinyle, tels que les copolymères éthylène/acétate de vinyle, les terpolymères éthylène/acétate de vinyle/chlorure de vinyle et les terpolymères éthylène/acétate de vinyle/ester de vinyle notamment C9-C1 lversatate de vinyle. characterized in that the latex has a pH of 4 to 6 and the intumescent agent is selected from thermodegradable polycarboxylic acids, preferably citric acid. The Applicant has in fact demonstrated that the use of a latex having a pH of 4 to 6 in combination with a thermodegradable polycarboxylic acid, especially citric acid, as intumescent agent allowed to ensure good processability, especially for the deposition of thick layers (for example of the order of a millimeter or more), and to obtain a coating having a high transparency and little blur, while having good intumescent properties. The latex is an aqueous dispersion of an organic binder. The organic binder is preferably a thermoplastic polymer. Examples of organic binders include homopolymers or copolymers derived from vinyl monomers or co-monomers. The vinyl monomers include especially alkenes such as ethylene, propylene or isoprene, vinyl chloride, vinylidene chloride, styrene, vinyltoluene, acrylonitrile and vinyl esters. Examples of vinyl esters include, for example, vinyl Cl-Cl 2 carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, sodium hexanoate and the like. vinyl 2-methylhexanoate, vinyl 2-ethylhexanoate, vinyl iso-octanoate, vinyl nonanoate, vinyl decanoate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl vinyl neodecanoate and vinyl C9-C11 versatates (also called VeoVa for vinyl ester of versatic acid). Preferred organic binders include copolymers based on α-alkenes, especially ethylene, and one or more vinyl and / or vinyl chloride esters, such as ethylene / vinyl acetate copolymers, ethylene terpolymers, and the like. / vinyl acetate / vinyl chloride and terpolymers ethylene / vinyl acetate / vinyl ester including C9-C1 vinyl loveratate.
Le latex présente un pH de 4 à 6 de préférence de 4,5 à 5,5, permettant notamment d’assurer une dispersion homogène de l’acide polycarboxylique thermodégradable dans la composition de revêtement tout en conservant une bonne processabilité. L’acide polycarboxylique thermodégradable est un composé comprenant au moins deux fonctions acide carboxylique, et qui se dégrade et libère un composé gazeux sous l’effet de l’élévation de la température (par exemple supérieure à l00°C, voire l50°C), ce qui permet l’expansion du revêtement organique. L’acide polycarboxylique thermodégradable présente de préférence une solubilité dans l’eau à 20°C supérieure à 50 g/L. L’acide polycarboxylique thermodégradable peut être un acide dicarboxylique, tel que l’acide oxalique, l’acide malonique, l’acide malique, l’acide tartrique, l’acide tartronique ou l’acide maléique, un acide tricarboxylique tel que l’acide citrique ou l’acide tricarballylique, ou un acide tétracarboxylique tel que l’acide 1, 2,3,4- butanetétracarboxylique. Le choix d’un acide polycarboxylique thermodégradable, notamment l’acide citrique, comme agent intumescent est quant à lui avantageux car, tout en procurant une bonne intumescence, il n’affecte pas ou peu la transmission lumineuse totale du revêtement formé et n’induit pas ou peu de flou. The latex has a pH of 4 to 6, preferably 4.5 to 5.5, in particular to ensure a homogeneous dispersion of the thermodegradable polycarboxylic acid in the coating composition while maintaining good processability. The thermodegradable polycarboxylic acid is a compound comprising at least two carboxylic acid functions, and which degrades and releases a gaseous compound under the effect of the rise in temperature (for example greater than 100 ° C. or even 150 ° C.) which allows the expansion of the organic coating. The thermodegradable polycarboxylic acid preferably has a solubility in water at 20 ° C of greater than 50 g / l. The thermodegradable polycarboxylic acid may be a dicarboxylic acid, such as oxalic acid, malonic acid, malic acid, tartaric acid, tartronic acid or maleic acid, a tricarboxylic acid such as citric acid or tricarballylic acid, or a tetracarboxylic acid such as 1,2,3,4-butanetetracarboxylic acid. The choice of a thermodegradable polycarboxylic acid, in particular citric acid, as an intumescent agent is advantageous because, while providing a good intumescence, it does not affect or slightly affect the total light transmission of the coating formed and does not induce no or little blur.
