Clear link and its applications

Abstract

Clear binder and its applications. Composition of clear binder comprising: (i) a plasticizing agent comprising at least one petroleum or synthetic hydrocarbon oil, (ii) a structuring agent comprising at least one plant-derived resin selected from natural rosins, modified rosins, rosin esters, and any mixture thereof, said plant-derived resin having an acidity value, determined according to ASTM D465, of 40 mg KOH / g or less, (iii) at least one polymer based on conjugated diene units and aromatic monovinyl hydrocarbon units, and (iv) optionally an adhesion enhancer. Figure for the abstract: None

Description

Description Title of the invention: Clear binder and its applications Technical field The present invention relates to a clear binder and its uses in road and / or industrial applications, in particular for the production of colored surface coating compositions. State of the prior art Conventional bituminous binders, due to the presence of asphaltenes, are black in color and are therefore difficult to color. Colored coatings are increasingly used because, among other things, they improve the safety of road users by clearly identifying specific routes such as pedestrian paths, cycle paths, and bus lanes. They also make it possible to mark certain danger zones such as city entrances or dangerous bends. Colored coatings improve visibility in low-light conditions, for example at night or in specific locations such as tunnels. Finally, they simply improve the aesthetic appearance of urban roads and can be used for public squares, building and school courtyards, sidewalks, pedestrian streets, garden and park paths, parking and rest areas. Therefore, for all the above applications, it is preferred to use clear synthetic binders, which do not contain asphaltenes and can be colored. The clear binders of the prior art generally consist of a plasticizing agent, for example an oil of petroleum origin, a structuring agent, for example a hydrocarbon resin, and a polymer. Application WO2018 / 046838 discloses a cold-solid clear binder. In particular, it describes a clear binder containing a synthetic oil from deasphalting unit cuts (DAO) and a copolymer based on butadiene and styrene units, for example an SB or SBS copolymer. Application WO2018 / 115729 discloses a cold-solid binder composition. In particular, the composition may be a clear binder and the plasticizing agent is in particular an oil of petroleum origin. Application WO2018 / 115730 describes a similar composition for the preparation of poured asphalts and the production of coatings. Document US2002 / 052431 discloses aqueous emulsions comprising on the one hand a clear synthetic binder and on the other hand a latex. During manufacture, and then in implementation, these binders are subjected to different types of external factors which modify their structure and cause their properties to evolve. Clear binders with a reduced environmental footprint compared to Clear binders discussed above have also been developed by seeking to at least partially substitute the plasticizing agent and / or the structuring agent with constituents of plant origin. Application FEP3081599 describes, for example, a binder of plant origin based on modified tall oil pitch, a modified resin and possibly a polymer. These clear binders are not, however, entirely satisfactory. Although they do indeed have a reduced environmental footprint compared to traditional clear binders, they present sustainability issues. Indeed, currently available clear binders incorporating a plasticizing agent and / or a structuring agent of plant origin have significantly reduced resistance to aging compared to traditional clear binders prepared from petroleum-based products. In particular, these binders prepared from plant-based compounds have significantly reduced resistance to aging of cold properties compared to traditional clear binders prepared from petroleum-based products. More regular replacement of road surfaces is therefore to be expected, which significantly reduces their environmental value. There is therefore still a need for bio-sourced clear binders, particularly those prepared from a structuring agent of plant origin, with improved mechanical properties compared to existing bio-sourced clear binders. In particular, there remains a need for bio-sourced clear binders (prepared from at least one structuring agent of plant origin) with improved resistance to aging, in particular resistance to aging of cold properties, compared to the bio-sourced clear binders currently available. In particular, there remains a need for bio-sourced clear binders (prepared from at least one structuring agent of plant origin) with equivalent, or even improved, properties compared to traditional clear binders prepared from a petroleum-based oil and a petroleum-based resin. More particularly, there remains a need for bio-sourced clear binders (prepared from at least one structuring agent of plant origin) exhibiting resistance to aging, in particular resistance to aging of cold properties, equivalent to, or even improved, compared to traditional clear binders prepared from an oil of petroleum origin and a resin of petroleum origin. Surprisingly, it has been found that the combination of (i) a hydrocarbon oil of petroleum or synthetic origin and (ii) a resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and their mixtures and whose acidity index, determined according to the ASTM D465 method, is less than or equal to 40 mg KOH / g made it possible to obtain a bio-sourced clear binder having improved properties compared to the bio-sourced clear binders of the prior art. In particular, the clear binders of the invention have better resistance to aging of their properties, in particular better resistance to aging of the cold properties, compared to the bio-sourced clear binders of the prior art. More particularly, it was found that this particular association made it possible to obtain a clear binder having similar, or even improved, properties compared to those of traditional clear binders, obtained from compounds of petroleum origin, in particular a resistance to aging of similar cold properties. Summary of the invention For the purposes of the invention, the term “bio-sourced clear binder” means a clear binder comprising at least one structuring agent of plant origin. In the remainder of the application, any reference to a standard (e.g. ASTM