Clear link and its applications

Abstract

The present invention relates to a clear binder composition and its uses in road and / or industrial applications. The present invention also relates to the use of a TDAE-type oil as a plasticizer in a clear binder base to improve the resistance to aging of cold-weather properties.

Description

Title of the invention: Clear binder and its applications Technical field

[0001] 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. The present invention also relates to the use of a TDAE type oil as a plasticizing agent in a clear binder composition for improving the aging resistance of the properties, in particular the cold properties, of the composition. State of the prior art

[0002] 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 they allow, among other things, to improve the safety of road users by clearly identifying specific lanes such as pedestrian paths, cycle paths, bus lanes. They also allow certain danger zones to be materialized such as the entrances to built-up areas or dangerous bends. Colored coatings improve visibility in low light conditions, for example at night or in particular sites such as tunnels. Finally, they simply allow the aesthetic appearance of urban roads to be improved and can be used for public squares, courtyards of buildings and schools, sidewalks, pedestrian streets, garden and park paths, parking and rest areas.

[0003] Therefore, for all the above-mentioned applications, it is preferred to use clear synthetic binders, not containing asphaltenes and which can be colored.

[0004] The clear binders of the prior art generally consist of a plasticizing agent, for example an oil of petroleum or vegetable origin, a structuring agent, for example a hydrocarbon resin, and a polymer.

[0005] 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.

[0006] Application WO2018 / 115729 discloses a cold-solid binder composition. In particular, the composition may be a clear binder and the plasticizing agent may be an oil of petroleum origin. Application WO2018 / 115730 describes a similar composition for the preparation of poured asphalts and the production of coatings.

[0007] Document FR 2765229 discloses a clear binder composition, comprising a petroleum oil and a polymer such as an SB, SBS, EVA copolymer, etc. This com- position further includes a wax.

[0008] 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 change. These are the phenomena of aging, essentially attributable to losses of volatile fractions and phenomena of oxidation by oxygen in the air.

[0009] Application WO2010 / 055491 describes a clear synthetic binder formulated, in part, from renewable raw materials, which is resistant to aging. The clear synthetic binder is prepared from a vegetable oil, a petroleum-based resin and at least one copolymer.

[0010] Application WO2016 / 166152 teaches a clear binder composition having improved physico-mechanical properties. This composition is prepared by mixing a synthetic oil from deasphalting unit cuts (DAO) and an SBS block copolymer.

[0011] Surprisingly, it has been found that the choice of a petroleum-based oil of the TDAE type (acronym for Treated Distillate Aromatic Extract) and a mixture of a first polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, in particular butadiene and styrene units (for example SB and / or SBS) and a second ethylene-vinyl acetate (EVA) polymer makes it possible to obtain a clear binder having improved properties compared to the clear binders of the prior art, in particular better resistance to aging of the properties of the clear binder, in particular better resistance to aging of the cold properties. Summary of the invention

[0012] The subject of the invention is a clear binder composition comprising: (i) a plasticizing agent comprising at least one oil which has 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 weight relative to the weight of the oil and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C ranging from 15 mm2 / s to 40 mm2 / s, measured according to the ASTM D445 method, and an aniline point ranging from 50°C to 80°C, measured by the ASTM D611 method, (ii) at least one structuring agent, (iii) at least one first polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, (iv) at least one second ethylene-vinyl acetate polymer, and, (v) possibly an adhesive dope.

[0013] According to a preferred embodiment of the invention, the oil is a synthetic oil obtained from the products of vacuum distillation of atmospheric residues and resulting from a double extraction of the raffinate using a polar solvent (TDAE).

[0014] According to a preferred embodiment of the invention, the oil comprises a total content of aromatic compounds of between 15% and 35% by weight, a total content of paraffinic compounds of between 40% and 60% by weight, and a total content of naphthenic compounds of between 15% and 35% by weight, measured according to the ASTM D2140 method, a kinematic viscosity at 100°C ranging from 16 mm2 / s to 30 mm2 / s, measured according to the ASTM D445 method, and an aniline point ranging from 60°C to 70°C, measured by the ASTM D611 method.