La composition de revêtement présente typiquement une teneur en matière sèche de 30 à 70 %, de préférence de 40 à 60 %, en poids. Elle comprend typiquement de 5 à 50 %, de préférence de 10 à 40 %, voire de 15 à 30 %, en poids sec d’agent intumescent. The coating composition typically has a solids content of 30 to 70%, preferably 40 to 60%, by weight. It typically comprises from 5 to 50%, preferably from 10 to 40%, or even from 15 to 30% by dry weight of intumescent agent.
La composition de revêtement peut également comprendre charges, notamment inorganiques ou organométalliques, tels que des particules de silice (notamment silice colloïdale), des silicates, des précurseurs d’oxydes métalliques sol-gel ou des agents de couplage à base de silanes. Les charges sont avantageusement choisies de façon à ne pas affecter les propriétés optiques du revêtement. A cette effet, des charges choisies parmi les précurseurs d’oxydes métalliques sol-gel, notamment de silicium et/ou de titane, sont préférées. Elle peut comprendre de 0,5 %, voire 1 % à 60 %, voire 50 %, 40 %, 20 %, ou même 15 % en poids de charges. Des teneurs inférieures à 5 %, voireThe coating composition may also comprise fillers, in particular inorganic or organometallic fillers, such as silica particles (in particular colloidal silica), silicates, precursors of sol-gel metal oxides or coupling based on silanes. The charges are advantageously chosen so as not to affect the optical properties of the coating. For this purpose, fillers selected from precursors of sol-gel metal oxides, in particular silicon and / or titanium, are preferred. It may comprise from 0.5%, or even 1% to 60%, or even 50%, 40%, 20% or even 15% by weight of fillers. Levels below 5% or
2 % en poids sec sont cependant préférables pour limiter l’apparition de flou. De préférence, la composition de revêtement ne comprend pas de charges. 2% by dry weight are however preferable to limit the appearance of blur. Preferably, the coating composition does not include fillers.
La composition de de revêtement peu également comprendre de 0,5 à 15 %, de préférence 1 à 10 %, en poids sec d’un agent retardateur de flamme. L’agent retardateur de flamme est de préférence choisi parmi les composés organophosphorés, notamment les phosphonates tels que l’éthylphosphonate de diéthyle ou le méthylphosphonate de diméthyle. The coating composition may also comprise from 0.5 to 15%, preferably 1 to 10%, by dry weight of a flame retardant. The flame retardant is preferably selected from organophosphorus compounds, especially phosphonates such as diethyl ethylphosphonate or dimethyl methylphosphonate.
La feuille de verre peut avoir une épaisseur qui varie de 1 à 8 mm, de préférence 2 à 6 mm. Le verre peut être un verre silico-sodo-calcique obtenu par flottage sur un bain d’étain (selon le procédé « float »), un verre borosilicate ou tout autre type de verre transparent. Il peut s’agir d’un verre clair ou coloré en fonction du rendu esthétique souhaité. Dans une première alternative, la feuille de verre est une feuille de verre non trempée. Dans une seconde alternative, il s’agit d’une feuille de verre trempée. The glass sheet may have a thickness ranging from 1 to 8 mm, preferably 2 to 6 mm. The glass may be a silico-soda-lime glass obtained by floating on a tin bath (according to the "float" method), a borosilicate glass or any other type of transparent glass. It can be a clear or colored glass according to the desired aesthetic rendering. In a first alternative, the glass sheet is a non-tempered glass sheet. In a second alternative, it is a sheet of tempered glass.
