EP1115793A1 - Bitumen and filled resin emulsion for road surfacing emulsion - Google Patents

Bitumen and filled resin emulsion for road surfacing emulsion

Info

Publication number
EP1115793A1
EP1115793A1 EP00949645A EP00949645A EP1115793A1 EP 1115793 A1 EP1115793 A1 EP 1115793A1 EP 00949645 A EP00949645 A EP 00949645A EP 00949645 A EP00949645 A EP 00949645A EP 1115793 A1 EP1115793 A1 EP 1115793A1
Authority
EP
European Patent Office
Prior art keywords
emulsion
resin
filler
composite
emulsion according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00949645A
Other languages
German (de)
French (fr)
Inventor
Graziella Durand
Eric Godard
Jean-François GAL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colas SA
Original Assignee
Colas SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colas SA filed Critical Colas SA
Publication of EP1115793A1 publication Critical patent/EP1115793A1/en
Withdrawn legal-status Critical Current

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/08—Coherent pavings made in situ made of road-metal and binders
    • E01C7/35—Toppings or surface dressings; Methods of mixing, impregnating, or spreading them
    • E01C7/358—Toppings or surface dressings; Methods of mixing, impregnating, or spreading them with a combination of two or more binders according to groups E01C7/351 - E01C7/356
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C08L95/005—Aqueous compositions, e.g. emulsions
    • 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
    • C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch
    • C09D195/005—Aqueous compositions, e.g. emulsions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a loaded composite emulsion based on a bituminous binder and one or more resin (s) for road surface protection layer against attack by petroleum derivatives.
  • the invention therefore has applications in civil and military engineering.
  • materials which have been soluble in organic solvents have hitherto been used, which gives the coating thus formed poor resistance to kerosene, organic oils, and hydrocarbons in general.
  • the road surface layers are susceptible to receiving such substances which damage them. It is therefore desirable to use materials which give the resulting coatings excellent chemical resistance to organic oils, kerosene and hydrocarbons in general, in particular for road coatings, industrial floors, parking lots, garages at service stations, airport runways, etc.
  • toxic products are meant in the present invention, a product which, by the carcinogenic substances which it contains, must be subjected to classification and labeling according to the regulations in force at present in France.
  • patent EP-231,417 describes an epoxy resin mixed with a bitumen emulsion and a crosslinking agent to improve its permeability to water vapor and its adhesion to metal.
  • it is a composition intended to modify the characteristics of the resin, which is in pasty, non-emulsified form and therefore difficult to manipulate.
  • Application FR-A-2,366,342 proposes a composition having the same constraints.
  • EP-695,788 belonging to the applicant, a composite emulsion giving a coating formed excellent chemical resistance to organic oils, kerosene and hydrocarbons in general, having no toxicity, neither during manufacture, nor during of its application, nor during the duration of its service, and free of solvent and any other substance likely to harm the environment.
  • This composite emulsion can be applied cold to a traffic surface on site.
  • This composite emulsion for surface layer or circulation surface is produced from a first emulsion comprising a bituminous binder and a crosslinking agent and a second emulsion comprising a resin.
  • the bituminous binder and the resin are therefore each used in the form of an emulsion in water.
  • the present invention proposes to remedy these drawbacks by means of a bitumen / resin composite emulsion for a surface protection layer for road surfaces against attacks by petroleum derivatives produced from the mixture of a first emulsion comprising at least one resin with a second. emulsion comprising a bituminous binder and a resin crosslinking agent.
  • This type of protection is also called A.K.
  • the composite emulsion further comprises a filler, said filler comprising individually or in combination at least one of the following elements defined by standard XP P 18-540:
  • combination corresponds to all possible mixtures of the three charge elements.
  • the filler is mineral.
  • the filler is siliceous.
  • the rate of the charge is between 10 and 90% by weight in the charged composite emulsion.
  • the rate of the charge is preferably between 25 and 50% by weight in the charged composite emulsion.
  • the charge rate is optimized at 35% plus or minus 5% by weight in the charged composite emulsion.
  • the filler is incorporated into the emulsion comprising the bituminous binder.
  • the filler is incorporated into the emulsion comprising resin.
  • the filler is incorporated into the composite emulsion.
  • the loaded composite emulsion further comprises a pigment preparation.
  • the pigment preparation is a liquid, solid or pasty coloring product and preferably of dark coloring.
  • the rate of the pigment preparation is between 0.05 and 2% by weight, the percentage being calculated relative to the composite emulsion loaded outside the weight of the load.
  • the coloring product is incorporated into the emulsion comprising the bituminous binder.