[0015] According to a preferred embodiment of the invention, the first polymer is a copolymer of styrene and butadiene.

[0016] According to a preferred embodiment of the invention, the first polymer comprises a styrene content by weight ranging from 20 to 40%.

[0017] According to a preferred embodiment of the invention, the first polymer has a mass average molecular mass of between 10,000 and 700,000 daltons.

[0018] According to a preferred embodiment of the invention, the first polymer is chosen from a styrene / butadiene / styrene block copolymer of radial structure, a butadiene / styrene block copolymer of radial structure and their mixtures.

[0019] According to a preferred embodiment of the invention, the composition has the following contents, by weight relative to the total weight of clear binder: - from 30 to 80% by weight of plasticizing agent, - from 30 to 60% by weight of structuring agent, - from 0.5 to 20% by weight of the first polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, - from 0.5 to 20% by weight of the second ethylene-vinyl acetate polymer, - optionally from 0.05% to 0.5% by weight of dope.

[0020] The invention also relates to a process for preparing a clear binder composition as described above and in detail below, comprising the steps: - mixing and heating the plasticizing agent to a temperature between 140 and 200°C, - adding the structuring agent, mixing and heating to a temperature between 140 and 200°C, - adding the first and second polymer, mixing and heating to a temperature between 140 and 200°C, - the addition of the possible adhesiveness dope, mixing and heating between 140 and 200°C.

[0021] The invention also relates to an emulsion comprising a clear binder composition as described above and in detail below, water, and an emulsifying agent.

[0022] The invention also relates to a coating comprising (i) a clear binder composition or an emulsion as described above and in detail below, (ii) aggregates and / or mineral fillers, and optionally (iii) one or more pigments.

[0023] The invention also relates to the use of an oil which 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 weight and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C ranging from 15 mm2 / s to 40 mm2 / s, measured according to the ASTM D445 method, and an aniline point ranging from 50°C to 80°C, measured by the ASTM D611 method, as a plasticizing agent in a clear binder composition for improving the aging resistance of the clear binder composition, in particular for improving the aging resistance of the cold properties of the clear binder composition.

[0024] The expression "consists essentially of" followed by one or more characteristics, means that 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, in addition to the components or steps explicitly listed.

[0025] The expression "between X and Y" includes the limits, unless explicitly stated otherwise. This expression therefore means that the interval in question includes the values ​​X, Y and all values ​​from X to Y.

[0026] The various embodiments, variants, 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

[0027] The essential constituents of a clear binder composition are: - a plasticizing agent, for example a natural or synthetic oil, free from asphaltenes, - a structuring agent, for example a hydrocarbon resin, - at least one polymer, - where appropriate, doping agents, or dopes, or adhesiveness dopes. The clear binder of the invention is characterized by the specific choice of the plasticizing agent and two particular copolymers. This selection of components makes it possible to obtain advantageous properties compared to the clear binders of the art prior.

[0028] For the purposes of the invention, the terms “clear binder” and “clear binder base” are used equivalently.

[0029] The invention relates to a clear binder comprising: (i) a plasticizing agent comprising at least one oil which 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 weight and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C ranging from 15 mm2 / s to 40 mm2 / s, measured according to the ASTM D445 method, and an aniline point ranging from 50°C to 80°C, measured by the ASTM D611 method, (ii) at least one structuring agent, (iii) at least one first polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, (iv) at least one second ethylene-vinyl acetate polymer, and, (v) possibly an adhesive dope. The plasticizing agent

[0030] 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.

[0031] According to the invention, the plasticizing agent comprises at least one oil whose characteristics are stated above. Oils having these characteristics are available in particular among the synthetic oils obtained from the products of vacuum distillation of atmospheric residues. 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.