D1982) refers to the version of said standard in force on the date of filing of this application. The invention firstly relates to a clear binder composition comprising: (i) a plasticizing agent comprising at least one hydrocarbon oil of petroleum or synthetic origin, (ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an acidity index, determined according to the ASTM D465 method, less than or equal to 40 mg KOH / g, (ii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and (iv) possibly an adhesive agent, Preferably, the hydrocarbon oil has a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds of between 35% and 65%, a total content of naphthenic compounds of between 10% and 40%, the contents being given by mass, relative to the total mass of the oil present and measured according to the ASTM D2140 method. According to one embodiment, the hydrocarbon oil has a kinematic viscosity at 100°C, measured according to the ASTM D445 method, ranging from 15 mm2 / s to 40 mm2 / s, and an aniline point, measured by the ASTM D61 1 method, ranging from 50°C to 80°C. According to an alternative embodiment, the hydrocarbon oil has a viscosity kinematic at 100°C, measured by ASTM D445 method, ranging from 40 mm2 / s to 90 mm2 / 5, and an aniline point, measured by ASTM D61 1 method, ranging from 45°C to 95°C. Preferably, the content of plasticizing agent in the clear binder composition of the invention ranges from 1% to 65% by mass, relative to the total mass of the composition, preferably from 5% to 55% by mass, more preferably from 10% to 50% by mass. Advantageously, the resin of plant origin is chosen from natural rosin esters, more preferably from natural rosin pentaerythritol esters, in particular from tall oil rosin pentaerythritol esters. Preferably, the content of structuring agent ranges from 25% to 90% by mass, relative to the total mass of the composition, preferably from 30% to 80% by mass, more preferably from 35% to 75% by mass. Preferably, the polymer is a copolymer of styrene and butadiene, preferably is chosen from a styrene / butadiene / styrene block copolymer of radial structure, a butadiene / styrene block copolymer of radial structure and their mixtures. According to a particular embodiment, the clear binder composition of the invention further comprises Fischer-Tropsch waxes, preferably from 0.1% to 10% by mass of Fischer-Tropsch waxes, relative to the total mass of the clear binder composition, preferably from 0.5% to 5% by mass, more preferably from 1% to 3% by mass. The invention also relates to a process for preparing a clear binder composition as defined above and described in detail below, comprising the steps: - bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140°C and 200°C, - mixing with stirring the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C, - adding the polymer, mixing and heating to a temperature ranging from 140°C to 200°C, - the addition of any adhesive dope and / or any Fischer-Tropsch waxes, mixing and heating to a temperature ranging from 140°C to 200°C. The invention also relates to an emulsion comprising a clear binder composition as defined above and described in detail below, water, and an emulsifying agent. The invention finally relates to a coating comprising (i) a clear binder composition as defined above and described in detail below or an emulsion as defined above and described in detail below, (ii) aggregates and / or mineral fillers, and optionally (iii) one or more pigments. The expression "consists essentially of" followed by one or more characteristics means that, in addition to the components or steps explicitly listed, components or steps which do not significantly modify the properties and characteristics of the invention may be included in the process or material of the invention. The expression "between X and YŸ" includes the limits, unless explicitly stated otherwise. This expression therefore means that the interval referred to includes the values ​​X, Y and all values ​​from X to Y. The various embodiments, variations, preferences and advantages described for each of the objects of the invention apply to all of the objects of the invention and may be taken separately or in combination. Detailed description The essential constituents of a clear binder composition are: - a plasticizing agent, - a structuring agent, - at least one polymer, - where appropriate, doping agents, or dopes, or adhesive dopes, or Fischer-Tropsch waxes. The clear binder of the invention is characterized by the combination of a hydrocarbon oil of petroleum or synthetic origin and a resin of specific plant origin. This selection of components makes it possible to obtain a clear binder with a reduced environmental footprint, compared to clear binders prepared from an oil of petroleum origin and a resin of petroleum origin. The clear binder of the invention has similar, or even improved, properties compared to clear binders prepared from an oil of petroleum origin and a resin of petroleum origin, particularly in terms of resistance to aging. For the purposes of the invention, the terms “clear binder” and “clear binder base” are used equivalently. The invention relates to a clear binder comprising: (i) a plasticizing agent comprising at least one hydrocarbon oil of petroleum or synthetic origin, (ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an acidity index, determined according to the ASTM D465 method, less than or equal to 40 mg KOH / g (ii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and (iv) possibly an adhesive dope and / or possibly a Fischer-Tropsch wax. The plasticizing agent For the purposes of the invention, the term "plasticizing agent" means a chemical constituent making it possible to fluidify and reduce the viscosity and modulus of the binder in which it is incorporated. The plasticizing agent comprises at least one hydrocarbon oil of petroleum or synthetic origin. Preferably the oil is a hydrocarbon oil of petroleum origin. It can be aromatic or paraffinic. According to one embodiment, the oil is composed of 90% to 100% by mass of at least one hydrocarbon oil of petroleum origin, advantageously 95% to 100%, even better 98% to 100% by mass of at least one hydrocarbon oil of petroleum origin. Even more advantageously, the oil consists of a hydrocarbon oil of petroleum origin or a mixture of hydrocarbon oils of petroleum origin. In a preferred embodiment of the invention, the hydrocarbon oil of petroleum origin is