  • the coloring product is incorporated into the emulsion comprising resin.
  • the coloring product is incorporated into the filler.
  • the coloring product is incorporated into the composite emulsion.
  • the resin is of the epoxy type.
  • the resin is chosen from liquid epoxy resins and solid emulsified epoxy resins. - one or more resins with known rheological properties are used in the emulsion comprising resin to adjust the rheological behavior of the loaded composite emulsion.
  • one or more liquid resins are associated with one or more solid resins in the emulsion comprising resin.
  • one or more solid emulsified epoxy resins are used in the emulsion comprising resin.
  • the crosslinking agent is in excess relative to the stoichiometry in the emulsion comprising the bituminous binder.
  • the crosslinking agent is introduced at a rate of 1.7 to 1.1 times relative to the stoichiometry.
  • the crosslinking is fully ensured compared to the case where the crosslinking agent is provided in a stoichiometric ratio. Indeed, part of the crosslinking agent is made inactive to ensure crosslinking because it is trapped by the other constituents of the loaded composite emulsion.
  • the percentage of resin in the emulsion containing resin can reach 80% by weight.
  • the percentage of resin in the emulsion comprising the resin is preferably between 50% and 80% by weight.
  • the loaded composite emulsion is used for producing a thin film type surface coating produced in one or more layers.
  • each new layer can only be applied after drying and polymerization of the previous layer.
  • the thickness of a layer is between 0.1 and 2 mm.
  • the thickness of a layer is preferably between 0.5 and 1.2 mm.
  • the loaded composite emulsion is used at a rate of 500 g / m 2 to 1 kg / m 2 ; - several fillers are used;
  • Bituminous binder is understood to mean a binder, either consisting of bitumen alone, or modified by the addition of a polymer, or fluidized by an oil. This term is retained when a crosslinking agent is incorporated into this product.
  • the term “resin” denotes any chemical entity which, by reaction with an appropriate crosslinking agent, leads to the production of a three-dimensional molecular network. These are two-component systems. They are chosen so that this system is active at room temperature. Of course, the nature of the crosslinking agent depends on the nature of the resin used. These resins are epoxy type resins.
  • Epoxy type resins are liquid or solid resins.
  • these are linear epoxy resins. They are conventionally obtained by polycondensation in an alkaline medium of a bisphenol A or F derivative and of epichlorohydrin. This derivative is preferably diglicydylether of bisphenol A.
  • Softer epoxy resins can be obtained from polyglycol derivatives. It is also possible, within the framework of the invention, to use a mixture of two or more different epoxy resins. These epoxy functional resins react with a chemical compound which is an amino functional crosslinking agent; this reaction takes place at room temperature (10 ° C ⁇ t o ⁇ 60 ° C).
  • the stoichiometry for the crosslinking reaction with the epoxy resin and the crosslinking agent corresponds to bringing the epoxy function of the resin into contact with an active hydrogen of the crosslinking agent.
  • the loaded composite emulsion has better behavior against environmental cycles because it has a reduced coefficient of thermal expansion. It has mechanical resistance to improved traffic. It has a lower manufacturing and implementation cost. It is more manageable because the polymerization time is extended, which lengthens the period of workability. Finally, it is simple to use, the end user only having to mix two products, or even three products in the case where the filler is not additive beforehand in one of the two emulsions. In the latter case, the two emulsions are sufficiently fluid to be pumped separately.
  • FIG. 1 represents the results of a comparative test.
  • a thin protective film is produced placed on a bituminous mix or any other support to be protected against chemical attack.
  • the products necessary for producing the thin film are in the form of a kit for three components which are the two emulsions and the filler.
  • the loaded composite emulsion is produced by mixing a first emulsion comprising the bituminous binder and the crosslinking agent with a second emulsion comprising resin and with the filler. After application in a layer of the loaded composite emulsion and chemical reaction (crosslinking), a protection of 0.1 to 2 mm thick depending on the dosage is obtained. The protection is intended to prevent contact between an aggressive agent and the underlying coating.
  • a comparative test was carried out in order to compare the resistance of a composite emulsion loaded according to the invention and an emulsion of coal pitch with a protective vocation AK
  • a first group of plates in duralumin® was covered by the emulsion of the invention and a second group by the coal pitch.
  • the plates were placed for 4 and 48 hours in kerosene and the mass loss was measured.
  • the following graph gives the value of the mass loss in%. It can be seen that the emulsion according to the invention has a much higher resistance.