[0032] 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 stated in the subject of the invention. Other preferential characteristics of these oils are reported below.

[0033] The contents of paraffinic, naphthenic and aromatic compounds mentioned in the present application are determined according to the ASTM D2140 standard, in % by weight relative to the total weight of the oil.

[0034] 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%, of preferably between 40% and 60%, for example between 45% and 55%.

[0035] 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%.

[0036] 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 30%.

[0037] In a preferred embodiment, the TDAE oil is chosen 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%.

[0038] 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 30%.

[0039] 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 mm2 / s, more advantageously of between 16 and 30 mm2 / s (ASTM Method D 445).

[0040] 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).

[0041] 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 mm2 / s, more advantageously of between 400 and 550 mm2 / s (ASTM Method D 445).

[0042] 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).

[0043] More preferably, the TDAE oils used in the clear binder composition according to the invention have a density at 15°C of between 400 kg / m3 and 1500 kg / m3, advantageously of between 600 kg / m3 and 1200 kg / m3, more advantageously of between 800 kg / m3 and 1100 kg / m3 (ASTM Method D4052).

[0044] 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 ®.

[0045] 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.

[0046] For example, Plaxolene ® TD346 ® is a TDAE (Treated Distillate Aromatic Extract) oil which has:

[0047] - a density at 15°C between 940 kg / m3 and 970 kg / m3 (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 mm2 / s (ASTM D 445 method), - an aniline point between 64 and 72°C (ASTM Method D611).

[0048] Advantageously, the quantity of plasticizing agent used in the process for preparing the clear binder represents between 30% and 80%, preferably between 40% and 70% by weight, preferably between 45% and 60% relative to the total weight of the clear binder composition.

[0049] Advantageously, in the clear binder compositions of the invention, the TDAE 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 at least 98%, and even more advantageously at least 99%.

[0050] In particular, in a preferred embodiment, the plasticizing agent according to the invention consists solely of a TDAE oil or a mixture of TDAE oils.

[0051] When the plasticizing agent comprises another type of oil in addition to TDAE oil, this can be chosen from oils of petroleum origin or oils of vegetable origin. The structuring agent

[0052] By "structuring agent" is meant any chemical constituent conferring mechanical properties and satisfactory cohesiveness to said binder. The structuring agent is a constituent of clear binder compositions well known to those skilled in the art.

[0053] The structuring agent used in the composition of the invention is a resin, preferably chosen from resins of hydrocarbon petroleum origin or resins of plant origin.

[0054] Among the hydrocarbon resins of petroleum origin, mention may be made, for example, of resins resulting from the copolymerization of aromatic, aliphatic, cyclopentadienic petroleum fractions, taken alone or as a mixture. Preferably, the structuring agent used in the composition of the invention is chosen from resins resulting from aromatic petroleum fractions. For example, it may be a polycycloaliphatic thermoplastic resin, for example a resin of the hydrogenated cyclopentadiene homopolymer type, with a low molecular weight.

[0055] More particularly, the hydrocarbon resin of the cyclopentane type has a softening point (or Ring-Ball temperature, RBT, according to standard NF T 66-008) greater than 125°C, and a Gardner color index (according to standard NF T 20-030) equal to a maximum of 7.

[0056] Other examples of resins that can be used as structuring agents include, but are not limited to, resins of plant origin obtained from plants and / or plants.

[0057] Resins of plant origin can be said to be harvested, that is to say harvested from the living plant. They can be used as they are, in which case we speak of natural resins, or they can be chemically transformed, in which case we speak of modified natural resins.

[0058] Among the harvesting resins are acrylate resins, dammar, natural rosins, modified rosins, rosin esters and metallic resinates. These can be taken alone or in 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.

[0059] Among the modified rosins, mention may be made of 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.