chosen from aromatic oils. More preferably, the aromatic oils have an aromatic compound content of between 30% and 95% by mass, advantageously between 50% and 95% by mass, more advantageously between 60 and 95% by mass relative to the total mass of the aromatic oil (SARA method: Saturates / Aromatics / Resins / Asphaltenes, according to standard ASTM D2007). More preferably, the aromatic oils have a content of saturated compounds of between 1% and 30% by mass, advantageously between 5 and 25% by mass, more advantageously between 7 and 23% by mass (SARA method: Saturates / Aromatics / Resins / Asphaltenes, according to standard ASTM D2007). More preferably, the aromatic oils have a resin compound content of between 1 and 10% by mass, advantageously between 3 and 5% by mass, (SARA method: Saturates / Aromatics / Resins / Asphaltenes, according to standard ASTM D2007). The contents of naphthenic, paraffinic and aromatic compounds mentioned in this application are determined according to ASTM D2140, in % by mass relative to the mass of the oil. Preferably, the oil used in the clear binder composition according to the invention has a total content of paraffinic compounds of between 35% and 65%, of preferably between 40% and 60%, for example between 45% and 58%. Preferably, the oil used in the clear binder composition according to the invention has a total content of naphthenic compounds of between 10% and 40%, and in particular of between 15% and 35%, preferably between 20 and 30%. Preferably, the oil used in the clear binder composition according to the invention has a total content of aromatic compounds of between 10% and 40%, and in particular of between 15% and 35%, for example of between 18 and 30%. More preferably, the hydrocarbon oil of the invention has a kinematic viscosity at 100°C of between 0.1 mm? / s and 150 mm? / s, advantageously of between 5 mm? / s and 120 mm? / s, more advantageously of between 7 mm? / s and 90 mm? / s (ASTM Method D 445). More preferably, the hydrocarbon oil of the invention has a kinematic viscosity at 40°C of between 100 mm? / s and 2500 mm? / s, advantageously of between 200 mm” / s and 2400 mm? / s, more advantageously of between 400 mm7 / s and 2250 mm? / s (ASTM Method D 445). More preferably, the hydrocarbon oil of the invention has a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C (Method EN ISO 2592). More preferably, the hydrocarbon oil of the invention has an aniline point of between 20°C and 120°C, advantageously of between 40°C and 120°C (ASTM Method D611). More preferably, the aromatic oils have a density at 15°C of between 400 kg / m* and 1500 kg / m°, advantageously of between 600 kg / m° and 1200 kg / m*, more advantageously of between 800 kg / m* and 1100 kg / m° (ASTM D4052 Method). According to this advantageous embodiment, the aromatic oil comprises aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues from distillations of petroleum cuts. Aromatic extracts are by-products of the crude oil refining process, obtained in particular from the products of vacuum distillation of atmospheric residues. They result from a single or double extraction of the raffinate that can be used in lubricants, using a polar solvent. The different extracts are classified into different categories depending on their production process and are as follows: - DAE (Distillate Aromatic Extract in English, or aromatic distillate extract); - MES (Mild Extract Solvate in English or mild extraction solvent), - TDAE (Treated Distillate Aromatic Extract in English or distilled extract) treated aromatic), - RAE (Residual Aromatic Extract), - TRAE (Treated Residual Aromatic Extract) According to a first embodiment, the plasticizing agent comprises at least one oil having a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds of between 35% and 65%, a total content of naphthenic compounds of between 10% and 40%, the contents being given by mass, relative to the total mass of the oil, and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C, measured according to the ASTM D445 method, ranging from 40 mm” / s to 90 mm” / s, and an aniline point, measured by the ASTM D61 1 method, ranging from 45°C to 95°C. These oils result from a (simple) extraction of the raffinate which can be used in lubricants, using a polar solvent, and are hereinafter referred to as “RAE oil”. However, oils obtained by a process other than the RAE process, but having the same physicochemical characteristics and the same composition, also fall within the scope of the invention. In the present application, the term “RÂE oil” means an oil defined both by its content of aromatic, paraffinic and naphthenic compounds, by its viscosity at 100°C and its aniline point as defined above in the context of this first embodiment. Other preferential characteristics of these oils are reported below. The contents of paraffinic, naphthenic and aromatic compounds mentioned in this application are determined according to ASTM D2140, in % by mass relative to the total mass of the oil. The RAE oils used in the clear binder composition according to the invention have a total content of paraffinic compounds of between 35% and 65%, preferably between 37% and 60%, for example between 40% and 55%. The RAE oils used in the clear binder composition according to the invention have a total content of naphthenic compounds of between 10% and 40%, and in particular of between 15% and 35%, preferably between 20 and 30%. The RÂE oils used in the clear binder composition according to the invention have a total content of aromatic compounds of between 10% and 40%, and in particular of between 15% and 35%, for example of between 25 and 30%. In a preferred embodiment, the RAE oil is selected from those comprising: - a total content of paraffinic compounds between 37% and 60%; - a total content of naphthenic compounds of between 15% and 35%; and - a total content of aromatic compounds between 15% and 35%. In a more particularly preferred embodiment, the RAE oil is chosen from those comprising: - a total content of paraffinic compounds between 40% and 55%; - a total content of naphthenic compounds of between 20% and 30%; and - a total content of aromatic compounds between 25% and 35%. The RÂE oils used in the clear binder composition according to the invention have a kinematic viscosity at 100°C of between 40 and 90 mm” / s, more advantageously of between 45 and 85 mm? / s (ASTM Method D 445). Preferably, the RÂE oils used