La composition de revêtement peut être appliquée sur la surface de la feuille de verre par toute technique connue de l’homme du métier, comme par exemple des techniques de dépôt par voie humide telles que par pulvérisation ( spray coating), par application au rideau ( curtain coating), par aspersion (flow coating), par application au rouleau {voiler coating) ou par coulée. Elle peut éventuellement être appliquée en plusieurs fois pour obtenir l’épaisseur finale de revêtement souhaitée. Après application, le dépôt est séché, typiquement à des températures de 20 à 80°C pendant 5 minutes à 24 heures, de préférence pendant 5 à 20 minutes, pour obtenir un revêtement organique intumescent. The coating composition may be applied to the surface of the glass sheet by any technique known to those skilled in the art, such as for example wet deposition techniques such as spray coating, curtain application ( curtain coating), by spraying (flow coating), by application to the roll (voiler coating) or by casting. It may optionally be applied in several times to obtain the desired final coating thickness. After In this application, the deposit is dried, typically at temperatures of 20 to 80 ° C for 5 minutes to 24 hours, preferably for 5 to 20 minutes, to obtain an intumescent organic coating.
Un autre aspect de la présente invention concerne un vitrage comprenant une feuille de verre revêtue d’un revêtement organique intumescent, notamment susceptible d’être obtenue par le procédé selon le procédé ci-dessus, caractérisé en ce que le revêtement organique comprend un liant organique et un agent intumescent, ledit agent intumescent étant choisi parmi les acides polycarboxyliques thermodégradables, de préférence l’acide citrique. Les caractéristiques de la composition de revêtement décrit ci-dessus concernant la nature des composants et leurs quantités s’appliquent également au revêtement organique intumescent. Another aspect of the present invention relates to a glazing unit comprising a glass sheet coated with an intumescent organic coating, in particular capable of being obtained by the process according to the above method, characterized in that the organic coating comprises an organic binder. and an intumescent agent, said intumescent agent being selected from thermodegradable polycarboxylic acids, preferably citric acid. The characteristics of the coating composition described above concerning the nature of the components and their amounts also apply to the intumescent organic coating.
Le revêtement organique intumescent présente typiquement une épaisseur de 0,01 à 3 mm, de préférence de 0,05 à 2 mm. Il présente typiquement une transmission lumineuse totale supérieure à 85 %, de préférence supérieure à 87 %, et un flou inférieur à 15 %, de préférence inférieur à 10 %, mesurés au Hazemeter selon la normeThe intumescent organic coating typically has a thickness of 0.01 to 3 mm, preferably 0.05 to 2 mm. It typically has a total light transmittance greater than 85%, preferably greater than 87%, and a blur of less than 15%, preferably less than 10%, measured by Hazemeter according to standard
ASTM D 1003-00 avec l’illuminant C. ASTM D 1003-00 with Illuminant C.
Le revêtement organique intumescent peut être en contact direct avec la feuille de verre. Au sens de la présente invention, un élément A « en contact direct » avec un élément B signifie qu’aucun autre élément n’est disposé entre lesdits éléments A et B.The intumescent organic coating may be in direct contact with the glass sheet. For the purposes of the present invention, an element A "in direct contact" with an element B means that no other element is disposed between said elements A and B.
Au contraire, un élément A « en contact » avec un élément B n’exclut pas la présence d’un autre élément entre lesdits éléments A et B. Alternativement, une couche de liaison, notamment à base de silanes, peut être disposée entre le revêtement organique intumescente et la feuille de verre afin d’améliorer son adhésion à la feuille de verre. Le revêtement organique intumescent présente la propriété de mousser sous l’effet de la température, typiquement à des températures supérieures à l00°C, voire supérieures à l80°C, par exemple entre 200 et 400°C, pour atteindre au moins huit fois, de préférence au moins 10 fois leur épaisseur initiale. Le vitrage peut être un vitrage simple ou un vitrage multiple (par exemple double ou un triple). Il peut comprendre plusieurs revêtements organiques intumescents. Dans le cas d’un vitrage simple par exemple, la feuille de verre peut être revêtue d’un revêtement organique intumescent sur chacune de ses faces. Dans le cas de vitrages multiples, plusieurs feuilles de verres, voire chaque feuille de verre, peuvent être revêtue sur