  • curve E corresponds to the emulsion of the invention and curve B to pitch.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Architecture (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Road Paving Structures (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention concerns a composite bitumen/resin emulsion for producing a layer to protect road surfaces against damage caused by oil derivatives, produced from a first emulsion comprising a resin and a second emulsion comprising a bituminous binder and a resin hardener. A pigment preparation and/or a filling agent consisting of a filler or sand or fine sand or combinations thereof can be incorporated in the first emulsion, the second emulsion or in the composite emulsion resulting from the mixture of the two emulsions. The filled composite emulsion enables to produce road surfaces of thin films in one or several layers.

Description

Emulsion de bitume et de résine chargée pour revêtement routier Bitumen and resin filled emulsion for road surfaces
La présente invention concerne une emulsion composite chargée à base d'un liant bitumineux et d'une ou plusieurs résine(s) pour couche de protection de surface de chaussées contre les agressions des dérivés du pétrole. L'invention a donc des applications en génie civil et militaire. Pour la fabrication de couches de surface de chaussées, on a jusqu'à présent utilisé des matériaux solubles dans des solvants organiques, ce qui confère au revêtement ainsi formé une mauvaise résistance au kérosène, aux huiles organiques, et aux hydrocarbures en général. Or, les couches de surface de chaussées sont susceptibles de recevoir de telles substances qui les endommagent. Il est donc souhaitable d'utiliser des matériaux conférant aux revêtements résultants une excellente résistance chimique aux huiles organiques, au kérosène et aux hydrocarbures en général, en particulier pour les revêtements de routes, de sols industriels, de parkings, de garages à stations services, de pistes d'aéroports, etc.. La plupart des emulsions connues de l'art antérieur, formulées à cet effet contiennent une proportion importante de goudrons ou de tout autre produit issu de la houille et sont reconnues comme toxiques. Par produits toxiques, on entend dans la présente invention, un produit qui, de par les substances cancérigènes qu'il contient, doit être soumis à une classification et à un étiquetage selon la réglementation en vigueur actuellement en France.The present invention relates to a loaded composite emulsion based on a bituminous binder and one or more resin (s) for road surface protection layer against attack by petroleum derivatives. The invention therefore has applications in civil and military engineering. For the manufacture of road surface layers, materials which have been soluble in organic solvents have hitherto been used, which gives the coating thus formed poor resistance to kerosene, organic oils, and hydrocarbons in general. However, the road surface layers are susceptible to receiving such substances which damage them. It is therefore desirable to use materials which give the resulting coatings excellent chemical resistance to organic oils, kerosene and hydrocarbons in general, in particular for road coatings, industrial floors, parking lots, garages at service stations, airport runways, etc. Most of the emulsions known from the prior art, formulated for this purpose contain a large proportion of tars or any other product obtained from coal and are recognized as toxic. By toxic products is meant in the present invention, a product which, by the carcinogenic substances which it contains, must be subjected to classification and labeling according to the regulations in force at present in France.
A ce jour, les produits à base de bitume et de résine sont compatibilisés par l'adjonction d'un troisième composant qui est un solvant dont l'évaporation après application à chaud contribue à nuire l'environnement.To date, products based on bitumen and resin are compatibilized by the addition of a third component which is a solvent whose evaporation after hot application contributes to harm the environment.
Par ailleurs, le brevet EP-231.417 décrit une résine époxy mélangée à une emulsion de bitume et à un agent réticulant pour améliorer sa perméabilité à la vapeur d'eau et son adhérence au métal. Mais il s'agit d'une composition destinée à modifier les caractéristiques de la résine, qui est sous forme pâteuse non émulsionnée et donc difficilement maπipulable.Furthermore, patent EP-231,417 describes an epoxy resin mixed with a bitumen emulsion and a crosslinking agent to improve its permeability to water vapor and its adhesion to metal. However, it is a composition intended to modify the characteristics of the resin, which is in pasty, non-emulsified form and therefore difficult to manipulate.
La demande FR-A-2.366.342 propose une composition présentant les mêmes contraintes.Application FR-A-2,366,342 proposes a composition having the same constraints.