[0060] Among the rosin esters, mention may be made of methyl esters of natural rosins, methyl esters of hydrogenated rosins, esters of glycerol and natural rosins, esters of glycerol and hydrogenated rosins, esters of glycerol and disproportionated rosins, esters of glycerol and polymerized rosins, esters of glycerol and maleated rosins, esters of pentaerythritol and natural rosins and esters of pentaerythritol and hydrogenated rosins. These rosin esters may be taken alone or as a mixture and come from rosins having undergone one or more disproportionation, polymerization and / or maleization treatments.

[0061] Esters of pentaerythritol and natural rosins and esters of pentaerythritol and hydrogenated rosins are the preferred rosin esters.

[0062] Among the metal resinates, mention may be made of metal carboxylates, for example of Ca, Zn, Mg, Ba, Pb, Co, obtained from natural rosins or modified rosins. Among the metal resinates, calcium resinates, zinc resinates, mixed calcium / zinc resinates, taken alone or as a mixture, are preferred.

[0063] For more information on resins of plant origin that can be used according to the invention, we can refer to article K340 by Bernard Delmond published in “Techniques de l'ingénieur”.

[0064] Preferably, the resins of plant origin have a softening temperature of between 60°C and 200°C, preferably between 80°C and 150°C, more preferably between 90°C and 110°C.

[0065] Preferably, the resins of plant origin have an acidity index of between 0.1 and 25 mg KOH / g, preferably between 0.2 and 20 mg KOH / g, more preferably between 0.5 mg and 16 mg KOH / g.

[0066] 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 0.3 and 2, for example between 0.5 and 1.5.

[0067] In a specific embodiment, the amount of structuring agent used in the process for preparing the clear binder is between 30% and 70%, preferably between 40% and 60% by weight relative to the total weight of the clear binder composition. The first polymer

[0068] The first 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 from 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.

[0069] The monovinyl aromatic hydrocarbon is preferably chosen from styrene, o-methyl styrene, p-methyl styrene, p-tert-butylstyrene, 2,3 dimethylstyrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and the like or mixtures thereof, in particular styrene.

[0070] Advantageously, the first polymer is chosen from copolymers of styrene and conjugated diene. More particularly, the first 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 first polymer consists of one or more copolymers chosen from copolymers of styrene and butadiene.

[0071] For example, the first polymer may be chosen 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 block copolymer in star), SBR (styrene-b-butadiene-rubber).

[0072] Advantageously, the first polymer is chosen from block copolymers.

[0073] A first preferred polymer is a copolymer based on butadiene units and styrene units, in particular such as a styrene / butadiene SB block copolymer or a styrene / butadiene / styrene SBS block copolymer, or a mixture of such copolymers.

[0074] More preferably, the first polymer is a blend of a styrene / butadiene / styrene SBS block copolymer and a styrene / butadiene SB block copolymer.

[0075] Advantageously, the first polymer is a mixture 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.

[0076] The block copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, advantageously has a weight content of styrene ranging from 5 to 50%, preferably from 20 to 40%, even better from 25 to 35%.

[0077] The copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, advantageously has a styrene content by weight ranging from 20 to 40%, preferably from 25 to 35% by mass relative to the total mass of the copolymer.

[0078] 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.

[0079] The first polymer may be of 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 as first polymer, has a radial structure.

[0080] In a preferred embodiment, the total quantity of the first 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 and 7%, for example between 1.5% and 5%, by mass relative to the total mass of the clear binder composition. The second polymer

[0081] The second polymer used in the process for preparing the clear binder according to the invention is an ethylene-vinyl acetate (EVA) copolymer.

[0082] Preferably, the second copolymer comprises a vinyl acetate content ranging from 5% to 50%, by mass relative to the total mass of the copolymer, advantageously from 10% to 30%, even more advantageously from 15% to 25%. The vinyl acetate content vinyl is known to be evaluated by Fourier transform infrared spectroscopy (FTIR).

[0083] Preferably, the second copolymer has a melt index or fluidity index of between 10 and 400 g / lOmin, preferably between 50 and 300 g / lOmin, even more preferably between 100 and 200 g / lOmin. The melt index or fluidity index is measured in a known manner by the ASTMD1238 method or by the ISO1133 method.