au moins une de leurs faces d’un revêtement organique intumescent. Le vitrage peut également comprendre des revêtements fonctionnels, notamment de contrôle solaire, low-e, photocatalytique, etc... Dans un mode de réalisation particulier, le vitrage selon l’invention est un vitrage anti-feu comprenant deux feuilles de verres séparées par un revêtement organique intumescent selon l’invention ou un empilement de couches comprenant le revêtement organique intumescent selon l’invention, ce vitrage anti-feu pouvant également être intégré dans un vitrage multiple comprenant éventuellement des revêtements fonctionnels. On the contrary, an element A "in contact" with an element B does not exclude the presence of another element between said elements A and B. Alternatively, a bonding layer, in particular based on silanes, can be placed between the intumescent organic coating and glass sheet to enhance its adhesion to the glass sheet. The intumescent organic coating has the property of foaming under the effect of temperature, typically at temperatures above 100 ° C, or even above 180 ° C, for example between 200 and 400 ° C, to reach at least eight times, preferably at least 10 times their initial thickness. The glazing may be single glazing or multiple glazing (for example double or triple). It can include several intumescent organic coatings. In the case of a single glazing for example, the glass sheet may be coated with an intumescent organic coating on each of its faces. In the case of multiple glazing, several glass sheets or even each glass sheet may be coated on at least one of their faces with an intumescent organic coating. The glazing may also comprise functional coatings, especially solar control, low-e, photocatalytic, etc. In a particular embodiment, the glazing according to the invention is a fireproof glazing comprising two sheets of glass separated by an intumescent organic coating according to the invention or a stack of layers comprising the intumescent organic coating according to the invention, this fireproof glazing can also be integrated in a multiple glazing optionally comprising functional coatings.
L’invention est illustrée à l’aide d’exemples non limitatifs suivants. The invention is illustrated with the following non-limiting examples.
EXEMPLES Les composition des exemples 1 (selon l’invention) et 2 à 6 (comparatifs) ont été préparées par mélange de divers latex et 20 % en poids sec d’agents intumescents. Ces compositions ont ensuite été déposées par coulée sur la surface d’une feuille de verre d’épaisseur 2,5 mm puis séchées pour obtenir un revêtement organique intumescent d’environ 2 mm. La transmission lumineuse totale (TL) et le flou des revêtements ont été mesurés au Hazemeter selon la norme ASTM D 1003-00 avec l’illuminant C. EXAMPLES The compositions of Examples 1 (according to the invention) and 2 to 6 (comparative) were prepared by mixing various latexes and 20% by dry weight of intumescent agents. These compositions were then cast onto the surface of a 2.5 mm thick glass sheet and dried to obtain an intumescent organic coating of about 2 mm. The total light transmission (TL) and the blur of the coatings Hazemeter measured according to ASTM D 1003-00 with Illuminant C.
Les feuilles de verres revêtues ont ensuite été soumises à des températures de 300 °C pendant 10 minutes. La qualité d’intumescence du revêtement organique lors de ce traitement thermique a été quantifiée par comparaison de l’épaisseur de la mousse obtenu par rapport à l’épaisseur initiale du revêtement intumescent. The coated glass sheets were then subjected to temperatures of 300 ° C for 10 minutes. The intumescence quality of the organic coating during this heat treatment was quantified by comparing the thickness of the foam obtained with respect to the initial thickness of the intumescent coating.
Contrairement aux exemples précédents, les compositions des exemples 7 à 9 n’ont pas été préparées à partir de latex mais à partir d’une résine réticulable à base d’acrylates (polyester acrylate et polyethylene glycol (PEG 400) acrylate - ratio 10 :90 en poids). On mélange la résine avec un photoamorceur, puis les agents intumescents (20% en poids sec) sont introduits dans le mélange. La formulation est ensuite déposée sur un substrat et réticulée sous lampe UV. In contrast to the previous examples, the compositions of Examples 7 to 9 were not prepared from latex but from a crosslinkable resin based on acrylates (polyester acrylate and polyethylene glycol (PEG 400) acrylate - ratio 10: 90 by weight). The resin is mixed with a photoinitiator, then the intumescent agents (20% by dry weight) are introduced into the mixture. The formulation is then deposited on a substrate and crosslinked under a UV lamp.