On connaît aussi par EP-695.788 appartenant à la demanderesse, une emulsion composite conférant à un revêtement formé une excellente résistance chimique aux huiles organiques, au kérosène et aux hydrocarbures en général, ne présentant aucune toxicité, ni en cours de fabrication, ni au cours de son application, ni pendant la durée de son service, et exempte de solvant et de tout autre substance susceptible de nuire à l'environnement. Cette emulsion composite peut être appliquée à froid sur une surface de circulation en chantier. Cette emulsion composite pour couche de roulement ou de surface de circulation est réalisée à partir d'une première emulsion comportant un liant bitumineux et un agent réticulant et une seconde emulsion comportant une résine. Le liant bitumineux et la résine sont donc chacun mis en oeuvre sous forme d'une emulsion dans l'eau.Also known from EP-695,788 belonging to the applicant, a composite emulsion giving a coating formed excellent chemical resistance to organic oils, kerosene and hydrocarbons in general, having no toxicity, neither during manufacture, nor during of its application, nor during the duration of its service, and free of solvent and any other substance likely to harm the environment. This composite emulsion can be applied cold to a traffic surface on site. This composite emulsion for surface layer or circulation surface is produced from a first emulsion comprising a bituminous binder and a crosslinking agent and a second emulsion comprising a resin. The bituminous binder and the resin are therefore each used in the form of an emulsion in water.
Cependant, la tenue d'une telle emulsion composite au cours du temps et/ou lorsqu'elle est soumise aux cycles environnementaux (variation de température, d'humidité...) et au trafic n'est pas optimale. Il se produit des décollements de la couche par rapport au support, des craquelures. Ces défauts entraînent une dégradation du support qui est alors directement soumis à l'environnement. Par ailleurs, la couleur noire résiduelle de l'émulsion composite appliquée en film mince évolue au cours du temps, notamment du fait de l'attaque des rayons ultraviolets solaires du fait de la présence de résine époxy : le film s'éclaircit, jaunit, ternit, jusqu'à devenir parfois translucide. Cette évolution de l'aspect dans le temps peut poser problème dans certains cas de figure.However, the behavior of such a composite emulsion over time and / or when it is subjected to environmental cycles (variation of temperature, humidity, etc.) and to traffic is not optimal. There is separation of the layer from the support, cracks. These defects cause degradation of the support which is then directly subjected to the environment. In addition, the residual black color of the composite emulsion applied as a thin film changes over time, in particular due to the attack of solar ultraviolet rays due to the presence of epoxy resin: the film lightens, yellows, tarnishes, sometimes becoming translucent. This change in appearance over time can be problematic in certain cases.
La présente invention propose de remédier à ces inconvénients grâce à une emulsion composite bitume/résine pour couche de protection de surface de chaussées contre les agressions des dérivés du pétrole réalisée à partir du mélange d'une première emulsion comportant au moins une résine avec une seconde emulsion comportant un liant bitumineux et un agent réticulant de la résine. Ce type de protection est aussi dite A.K. Selon l'invention, l'émulsion composite comporte en outre une charge, ladite charge comportant isolément ou en combinaison au moins un des éléments suivants définis par la norme XP P 18-540:The present invention proposes to remedy these drawbacks by means of a bitumen / resin composite emulsion for a surface protection layer for road surfaces against attacks by petroleum derivatives produced from the mixture of a first emulsion comprising at least one resin with a second. emulsion comprising a bituminous binder and a resin crosslinking agent. This type of protection is also called A.K. According to the invention, the composite emulsion further comprises a filler, said filler comprising individually or in combination at least one of the following elements defined by standard XP P 18-540:
- un filler;- a filler;
- un sable; - un sablon.- a sand; - a sablon.
Le terme combinaison correspond à tous les mélanges possibles des trois éléments de charge.The term combination corresponds to all possible mixtures of the three charge elements.
Selon la norme XP P 18-540 on définit les familles suivantes: pour les fillers 0/D: D < 2 mm avec au moins 70% de passant à 0,063 mm; pour les sablons 0/D: D < 1 mm avec moins de 70% de passant à 0,063 mm; pour les sables 0/D: 1 < D < 6,3 mm.According to the XP P 18-540 standard, the following families are defined: for 0 / D fillers: D <2 mm with at least 70% passing to 0.063 mm; for 0 / D sand bars: D <1 mm with less than 70% passing to 0.063 mm; for sands 0 / D: 1 <D <6.3 mm.
Où D est la plus grande de dimensions du produit.Where D is the largest dimension of the product.
Dans diverses formes de mise en oeuvre de l'invention, les moyens suivants peuvent être mis en oeuvre, isolément ou selon toutes leurs combinaisons techniquement possibles :In various embodiments of the invention, the following means can be implemented, alone or in any technically possible combination:
- la charge est minérale.- the filler is mineral.
- la charge est siliceuse.- the filler is siliceous.
- le taux de la charge est compris entre 10 et 90 % en poids dans l'émulsion composite chargée . - le taux de la charge est préférentiellement compris entre 25 et 50 % en poids dans l'émulsion composite chargée .- The rate of the charge is between 10 and 90% by weight in the charged composite emulsion. - The rate of the charge is preferably between 25 and 50% by weight in the charged composite emulsion.