in the clear binder composition according to the invention have a kinematic viscosity at 40°C of between 1000 and 2500 mm? / s, more advantageously of between 1200 and 2500 mm? / s (ASTM Method D 445). The RÂE oils used in the clear binder composition according to the invention have an aniline point between 45°C and 95°C, more advantageously between 50°C and 75°C (ASTM Method D611). Preferably, the RÂE oils used in the clear binder composition according to the invention have a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C, even better, between 200°C and 250°C (ASTM Method D92). More preferably, the RAE oils used in the clear binder composition according to the invention have a density at 15°C of between 400 kg / m° and 1500 kg / m°, advantageously of between 600 kg / m° and 1200 kg / m°, more advantageously of between 800 kg / m* and 1100 kg / m° (ASTM Method D4052). For example, an RAE oil usable in the clear binder compositions according to the invention may be a product marketed by the company TotalEnergies under the name: REGENIS® 50. The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil from which the oils are derived and the refining process used. For example, REGENIS® 50 is a RAE (Residual Aromatic Extract) which presents - a density at 15°C between 980 kg / m° and 1010 kg / m° (ASTM D4052 method), - a flash point (Cleveland) of approximately 230°C (Method EN ISO 2592), - a kinematic viscosity at 100°C between 60 and 85 mm? / s (ASTM D 445 method), - an aniline point between 53 and 65°C (ASTM D611 method). According to a second embodiment, the plasticizing agent comprises at least one oil having a total aromatic compound content of between 10% and 40%, a total paraffinic compound content of between 35% and 65%, a total naphthenic compound content of between 10% and 40%, the contents being given by mass, relative to the total mass of the oil, and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C, measured according to the ASTM D445 method, ranging from 15 mm' / s to 40 mm” / s, and an aniline point, measured by the ASTM D61 1 method, ranging from 50°C to 80°C. These oils result from a double extraction of the raffinate which can be used in lubricants, using a polar solvent, and are hereinafter referred to as “TDAE oil”. However, oils obtained by a process other than the TDAE process, but having the same physicochemical characteristics and the same composition, also fall within the scope of the invention. In the present application, the term "TDAE oil" means an oil defined both by its content of aromatic, paraffinic and naphthenic compounds, by its viscosity at 100°C and its aniline point as defined above in the context of this first embodiment. Other preferential characteristics of these oils are reported below. The contents of paraffinic, naphthenic and aromatic compounds mentioned in this application are determined according to ASTM D2140, in % by mass relative to the total mass of the oil. The TDAE oils used in the clear binder composition according to the invention have a total content of paraffinic compounds of between 35% and 65%, preferably between 40% and 60%, for example between 45% and 55%. The TDAE oils used in the clear binder composition according to the invention have a total content of naphthenic compounds of between 10% and 40%, and in particular of between 15% and 35%, preferably between 20 and 30%. The TDAE oils used in the clear binder composition according to the invention have a total content of aromatic compounds of between 10% and 40%, and in particular of between 15% and 35%, for example of between 20 and 25%. In a preferred embodiment, the TDAE oil is selected from those comprising: - a total content of paraffinic compounds between 40% and 60%; - a total content of naphthenic compounds of between 15% and 35%; and - a total content of aromatic compounds between 15% and 35%. In a more particularly preferred embodiment, the TDAE oil is chosen from those comprising: - a total content of paraffinic compounds between 45% and 55%; - a total content of naphthenic compounds of between 20% and 30%; and - a total content of aromatic compounds between 20% and 25%. The TDAE oils used in the clear binder composition according to the invention have a kinematic viscosity at 100°C of between 15 and 40 mm” / s, more advantageously of between 16 and 30 mm? / s (ASTM Method D 445). Preferably, the TDAE oils used in the clear binder composition according to the invention have a kinematic viscosity at 40°C of between 300 and 600 mm? / s, more advantageously of between 400 and 550 mm? / s (ASTM Method D 445). The TDAE oils used in the clear binder composition according to the invention have an aniline point between 50°C and 80°C, more advantageously between 60°C and 70°C (ASTM Method D611). Preferably, the TDAE oils used in the clear binder composition according to the invention have a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C, even better, between 250°C and 300°C (ASTM Method D92). More preferably, the TDÂE oils used in the clear binder composition according to the invention have a density at 15°C of between 400 kg / m° and 1500 kg / m°, advantageously of between 600 kg / m° and 1200 kg / m°, more advantageously of between 800 kg / m* and 1100 kg / m° (ASTM Method D4052). For example, a TDAE oil usable in the clear binder compositions according to the invention may be a product marketed by the company TotalEnergies under the name: Plaxolene TD346 ®. The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil from which the oils are derived and the refining process used. For example, Plaxolene TD346 ® is a TDAE (Treated Distillate Aromatic Extract) oil which has: - a density at 15°C between 940 kg / m° and 970 kg / m°* (ASTM D4052 method), - a flash point (Cleveland) of approximately 260 to 280°C (ASTM Method D92), - a kinematic viscosity at 100°C between 16 and 23 mm / s (ASTM D 445 method), - an aniline point between 64 and 72°C (ASTM D611 method). Advantageously, the clear binder of the invention has a plasticizing agent content ranging from 1% to 65% by mass, relative to the total mass of the clear binder, preferably from 5% to 55% by mass, more preferably from 10% to 50% by mass. Advantageously, in the clear binder compositions of the invention, the oils as defined above represent at least 90% by mass relative to the total mass of the plasticizing agent, preferably at least 95%, even more advantageously preferably at least 98%, and