Le tableau 1 ci-dessous résume la nature des compositions de revêtement et les propriétés des revêtements intumescents obtenus. La processabilité, prenant en compte la facilité de mise en œuvre de la composition et la qualité du revêtement obtenu, est notée comme suit : ® application impossible ; <S> application possible mais revêtement de mauvaise qualité ; O application possible et revêtement de bonne qualité. Table 1 below summarizes the nature of the coating compositions and the properties of intumescent coatings obtained. The processability, taking into account the ease of implementation of the composition and the quality of the coating obtained, is noted as follows: ® impossible application; <S> possible application but poor quality coating; O possible application and good quality coating.
Tableau 1 Table 1
Figure imgf000010_0001
Figure imgf000010_0001
n.m. : non mesurable  n.m. : Unmeasurable
Seule la composition de l’exemple 1 présente une bonne processabilité et permet d’obtenir un revêtement ayant à la fois des propriétés optiques et intumescentes satisfaisantes. Au contraire, les compositions de revêtement des exemples 2 et 3 ne permettent pas d’obtenir un revêtement présentent pas un flou et/ou une intumescente suffisante pour une application sur verre. Les compositions des exemples 4 à 9 ne présentent pas quant à elles une processabilité suffisante : pour les exemples 4 à 6, la composition gélifie rapidement empêchant toute application ; pour les exemples 7 à 9, le revêtement obtenu craquèle et/ou délamine après séchage et réticulation. Only the composition of Example 1 exhibits good processability and makes it possible to obtain a coating having both satisfactory optical and intumescent properties. On the contrary, the coating compositions of Examples 2 and 3 do not make it possible to obtain a coating that does not have a blur and / or intumescent sufficient for application to glass. The compositions of Examples 4 to 9 However, they do not exhibit sufficient processability: for Examples 4 to 6, the composition gels rapidly, preventing any application; for Examples 7 to 9, the coating obtained cracks and / or delaminates after drying and crosslinking.

Claims

REVENDICATIONS
1. Procédé de dépôt d’un revêtement intumescent organique sur une feuille de verre comprenant : A method of depositing an organic intumescent coating on a glass sheet comprising:
- la préparation d’une composition de revêtement intumescent organique par mélange d’un latex et d’un agent intumescent; et  the preparation of an organic intumescent coating composition by mixing a latex and an intumescent agent; and
- l’application de la composition de revêtement intumescent organique sur la feuille de verre ;  the application of the organic intumescent coating composition to the glass sheet;
caractérisé en ce que le latex présente un pH de 4 à 6 et l’agent intumescent est choisi parmi les acides polycarboxyliques thermodégradables. characterized in that the latex has a pH of 4 to 6 and the intumescent agent is selected from thermodegradable polycarboxylic acids.
2. Procédé selon la revendication 1, caractérisé en ce que le latex est une dispersion aqueuse d’un liant organique polymère dérivé de monomères vinyliques choisis parmi les a-alcènes tels que l’éthylène, le propylène ou l’isoprène, le chlorure de vinyle, le chlorure de vinylidène, le styrène, le vinyltoluène, l’acrylonitrile et les esters de vinyle.. 2. Method according to claim 1, characterized in that the latex is an aqueous dispersion of a polymeric organic binder derived from vinyl monomers selected from α-alkenes such as ethylene, propylene or isoprene, sodium chloride. vinyl, vinylidene chloride, styrene, vinyltoluene, acrylonitrile and vinyl esters.
3. Procédé selon la revendication 2, caractérisé en ce que le liant organique est un copolymère à base d’a-alcène, et d’un ou plusieurs esters de vinyle et/ou de chlorure de vinyle. 3. Method according to claim 2, characterized in that the organic binder is a copolymer based on α-alkene, and one or more vinyl esters and / or vinyl chloride.
4. Procédé selon l’une des revendications 1 à 3, caractérisé en ce que l’agent intumescent est choisi parmi l’acide oxalique, l’acide malonique, l’acide malique, l’acide tartrique, l’acide tartronique, l’acide maléique, l’acide citrique, l’acide tricarballylique et l’ acide 1 ,2,3 ,4-butanetétracarboxylique. 4. Method according to one of claims 1 to 3, characterized in that the intumescent agent is selected from oxalic acid, malonic acid, malic acid, tartaric acid, tartronic acid maleic acid, citric acid, tricarballylic acid and 1,2,3,4-butanetetracarboxylic acid.