- le taux de la charge est optimisé à 35 % plus ou moins 5 % en poids dans l'émulsion composite chargée .- The charge rate is optimized at 35% plus or minus 5% by weight in the charged composite emulsion.
- la charge est incorporée dans l'émulsion comportant le liant bitumineux.- The filler is incorporated into the emulsion comprising the bituminous binder.
- la charge est incorporée dans l'émulsion comportant de la résine.- The filler is incorporated into the emulsion comprising resin.
- la charge est incorporée dans l'émulsion composite.- the filler is incorporated into the composite emulsion.
- l'émulsion composite chargée comporte en outre une préparation pigmentaire. - la préparation pigmentaire est un produit de coloration liquide, solide ou pâteux et de préférence de coloration sombre.- The loaded composite emulsion further comprises a pigment preparation. - the pigment preparation is a liquid, solid or pasty coloring product and preferably of dark coloring.
- le taux de la préparation pigmentaire est compris entre 0,05 et 2 % en poids, le pourcentage étant calculé par rapport à l'émulsion composite chargée hors du poids de la charge. - le produit de coloration est incorporé dans l'émulsion comportant le liant bitumineux.- The rate of the pigment preparation is between 0.05 and 2% by weight, the percentage being calculated relative to the composite emulsion loaded outside the weight of the load. - the coloring product is incorporated into the emulsion comprising the bituminous binder.
- le produit de coloration est incorporé dans l'émulsion comportant de la résine.- the coloring product is incorporated into the emulsion comprising resin.
- le produit de coloration est incorporé dans la charge. - le produit de coloration est incorporé dans l'émulsion composite.- the coloring product is incorporated into the filler. - the coloring product is incorporated into the composite emulsion.
- la résine est du type époxy.- the resin is of the epoxy type.
- la résine est choisie parmi les résines époxy liquides et les résines époxy solides émulsionnées. - une ou plusieurs résines à propriétés rhéologiques connues sont utilisées dans l'émulsion comportant de la résine pour ajuster le comportement rhéologique de l'émulsion composite chargée.the resin is chosen from liquid epoxy resins and solid emulsified epoxy resins. - one or more resins with known rheological properties are used in the emulsion comprising resin to adjust the rheological behavior of the loaded composite emulsion.
- une ou plusieurs résines liquides sont associées à une ou plusieurs résines solides dans l'émulsion comportant de la résine.one or more liquid resins are associated with one or more solid resins in the emulsion comprising resin.
- une ou plusieurs résines époxy solides émulsionnées sont utilisées dans l'émulsion comportant de la résine.- one or more solid emulsified epoxy resins are used in the emulsion comprising resin.
- l'agent réticulant est en excès par rapport à la stoechiométrie dans l'émulsion comportant le liant bitumineux. - l'agent réticulant est introduit à raison de 1 ,7 à 1,1 fois par rapport à la stoechiométrie. Lors de la réalisation de l'émulsion composite chargée, la réticulation est pleinement assurée par rapport au cas où l'agent réticulant est apporté dans un rapport stoechiometrique. En effet, une partie de l'agent de réticulation est rendue inactive pour assurer la réticulation car piégée par les autres constituants de l'émulsion composite chargée.- The crosslinking agent is in excess relative to the stoichiometry in the emulsion comprising the bituminous binder. - The crosslinking agent is introduced at a rate of 1.7 to 1.1 times relative to the stoichiometry. During the production of the loaded composite emulsion, the crosslinking is fully ensured compared to the case where the crosslinking agent is provided in a stoichiometric ratio. Indeed, part of the crosslinking agent is made inactive to ensure crosslinking because it is trapped by the other constituents of the loaded composite emulsion.
- le pourcentage de résine dans l'émulsion comportant de la résine peut atteindre 80 % en poids.- The percentage of resin in the emulsion containing resin can reach 80% by weight.
- le pourcentage de résine dans l'émulsion comportant de la résine est préférentiellement compris entre 50 % et 80 % en poids. - l'émulsion composite chargée est mise en oeuvre pour la réalisation d'un revêtement de surface du type film mince réalisé en une ou plusieurs couches.- The percentage of resin in the emulsion comprising the resin is preferably between 50% and 80% by weight. - The loaded composite emulsion is used for producing a thin film type surface coating produced in one or more layers.