[0084] In a specific embodiment, the total quantity of the second polymer used in the process of the invention is between 0.5 and 20% by mass, preferably between 0.5 and 10%, preferably between 1 and 7%, for example between 1% and 5%, relative to the total mass of the clear binder composition. Stickiness drugs

[0085] To improve the mutual affinity between the binder and the aggregates and ensure their durability, adhesive dopes can also be used. These are, for example, nitrogenous surfactant compounds derived from fatty acids (amines, polyamines, alkyl-polymannan, etc.).

[0086] When added to the clear binder, the tackifier dopes 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

[0087] The clear binder may also comprise one or more coloring agents, such as mineral pigments or organic dyes. The pigments are selected according to the shade, the color desired 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 coating (in a mixture with the aggregates for example) or in an emulsion of the clear binder. Clear binder preparation process

[0088] 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) mixing the plasticizing agent, for example TDAE oil or TDAE oil blend, and heating to a temperature of between 140-200°C, for example 10 minutes to 30 minutes, (ii) adding the structuring agent, for example hydrocarbon resin, mixing and heating to a temperature between 140-200°C, for example 30 minutes to 2 hours, (iii) adding the first and second polymer, for example SB and / or SBS and EVA, 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 at a temperature between 140-200°C, for example, from 5 minutes to 30 minutes. The order of steps (i) to (iv) may be changed.

[0089] Advantageously, a clear binder composition according to the invention comprises, by weight relative to the total weight of clear binder, or better still consists essentially of: - from 30 to 80% by weight, preferably from 40 to 70% by weight of plasticizing agent, preferably between 45% and 60% by weight of plasticizing agent, for example a TDAE oil or a mixture of TDAE oils, - from 30 to 60% by weight, preferably from 40 to 50% by weight of structuring agent, for example a hydrocarbon resin, - from 0.5 to 20% by weight, preferably from 1 to 10%, even better from 1 to 7%, advantageously from 1.5 to 5% by weight of the first polymer, for example a copolymer of styrene and butadiene, - from 0.5 to 20% by weight, preferably from 0.5 to 10%, even better from 1 to 7%, advantageously from 1 to 5% by weight of the second polymer (EVA), - optionally from 0.05% to 0.5% by weight of dope, preferably between 0.1% and 0.3% by weight of dope, for example a dope chosen from amines.

[0090] Preferably the mass ratio between the first and the second polymer is from 1:10 to 10:1, advantageously from 1:5 to 5:1, even better from 1:3 to 3:1 and even more advantageously from 1:2 to 2:1.

[0091] Preferably, the total amount of the first and second polymer represents from 1 to 20% by mass, preferably from 1 to 10%, advantageously between 2% and 8% by mass relative to the total mass of the clear binder composition.

[0092] 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.

[0093] 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, preferably 45 to 70°C. Applications of clear binder

[0094] 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.

[0095] 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" coatings such as bitumen gravels, high modulus coatings, 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 coatings, asphalts and coatings of all types, and in particular those mentioned above.

[0096] The invention therefore also relates to coatings comprising a clear binder composition according to the invention, aggregates, optionally fillers and optionally pigments.

[0097] Fillers (or fines) are particles with dimensions less than 0.063 mm. Aggregates include particles with dimensions 0 / 2 (sand), 2 / 4 (gravel), 4 / 6 and 6 / 10.

[0098] The coating generally comprises from 1 to 10% by weight of clear binder, relative to the total weight of the coating, 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 coating, the fillers represent a quantity by weight of 0 to 2% of the coating.

[0099] 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).

[0100] 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 asphalts, cold asphalts, cold bituminous concretes, emulsion gravels, storable cold asphalts. The clear binder composition according to the invention is suitable for the preparation of the products mentioned above.

[0101] 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 mixture of a first and a second polymer, as defined above.