advantageously still at least 99%. The structuring agent By “structuring agent” we mean any chemical constituent conferring mechanical properties and satisfactory cohesiveness to said binder. The structuring agent used in the composition of the invention is a resin chosen from resins of plant origin. Resins of plant origin can be said to be harvested, that is, harvested from the living plant. They can be used as is, in which case we speak of natural resins, or they can be chemically transformed, in which case we speak of modified natural resins. Harvesting resins include natural rosins, modified rosins, and rosin esters. These can be used alone or in a mixture. Natural rosins include gem and wood rosins, especially pine rosins, and / or tall oil rosins. These natural rosins can be used alone or in a mixture. Modified rosins include hydrogenated rosins, disproportionated rosins, polymerized rosins and / or maleized rosins. These modified natural rosins may be taken alone or in a mixture, and undergo one or more disproportionation, polymerization and / or maleization treatments. Preferably, the resin is chosen from rosin esters, optionally modified. More preferably, the resin is chosen from modified rosin esters. Even more preferably, the resin is chosen from tall oil rosin esters, possibly modified. Advantageously, the resin is chosen from modified tall oil rosin esters. Rosin esters include natural rosin methyl esters, hydrogenated rosin methyl esters, natural rosin glycerol esters, hydrogenated rosin glycerol esters, disproportionated rosin glycerol esters, polymerized rosin glycerol esters, maleated rosin glycerol esters, natural rosin pentaerythritol esters, and hydrogenated rosin pentaerythritol esters. These rosin esters may be taken alone or as a mixture and may be derived from rosins that have undergone one or more disproportionation, polymerization, and / or maleization treatments. Advantageously, the resin is chosen from co-pentaerythritol esters natural rosins, pentaerythritol esters of hydrogenated rosins and any mixture thereof, more preferably among pentaerythritol esters of natural rosins. According to a preferred embodiment, the resin is chosen from pentaerythritol esters of tall oil rosins. For more information on the plant-based resins that can be used according to the invention, please refer to article K340 by Bernard Delmond published in “Techniques de l'ingénieur”. Preferably, the resin of plant origin has a softening temperature, determined according to the AQCM 003 method, of between 60°C and 200°C, preferably between 80°C and 150°C, more preferably between 90°C and 110°C. The plant-based resin typically has an acidity index, determined according to the ASTM D465 method, less than or equal to 40 mg KOH / g, preferably ranging from 0.1 to 40 mg KOH / g, more preferably ranging from 0.5 to 40 mg KOH / g. According to a preferred embodiment, the resin of plant origin typically has an acidity index, determined according to the ASTM D465 method, of less than 8 mg KOH / g, preferably less than or equal to 5 mg KOH / g. Preferably, according to this preferred embodiment, the resin of plant origin has an acidity index, determined according to the ASTM D465 method, of between 0.1 and 8 mg KOH / g, preferably between 0.2 and 7 mg KOH / g, more preferably between 0.5 mg and 6 mg KOH / e. Preferably, the resin has a Gardner color index, determined according to ASTM D6166, of less than or equal to 10, more preferably less than or equal to 5, even more preferably less than or equal to |, typically 0.9. Preferably, the resin of plant origin has a glass transition temperature, measured according to the AQCM 218 method, of between 10°C and 80°C, preferably between 20°C and 60°C, more preferably between 40°C and 50°C. Preferably, the resin of plant origin has a Brookfield viscosity at 125°C, measured according to the AQCM 004 method, greater than or equal to 5,000 mPa.s, preferably between 7,500 mPa.s and 15,000 mPa.s, more preferably between 10,000 mPa.s and 11,000 mPa.s. Preferably, the resin of plant origin has a Brookfield viscosity at 150°C, measured according to the AQCM 004 method, greater than or equal to 500 mPa.s, preferably between 750 mPa.s and 1500 mPa.s, more preferably between 900 mPa.s and 1000 mPa.s. Preferably, the resin of plant origin has a Brookfield viscosity at 177°C, measured according to the AQCM 004 method, greater than or equal to 80 mPa.s, preferably between 100 mPa.s and 500 mPa.s, more preferably between 150 mPa.s and 200 mPa.s. For example, a resin usable in the clear binder compositions according to the invention may be a product marketed by the company KRATON under the name: SYLVALITE® 2100 Rosin Ester. Preferably, the weight ratio between the structuring agent and the plasticizing agent used for the preparation of the clear binder composition according to the invention is between 0.5 and 10, for example between 1 and 5. In a specific embodiment, the content of structuring agent in the clear binder composition of the invention ranges from 25% to 90% by mass, relative to the total mass of the composition, preferably from 30% to 80% by mass, more preferably from 35% to 75% by mass. The polymer The polymer used in the process for preparing the clear binder according to the invention is a copolymer based on conjugated diene units and monovinyl aromatic hydrocarbon units. The conjugated diene is preferably chosen from those comprising 4 to 8 carbon atoms per monomer, for example butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,2-hexadiene, chloroprene, carboxylated butadiene, carboxylated isoprene, in particular butadiene and isoprene, and mixtures thereof. The monovinyl aromatic hydrocarbon is preferably selected from styrene, o-methyl styrene, p-methyl styrene, p-tert-butylstyrene, 2,3 dimethyl styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and the like or mixtures thereof, in particular styrene. Advantageously, the polymer is chosen from copolymers of styrene and conjugated diene. More particularly, the polymer consists of one or more copolymers chosen from block copolymers of styrene and butadiene, of styrene and isoprene, of styrene and chloroprene, of styrene and carboxylated butadiene or of styrene and carboxylated isoprene. Preferably, the polymer consists of one or more copolymers chosen from copolymers of styrene and butadiene. For example, the polymer may be selected from one or more of the following copolymers: SB copolymers (styrene and butadiene block copolymers), SBS (styrene-butadiene-styrene block copolymers), SIS (styrene-isoprene-styrene), SBS* (styrene-butadiene-styrene star block copolymer), SBR (styrene-b-butadiene-rubber). Advantageously, the polymer is chosen from block copolymers. A preferred polymer is a copolymer based on butadiene units and styrene units, in particular such as a styrene / butadiene SB block copolymer or a co- styrene / butadiene / styrene SBS block polymer, or a mixture of such copolymers. More preferably, the polymer is a blend of a styrene / butadiene / styrene SBS block copolymer and a styrene / butadiene SB block copolymer. Advantageously, the polymer is a blend of a styrene / butadiene / styrene SBS block copolymer and a styrene / butadiene SB block copolymer in a SB / SBS mass ratio ranging from 0.1:99.9 to 30:70, advantageously from 1:99 to 20:80, even more advantageously from 5:95 to 15:85. The styrene-conjugated diene block copolymer, in particular the styrene-butadiene copolymer, advantageously has a styrene content by weight ranging from 5 to 50%, preferably from 20 to 40%, even better from 25 to 35%. The copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, advantageously has a weight content of styrene ranging from 20 to 40%, preferably from 25 to 35% by mass relative to the total mass of the copolymer. According to one embodiment, the average molecular mass of the copolymer of styrene and conjugated diene, and in particular that of the copolymer of styrene and butadiene, may be, for example, between 10,000 and 700,000, preferably between 50,000 and 500,000 and more preferably from 200,000 to 400,000 daltons. According to one variant, the average molecular mass of the copolymer of styrene and conjugated diene, and in particular that of the copolymer of styrene and butadiene, may be, for example, between 10,000 and 500,000, preferably between 20,000 and 100,000, more preferably from 30,000 to 75,000 daltons, advantageously between 50,000 and 60,000. The polymer may have a linear, branched or radial structure. Preferably, the copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, used in the clear binder composition according to the invention, has a radial structure. In a preferred embodiment, the total amount of polymer used in the process for preparing the clear binder of the invention is between 0.5 and 20% by mass, preferably between 1 and 10%, preferably between 1.5 and 7.5%, for example between 2.5% and 5%, by mass relative to the total mass of the clear binder composition. Stickiness drugs To improve the mutual affinity between the binder and the aggregates and ensure their durability, adhesive dopes can also be used. These include, for example, nitrogenous surfactant compounds derived from fatty acids (amines, polyamines, alkylpolymannan, etc.). When added to the clear binder, the tackifiers generally represent between 0.05% and 0.5% by weight relative to the total weight of the clear binder composition. For example, in a specific embodiment, between 0.05% and 0.5% of amine, preferably between 0.1% and 0.3% of amine, by weight relative to the total weight of the clear binder composition, will be added. Coloring agents The clear binder may also include one or more coloring agents, such as mineral pigments or organic dyes. The pigments are selected according to the desired shade or color for the coating. For example, metal oxides such as iron oxides, chromium oxides, cobalt oxides, titanium oxides will be used to obtain the colors red, yellow, gray, blue-green or white. The pigments can be added, indifferently in the clear binder or in the asphalt (mixed with aggregates for example) or in an emulsion of the clear binder. Optional additive(s) According to one embodiment, the clear binder composition of the invention further comprises at least one Fischer-Tropsch wax. The waxes (or paraffins) used are synthetic waxes derived from the Fischer-Tropsch synthesis process. These Fischer-Tropsch waxes are generally prepared by reacting carbon monoxide with hydrogen, typically at high pressures over a metal catalyst. Preferred Fischer-Tropsch waxes are the Fischer-Tropsch waxes described in application WO991 1737. The Fischer-Tropsch waxes described in this document are Fischer-Tropsch waxes comprising a mixture of paraffins. Fischer-Tropsch waxes comprise a majority of n-paraffins, often more than 90%, with the remainder being iso-paraffins. The average length of the paraffinic chains of Fischer-Tropsch waxes is between 30 and 115 carbon atoms, preferably between 40 and 100, more preferably between 60 and 90. Fischer-Tropsch waxes have a melting point (freezing point) between 65 and 105°C, preferably between 68 and 100°C. The Fischer-Tropsch waxes used in the invention may be partially oxidized or fully oxidized. A preferred example of Fischer-Tropsch wax is that sold under the brand name Sasobit®, which has a freezing point of 100°C (ASTM D 938), a penetrability at 25°C of less than 1 1 / 10 mm (ASTM D 1321), and a penetrability at 65°C of 7 1 / 10 mm (ASTM 1321). Another type of Fischer-Tropsch waxes that can be used are the Fischer-Tropsch waxes described in patent EP1951818. These Fischer-Tropsch waxes comprise a slightly larger quantity of isomerized paraffins than conventional Fischer-Tropsch waxes. These Fischer-Tropsch waxes comprising more iso-paraffins are characterized by a freezing point (ISO 2207) between 85 and 120°C and a PEN value at 43°C, expressed in 0.1 mm, determined according to IP 376, greater than 5. Preferably, when present, the amount of Fischer-Tropsch waxes is between 0.1% and 10% by mass, relative to the total mass of the clear binder composition, preferably between 0.5% and 5%, more preferably between 1% and 3%. The clear binder composition Advantageously, a clear binder composition according to the invention comprises, preferably consists essentially of, more preferably consists of: - from 1% to 65% by mass of plasticizing agent, in particular a hydrocarbon oil of petroleum or synthetic origin, preferably from 5% to 55% by mass, more preferably between 10% and 50% by mass, - from 25% to 90% by mass of structuring agent, in particular resin of plant origin, preferably from 30% to 80% by mass, more preferably from 35% to 75% by mass, - from 0.5% to 20% by mass of polymer, in particular copolymer of styrene and butadiene, preferably from 1% to 10% by mass, even better from 1.5% to 7.5% by mass, advantageously from 2.5% to 5% by