- dans le cas de plusieurs couches, chaque nouvelle couche ne peut être appliquée qu'après séchage et polymérisation de la couche précédente. - l'épaisseur d'une couche est comprise entre 0,1 et 2 mm.- in the case of several layers, each new layer can only be applied after drying and polymerization of the previous layer. - the thickness of a layer is between 0.1 and 2 mm.
- l'épaisseur d'une couche est préférentiellement comprise entre 0,5 et 1 ,2 mm.- The thickness of a layer is preferably between 0.5 and 1.2 mm.
- l'émulsion composite chargée est mise en œuvre à raison de 500 g/m2 à 1 kg/m2 ; - plusieurs fillers sont utilisés;- The loaded composite emulsion is used at a rate of 500 g / m 2 to 1 kg / m 2 ; - several fillers are used;
- plusieurs sablons sont utilisés;- several sablons are used;
- plusieurs sables sont utilisés.- several sands are used.
On entend par liant bitumineux un liant, soit constitué de bitume seul, soit modifié par l'addition d'un polymère, soit fluidifié par une huile. Ce terme est conservé lorsqu'à ce produit est incorporé un agent réticulant. On désigne par résine toute entité chimique qui, par réaction avec un agent réticulant approprié, conduit à l'obtention d'un réseau moléculaire tridimensionnel. Il s'agit de systèmes à deux composants. Ils sont choisis de telle sorte que ce système soit actif à température ambiante. Bien entendu, la nature de l'agent réticulant dépend de la nature de la résine employée. Ces résines sont des résines de type époxy.Bituminous binder is understood to mean a binder, either consisting of bitumen alone, or modified by the addition of a polymer, or fluidized by an oil. This term is retained when a crosslinking agent is incorporated into this product. The term “resin” denotes any chemical entity which, by reaction with an appropriate crosslinking agent, leads to the production of a three-dimensional molecular network. These are two-component systems. They are chosen so that this system is active at room temperature. Of course, the nature of the crosslinking agent depends on the nature of the resin used. These resins are epoxy type resins.
Les résines de type époxy sont des résines liquides ou solides. Avantageusement, il s'agit de résines époxy linéaires. Elles sont classiquement obtenues par polycondensation en milieu alcalin d'un dérivé de bisphénol A ou F et de l'epichlorhydrine. Ce dérivé est de préférence du diglicydylether de bisphénol A. Des résines époxy plus souples peuvent être obtenues à partir de dérivés polyglycolés. On peut aussi utiliser, dans le cadre de l'invention, un mélange de deux ou plusieurs résines époxy différentes. Ces résines à fonctionnalité époxydique réagissent avec un composé chimique qui est un agent réticulant à fonctionnalités aminées ; cette réaction s'opère à température ambiante (10°C<to<60°C).Epoxy type resins are liquid or solid resins. Advantageously, these are linear epoxy resins. They are conventionally obtained by polycondensation in an alkaline medium of a bisphenol A or F derivative and of epichlorohydrin. This derivative is preferably diglicydylether of bisphenol A. Softer epoxy resins can be obtained from polyglycol derivatives. It is also possible, within the framework of the invention, to use a mixture of two or more different epoxy resins. These epoxy functional resins react with a chemical compound which is an amino functional crosslinking agent; this reaction takes place at room temperature (10 ° C <t o <60 ° C).
La stoechiométrie pour la réaction de réticulation avec la résine époxy et l'agent réticulant, correspond à la mise en présence d'une fonction époxyde de la résine avec un hydrogène actif de l'agent réticulant. L'émulsion composite chargée a un meilleur comportement face aux cycles environnementaux car elle a un coefficient de dilatation thermique réduit. Elle présente une résistance mécanique au trafic amélioré. Elle présente un coût de fabrication et de mise en oeuvre moindre. Elle est plus maniable car le temps de polymérisation est allongé, ce qui allonge la période d'ouvrabilite. Enfin, elle est simple d'utilisation, l'utilisateur final n'ayant qu'à mélanger deux produits, voire trois produits dans le cas où la charge n'est pas additivée au préalable dans l'une des deux emulsions. Dans ce dernier cas de figure, les deux emulsions sont suffisamment fluides pour être pompées séparément. La présente invention sera mieux comprise par la description détaillée d'un exemple de mise en œuvre d'émulsion composite chargée et où la figure 1 représente les résultats d'un test comparatif.The stoichiometry for the crosslinking reaction with the epoxy resin and the crosslinking agent, corresponds to bringing the epoxy function of the resin into contact with an active hydrogen of the crosslinking agent. The loaded composite emulsion has better behavior against environmental cycles because it has a reduced coefficient of thermal expansion. It has mechanical resistance to improved traffic. It has a lower manufacturing and implementation cost. It is more manageable because the polymerization time is extended, which lengthens the period of workability. Finally, it is simple to use, the end user only having to mix two products, or even three products in the case where the filler is not additive beforehand in one of the two emulsions. In the latter case, the two emulsions are sufficiently fluid to be pumped separately. The present invention will be better understood from the detailed description of an example of implementation of a loaded composite emulsion and in which FIG. 1 represents the results of a comparative test.