[0102] The invention therefore also relates to a process for preparing a clear binder emulsion comprising: (i) preparing a clear binder composition by mixing at least one plasticizing agent, at least one structuring agent and at least one mixture of a first and a second polymer, as defined above, (ii) preparing an emulsifying solution by mixing the water and the emulsifying agent, (iii) dispersing the clear binder from step (i) in the emulsifying solution from step (ii).

[0103] 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.

[0104] Use of a TDAE oil as a plasticizing agent in a clear debonding base

[0105] The invention also relates to the use of a TDAE oil or a mixture of TDAE oils, as defined above, in a clear binder base to improve the resistance to aging of the properties of the clear binder, in particular to improve the resistance to aging of the cold properties.

[0106] As described above, the clear binder base comprises: - a plasticizing agent, - a structuring agent, for example a hydrocarbon resin, - at least one mixture of a first and a second polymer, - where appropriate, doping agents, or dopes, or adhesiveness dopes.

[0107] TDAE, or TDAE oil blend, for use as a plasticizing agent in a clear binder base is described above under "Plasticizing Agent".

[0108] The various embodiments, variations, preferences and advantages described above for the TDAE oil and the other components of the clear binder composition apply to the use according to the invention.

[0109] Surprisingly, in fact, it has been observed that the use of a so-called TDAE oil in a clear binder composition makes it possible, by comparison with other oils of petroleum origin, to obtain improved properties of resistance to aging of cold properties. This improvement was observed by means of a standardized test called BBR for determining the flexural rigidity modulus (NF EN14771: 2012), this test being carried out before and after an aging protocol applied to the sample. This better resistance to aging of cold properties makes it possible to formulate surface coatings, particularly in the road sector, which degrade less under the effect of time and / or climatic conditions.

[0110] The invention is illustrated by the following examples given without limitation. Examples

[0111] In the Examples, parts and percentages are expressed by weight unless otherwise indicated.

[0112] Materials and methods:

[0113] Plasticizers: The composition and properties of the plasticizers used in the experimental part are reported in Table 1.

[0114] [Tables 1] TDAE RAE Trade name Plaxolene ® TD346 Regenis ® 50 CAS No. 68783-04-0 64742-10-5 Aromatic content (% -ASTM D3238) 25 30 Paraffinic content (% -ASTM D3238) 50 49 Naphthenic content (% - ASTM D3238) 25 21 Viscosity at 100°C (mm2 / s - ASTM D445) 20.87 67.0 Viscosity at 40°C (mm2 / s - ASTM D445) 480.2 - Aniline point (°C - ASTM D611) 67.0 69.2 Cleveland point (°C - ASTM D92) 272 310

[0115] RAE stands for “Residual Aromatic Extract” and refers to the residues of aromatic extracts from petroleum products.

[0116] Resin: The resin available under the trade name SK 140 from Yuen Liang Industrial & Co., Ltd was used. It is a hydrocarbon resin obtained by polymerization of unsaturated aromatic hydrocarbons C9-C10. Its melting temperature is between 135 and 145°C according to ASTM D 3461.

[0117] Styrene and butadiene copolymer: a mixture of thermoplastic SB and SBS block copolymers was used, having a content of constituent units derived from 70 / 30 Butadiene / Styrene monomers, of radial structure, obtained by solution polymerization, with a molecular mass of approximately 330,000 daltons polystyrene equivalent (PS), commercially available under the name Calprene ® 411 from the company Dynasol.

[0118] EVA copolymer: A commercially available copolymer under the name Evatane ® 18-150 was used, which has a melt index of 135-175 g / 10 min (ASTMD1238 / ISO1133 method) and a vinyl acetate content of 17-19% (FTIR).

[0119] Adhesive dope: amine-type compound (Cecabase ® 200 commercially available from ARKEMA).