mass, - optionally, from 0.05% to 0.5% by mass of dope(s), for example chosen from amines, preferably between 0.1% and 0.3% by mass, - optionally, from 0.1% to 10% by mass of Fischer-Tropsch wax(es), preferably from 0.5% to 5% by mass, more preferably from 1% to 3% by mass, relative to the total mass of the clear binder composition. Preferably, the clear binder according to the invention has a penetrability at 25°C, measured according to standard NF EN 1426, of between 10 and 220 1 / 10 mm, preferably between 20 and 160 1 / 10 mm, more preferably between 30 and 100 1 / 10 mm. A person skilled in the art can modulate the penetrability of the clear binder, in particular by judiciously choosing the weight ratio [structuring agent / plasticizing agent] in the composition of the clear binder. Indeed, it is known that an increase in this ratio makes it possible to reduce the penetrability at 25°C. Advantageously, the clear binder according to the invention has a ring and ball softening temperature (RBT), measured according to the NF EN 1427 method, ranging from 40 to 80°C, advantageously from 45 to 70°C. Clear binder preparation process The present invention also relates to a process for preparing the clear binder composition which has been described above. This process comprises the following steps: (i) bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature of between 140-200°C, for example for 10 minutes to 1 hour, (ii) mixing with stirring the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C, for example from 30 minutes to 2 hours, (iii) adding the polymer, for example SB and / or SBS, mixing and heating at a temperature between 140-200°C, for example, from 90 minutes to 3 hours, preferably from 90 minutes to 2 hours 30, (iv) optionally adding an adhesive dope, mixing and heating to a temperature between 140-200°C, for example, from 5 minutes to 30 minutes, (v) optional addition of one or more Fischer-Tropsch wax(es), mixing and heating to a temperature between 140-200°C, for example, from 5 minutes to 30 minutes. The order of steps (i) to (v) may be changed. Certain steps may also be carried out together or separately, in particular steps (iii) and / or (iv) and / or (v). Preferably, step (iii) is carried out separately, before steps (iv) and (v), and steps (iv) and (v) may be carried out together or separately. Applications of clear binder The clear binder composition according to the invention can be used and applied indifferently via the so-called “hot”, “warm” or “cold” techniques well known to those skilled in the art. Hot techniques are understood to mean techniques in which the clear binder composition is brought to relatively high temperatures during its application. Hot techniques lead to coatings, asphalts and so-called "hot" mixes such as bitumen gravels, high modulus mixes, bitumen sands, semi-granular bituminous concretes (BBSG), high modulus bituminous concretes (BBME), flexible bituminous concretes (BBS), thin bituminous concretes (BBM), permeable bituminous concretes (BBDr), very thin bituminous concretes (BBTM), ultra-thin bituminous concretes (BBUM). The clear binder composition according to the invention is suitable for the preparation of mixes, asphalts and coatings of all types, and in particular those mentioned above. The invention therefore also relates to coatings comprising a clear binder composition according to the invention, aggregates, optionally fillers and optionally pigments. Fillers (or fines) are particles with dimensions less than 0.063 mm. aggregates include particles of dimensions 0 / 2 (sand), 2 / 4 (gravel), 4 / 6 and 6 / 10. The mix generally comprises from 1 to 10% by weight of clear binder, relative to the total weight of the mix, preferably from 4 to 8% by mass, the remainder being made up of aggregates, possibly fillers and possibly pigments. Usually, the pigments represent a quantity by mass of 0 to 1% of the mix, the fillers represent a quantity by weight of 0 to 2% of the mix. Another subject of the invention is poured asphalts comprising a clear binder composition according to the invention, mineral fillers and optionally pigments. The asphalt comprises from 1 to 20% by weight of clear binder, relative to the total weight of the asphalt, preferably from 5 to 10% by weight, the remainder being made up of the fillers and optionally the pigments (the pigments representing a quantity by mass of 0 to 1% of the asphalt). Cold techniques are understood to mean techniques based on the use of clear binder emulsions in aqueous phase, at lower temperatures. Cold techniques lead to surface coatings, grouts, cold-cast asphalt mixes, cold asphalt mixes, cold bituminous concretes, emulsion-gravel, storable cold asphalt mixes. The clear binder composition according to the invention is suitable for the preparation of the products mentioned above. The invention therefore also relates to a clear binder emulsion comprising a clear binder composition according to the invention, water and an emulsifying agent. The clear binder comprises at least one plasticizing agent, at least one structuring agent and at least one polymer, as defined above. The invention therefore also relates to a process for preparing a clear binder emulsion comprising: (i) the preparation of a clear binder composition by mixing at least one plasticizing agent, at least one structuring agent and at least one polymer, as defined above, (ii) preparing an emulsifying solution by mixing the water and the emulsifying agent, (iii) dispersing the clear binder of step (i) in the emulsifying solution of step (ii. The clear binder emulsion according to the invention preferably comprises from 50% to 80% by weight of the clear binder composition, preferably from 60% to 70%, relative to the total weight of the clear binder emulsion. The various embodiments, variations, preferences and advantages described above for the plasticizing agent, the structuring agent and the other components of the clear binder composition apply to the use according to the invention. Surprisingly, it has been observed that the combination of a hydrocarbon oil of petroleum or synthetic origin and a particular rosin resin in a clear binder composition makes it possible to obtain improved cold aging resistance properties. This improved cold aging resistance makes it possible to formulate surface coatings, particularly in the road sector, which deteriorate less under the effect of time and / or climatic conditions.