On réalise un film mince de protection placé sur un enrobé bitumineux ou tout autre support à protéger contre des agressions chimiques. Les produits nécessaires à la réalisation du film mince se présentent sous forme d'un kit à trois composants qui sont les deux emulsions et la charge. L'émulsion composite chargée est réalisée par le mélange d'une première emulsion comportant le liant bitumineux et l'agent réticulant avec une seconde emulsion comportant de la résine et avec la charge. Après application en une couche de l'émulsion composite chargée et réaction chimique (réticulation), une protection de 0,1 à 2 mm d'épaisseur selon le dosage est obtenue. La protection est destinée à empêcher le contact entre un agent agressif et le revêtement sous- jacent.A thin protective film is produced placed on a bituminous mix or any other support to be protected against chemical attack. The products necessary for producing the thin film are in the form of a kit for three components which are the two emulsions and the filler. The loaded composite emulsion is produced by mixing a first emulsion comprising the bituminous binder and the crosslinking agent with a second emulsion comprising resin and with the filler. After application in a layer of the loaded composite emulsion and chemical reaction (crosslinking), a protection of 0.1 to 2 mm thick depending on the dosage is obtained. The protection is intended to prevent contact between an aggressive agent and the underlying coating.
Un test comparatif a été réalisé afin de comparer la résistance d'une emulsion composite chargée selon l'invention et une emulsion de brai de houille à vocation de protection A.K. Un premier groupe de plaques en duralumin ® a été recouvert par l'émulsion de l'invention et un second groupe par le brai de houille. Les plaques ont été placées pendant 4 et 48 heures dans du kérosène et la perte de masse a été mesurée. Le graphique suivant donne la valeur de la perte de masse en %. On peut constater que l'émulsion selon l'invention présente une résistance bien supérieure. Sur la figure 1 la courbe E correspond à l'émulsion de l'invention et la courbe B au brai.A comparative test was carried out in order to compare the resistance of a composite emulsion loaded according to the invention and an emulsion of coal pitch with a protective vocation AK A first group of plates in duralumin® was covered by the emulsion of the invention and a second group by the coal pitch. The plates were placed for 4 and 48 hours in kerosene and the mass loss was measured. The following graph gives the value of the mass loss in%. It can be seen that the emulsion according to the invention has a much higher resistance. In FIG. 1, curve E corresponds to the emulsion of the invention and curve B to pitch.
Cet exemple de mise en œuvre et d'utilisation est donné à titre illustratif et non limitatif de la présente invention. La présentation de ces deux emulsions et de la charge pourra varier en fonction du volume et de la destination finale de l'émulsion composite chargée ainsi réalisée. En particulier dans le cas d'un kit de préparation le nombre de composants pourra être quelconque et non pas limité à 3 comme dans l'un des exemples. Ainsi un kit à deux composants est envisageable, la charge étant préalablement incluse dans l'une, voire les deux emulsions. Par ailleurs plusieurs fillers et/ou sablons et/ou sables d'origine différente, par exemple organique et/ou minéral, éolien et/ou maritime, siiicieux et/ou carboné peuvent être combinés en fonction des disponibilités et/ou avantages particuliers. This example of implementation and use is given by way of illustration and without limitation of the present invention. The presentation of these two emulsions and the charge may vary depending on the volume and the final destination of the charged composite emulsion thus produced. In particular in the case of a preparation kit, the number of components may be any and not limited to 3 as in one of the examples. Thus a two-component kit can be envisaged, the filler being previously included in one, or even the two emulsions. In addition, several fillers and / or sand and / or sands of different origin, for example organic and / or mineral, wind and / or maritime, siiicious and / or carbonaceous can be combined according to availability and / or particular advantages.