5. Procédé selon l’une des revendications 1 à 4, caractérisé en ce que l’agent intumescent est l’acide citrique. 5. Method according to one of claims 1 to 4, characterized in that the intumescent agent is citric acid.
6. Procédé selon l’une des revendications 1 à 5, caractérisé en ce que la composition de revêtement comprend 5 à 50 % en poids sec d’agent intumescent. 6. Method according to one of claims 1 to 5, characterized in that the coating composition comprises 5 to 50% by dry weight of intumescent agent.
7. Procédé selon l’une des revendications 1 à 6, caractérisé en ce que la composition de revêtement comprend 0,5 à 15 % en poids sec d’un agent retardateur de flamme. 7. Method according to one of claims 1 to 6, characterized in that the coating composition comprises 0.5 to 15% by dry weight of a flame retardant agent.
8. Procédé selon la revendication 7, caractérisé en ce que l’agent retardateur de flamme est un composé organophosphoré. 8. Method according to claim 7, characterized in that the flame retardant is an organophosphorus compound.
9. Vitrage comprenant une feuille de verre revêtue d’un revêtement organique intumescent, notamment susceptible d’être obtenue par le procédé selon l’une des revendications 1 à 6, caractérisé en ce que le revêtement organique comprend un liant organique et un agent intumescent, ledit agent intumescent étant choisi parmi les acides polycarboxyliques thermodégradables. 9. Glazing comprising a glass sheet coated with an intumescent organic coating, in particular obtainable by the method according to one of claims 1 to 6, characterized in that the organic coating comprises an organic binder and an intumescent agent said intumescent agent being selected from thermodegradable polycarboxylic acids.
10. Vitrage selon la revendication 9, caractérisé en ce que ledit revêtement présente une transmission lumineuse totale supérieure à 85%. 10. Glazing according to claim 9, characterized in that said coating has a total light transmission greater than 85%.
11. Vitrage selon la revendication 9 ou 10, caractérisé en ce que ledit revêtement présente un flou inférieur à 15%. 11. Glazing according to claim 9 or 10, characterized in that said coating has a blur of less than 15%.
12. Vitrage selon l’une des revendications 9 à 11, caractérisé en ce que le liant organique est un homopolymère ou copolymère dérivé de monomères vinyliques choisis parmi les a-alcènes tels que l’éthylène, le propylène ou l’isoprène, le chlorure de vinyle, le chlorure de vinylidène, le styrène, le vinyltoluène, l’acrylonitrile et les esters de vinyle. 12. Glazing according to one of claims 9 to 11, characterized in that the organic binder is a homopolymer or copolymer derived from vinyl monomers selected from a-alkenes such as ethylene, propylene or isoprene, chloride vinylidene chloride, styrene, vinyltoluene, acrylonitrile and vinyl esters.
13. Vitrage selon l’une des revendications 9 à 12, caractérisé en ce que l’agent intumescent est choisi parmi l’acide oxalique, l’acide malonique, l’acide malique, l’acide tartrique, l’acide tartronique, l’acide maléique, l’acide citrique, l’acide tricarballylique et G acide 1 ,2,3 ,4-butanetétracarboxylique. 13. Glazing according to one of claims 9 to 12, characterized in that the intumescent agent is selected from oxalic acid, malonic acid, malic acid, acid tartaric acid, tartaric acid, maleic acid, citric acid, tricarballylic acid and 1, 2,3, 4-butanetetracarboxylic acid.
14. Vitrage selon l’une des revendications 9 à 13, caractérisé en ce que l’agent intumescent est l’acide citrique. 14. Glazing according to one of claims 9 to 13, characterized in that the intumescent agent is citric acid.
PCT/FR2019/050331 2018-02-16 2019-02-14 Method for depositing an organic intumescent coating on a glass sheet WO2019158866A1 (en)

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