Claims

Claims

1. A clear binder composition comprising: (1) a plasticizing agent comprising at least one hydrocarbon oil of petroleum or synthetic origin, (it) a structuring agent comprising at least one original resin vegetable chosen from natural rosins, rosins modified, rosin esters, and any of their mixtures, said resin of plant origin having an acidity index, determined according to ASTM D465 method, less than or equal to 40 mg KOH / g, (iii) at least one polymer based on conjugated diene units and units monovinyl aromatic hydrocarbon, and (iv) possibly an adhesive agent.

2. A composition according to claim 1, wherein said hydro- carbonaceous has a total content of aromatic compounds included between 10% and 40%, a total content of paraffinic compounds, between 35% and 65%, a total content of naph- compounds tenics between 10% and 40%, the contents being given in mass, relative to the total mass of oil present and measured according to ASTM D2140 method.

3. A composition according to claim 2, wherein said hydro- carbonaceous has a kinematic viscosity at 100 °C, measured according to the ASTM D445 method, ranging from 15 mm° / s to 40 mm? / s, and one point of aniline, measured by ASTM D61 1 method, ranging from 50°C to 80°C,

4. A composition according to claim 2, wherein said hydro- carbonaceous has a kinematic viscosity at 100 °C, measured according to the ASTM D445 method, ranging from 40 mm° / s to 90 mm? / s, and one point of aniline, measured by ASTM D61 1 method, ranging from 45°C to 95°C,

5. A composition according to any one of claims 1 to 4, in in which the plasticizing agent content ranges from 1% to 65% by mass, by relative to the total mass of the composition, preferably from 5% to 55% by mass, more preferably from 10% to 50% by mass.

6. Composition according to any one of the preceding claims, in which the resin of plant origin is chosen from esters of natural rosins, more preferably among the esters of pentaerythritol of natural rosins, especially among the esters of pentaerythritol from tall oil rosin.

7. Composition according to any one of the preceding claims, in which the structuring agent content ranges from 25% to 90% by mass, relative to the total mass of the composition, preferably from 30% to 80% by mass, more preferably from 35% to 75% by mass.

8. Composition according to any one of the preceding claims, wherein the polymer is a copolymer of styrene and butadiene, preferably is chosen from a styrene / block copolymer radial butadiene / styrene structure, a butadiene / block copolymer radial structure styrene and their mixtures.

9. Composition according to any one of the preceding claims, further comprising Fischer-Tropsch waxes, preferably of 0.1% to 10% by mass of Fischer-Tropsch waxes, relative to the total mass of the clear binder composition, preferably from 0.5% to 5% by mass, more preferably from 1% to 3% by mass.

10. | Process for preparing a clear binder composition according to one of any of the preceding claims, comprising the steps: - bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140°C and 200°C, - mixing with stirring of the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C, - adding the polymer, mixing and heating to a temperature ranging from 140°C to 200°C, - the addition of any adhesive dope and / or any waxes Fischer-Tropsch, mixing and heating to a temperature ranging from 140°C to 200°C.

11. | Emulsion comprising a clear binder composition according to one of any of claims | to 9, water, and an emulsifying agent.

12. A coating comprising (i) a clear binder composition according to one any of claims 1 to 9 or an emulsion according to reven- dication 9, (ii) aggregates and / or mineral fillers, and possibly (iii) one or more pigments.