Claims

REVENDICATIONS
1. Emulsion composite bitume/résine pour couche de protection de surface de chaussées contre les agressions des dérivés du pétrole réalisée à partir du mélange d'une première emulsion comportant au moins une résine avec une seconde emulsion comportant un liant bitumineux et un agent réticulant de la résine, caractérisé en ce que l'émulsion composite comporte en outre une charge, ladite charge comportant isolément ou en combinaison au moins un des éléments suivants définis par la norme XP P 18-540:1. Bitumen / resin composite emulsion for road surface protection layer against attack by petroleum derivatives produced from the mixture of a first emulsion comprising at least one resin with a second emulsion comprising a bituminous binder and a crosslinking agent the resin, characterized in that the composite emulsion further comprises a filler, said filler comprising individually or in combination at least one of the following elements defined by standard XP P 18-540:
- un filler; - un sable;- a filler; - a sand;
- un sablon.- a sablon.
2. Emulsion selon la revendication 1 caractérisée en ce que le taux de la charge est compris entre 10 et 90 % en poids dans l'émulsion composite chargée et est préférentiellement compris entre 25 et 50 % en poids dans l'émulsion composite chargée .2. Emulsion according to claim 1 characterized in that the content of the filler is between 10 and 90% by weight in the loaded composite emulsion and is preferably between 25 and 50% by weight in the loaded composite emulsion.
3. Emulsion selon la revendication 1 ou 2 caractérisée en ce que la charge est siliceuse.3. Emulsion according to claim 1 or 2 characterized in that the filler is siliceous.
4. Emulsion selon l'une quelconque des revendications précédentes caractérisée en ce qu'elle comporte en outre une préparation pigmentaire. 4. Emulsion according to any one of the preceding claims, characterized in that it also comprises a pigment preparation.
5. Emulsion selon la revendication 4 caractérisée en ce que le taux de la préparation pigmentaire est compris entre 0,05 et 2% en poids, le pourcentage étant calculé par rapport à l'émulsion composite chargée hors du poids de la charge.5. Emulsion according to claim 4 characterized in that the rate of the pigment preparation is between 0.05 and 2% by weight, the percentage being calculated relative to the composite emulsion loaded outside the weight of the load.
6. Emulsion selon l'une quelconque des revendication précédentes, caractérisée en ce que la charge est incorporée dans l'émulsion comportant le liant bitumineux.6. Emulsion according to any one of the preceding claims, characterized in that the filler is incorporated in the emulsion comprising the bituminous binder.
7. Emulsion selon l'une quelconque des revendications précédentes, caractérisée en ce que la charge est incorporée dans l'émulsion comportant de la résine. 7. Emulsion according to any one of the preceding claims, characterized in that the filler is incorporated in the emulsion comprising resin.
8. Emulsion selon l'une quelconque des revendications 1 à 5, caractérisée en ce que la charge est incorporée dans l'émulsion composite.8. Emulsion according to any one of claims 1 to 5, characterized in that the filler is incorporated in the composite emulsion.
9. Emulsion selon l'une quelconque des revendications précédentes caractérisée en ce que la résine est du type époxy et est choisie parmi les résines époxy liquides et les résines époxy solides émulsioπnées. 9. Emulsion according to any one of the preceding claims, characterized in that the resin is of the epoxy type and is chosen from liquid epoxy resins and solid emulsified epoxy resins.
10. Emulsion selon l'une quelconque des revendications précédentes caractérisée en ce que l'agent réticulant est introduit à raison de 1 ,7 à 1 ,1 fois par rapport à la stoechiométrie.10. Emulsion according to any one of the preceding claims, characterized in that the crosslinking agent is introduced in an amount of 1.7 to 1.1 times compared to the stoichiometry.
11. Emulsion selon l'une quelconque des revendications précédentes caractérisée en ce que le pourcentage de résine dans l'émulsion comportant de la résine peut atteindre 80 % en poids.11. Emulsion according to any one of the preceding claims, characterized in that the percentage of resin in the emulsion comprising resin can reach 80% by weight.
12. Emulsion selon l'une quelconque des revendications précédentes caractérisée en ce qu'elle est mise en œuvre pour la réalisation d'un film mince en une ou plusieurs couches, l'épaisseur d'une couche étant comprise entre 0,1 à 2 mm. 12. Emulsion according to any one of the preceding claims, characterized in that it is used for producing a thin film in one or more layers, the thickness of a layer being between 0.1 to 2 mm.
EP00949645A 1999-07-05 2000-07-05 Bitumen and filled resin emulsion for road surfacing emulsion Withdrawn EP1115793A1 (en)

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FR9908658A FR2796075B1 (en) 1999-07-05 1999-07-05 BITUMEN AND RESIN LOADED EMULSION FOR ROAD COVERING
FR9908658 1999-07-05
PCT/FR2000/001934 WO2001002491A1 (en) 1999-07-05 2000-07-05 Bitumen and filled resin emulsion for road surfacing emulsion

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