[0120] Preparation of a clear binder composition according to the invention (Cl) and comparative compositions Clear binders are prepared according to the following process: - Heat the oil to 170°C; - Add the resin and mix for 1 to 2 hours at 170°C with a stirring speed of 300 rpm; - The powdered styrene and butadiene copolymer and the EVA copolymer are added and mixed for 2 hours at 170°C with a stirring speed of 250 rpm; - Add the adhesive dope in liquid form and mix for 15 minutes at 170°C.

[0121] Methods for determining the properties of clear binder compositions

[0122] [Tables2] Property Abbreviation Unit Measurement standard Needle penetration at 25°C P25 1 / 10 mm NF EN 1426 Ring and ball softening temperature TBA °C NF EN 1427 Viscosity at 100°C V100 °C ASTM D445-21 BBR test (determination of flexural rigidity modulus) Ts and Tm °c NFEN 14771 Elastic return measurement - % NF EN 13398 Aging acceleration protocol (PAV) - - NF EN 14769 Clear binder compositions

[0123] The clear binder compositions according to the invention C1 and comparative Tl are prepared according to the description in the preceding paragraph with the constituents and proportions (in percentage by weight relative to the total weight of clear binder) reported in table 3.

[0124] [Table 3]: Composition Cl Tl TDAE Oil 49.7 - RAE Oil - 59.2 Resin 45.1 35.6 SB Copolymer 3.0 3.0 EVA Polymer 2.0 2.0 Dope 0.2 0.2 Characterization Penetrability at 25 °C 53 60 TBA 53.6 53.6 Elastic recovery (%) 81 88 Viscosity at 160°C (mPa.s) 252 285 Properties at T = 0 T°@S=300MPa -17.3 -15.4 T @m=0.3 -18.8 -17.5 Properties after 72 h PAV T°@S=300MPa -15.3 -13.1 T @m=0.3 -16.5 -15.9

[0125] The compositions are formulated at an equivalent grade, in this case a 50 / 70 grade. Results

[0126] It is noted that the composition according to the invention C1 has superior properties compared to the control composition Tl: the values ​​Ts and Tm are lower for C1, which shows that the composition according to the invention C1 has better cold resistance before aging. The difference in performance from the point of view of this property is further increased after aging.

Claims

Claims

1. Clear binder composition comprising: (i) a plasticizing agent comprising at least one oil which has 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 weight relative to the weight of the oil and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C ranging from 15 mm2 / s to 40 mm2 / s, measured according to the ASTM D445 method, and an aniline point ranging from 50°C to 80°C, measured by the ASTM D611 method, (ii) at least one structuring agent, (iii) at least one first polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, (iv) at least one second ethylene acetate polymer vinyl, and, (v) possibly an adhesive dope.

2. A composition according to claim 1, wherein the oil is a synthetic oil obtained from the products of vacuum distillation of atmospheric residues and resulting from a double extraction of the raffinate using a polar solvent (TDAE).

3. A composition according to any one of claims 1 or 2, wherein the oil comprises a total aromatic content of between 15% and 35% by weight, a total paraffinic content of between 40% and 60% by weight, and a total naphthenic content of between 15% and 35% by weight, measured according to the ASTM D2140 method, a kinematic viscosity at 100°C of between 16 mm2 / s and 30 mm2 / s, measured according to the ASTM D445 method, and an aniline point of between 60°C and 70°C, measured by the ASTM D611 method.

4. A composition according to any preceding claim, wherein the first polymer is a copolymer of styrene and butadiene.

5. A composition according to any preceding claim, wherein the first polymer comprises a styrene content by weight of from 20 to 40%.

6. Composition according to any one of the preceding claims, wherein the first polymer has a mass average molecular weight of between 10,000 and 700,000 daltons.

7. Composition according to any one of the preceding claims, in which the first polymer is selected from a styrene / butadiene / styrene block copolymer of radial structure, a butadiene / styrene block copolymer of radial structure and mixtures thereof.

8. Composition according to any one of the preceding claims, which has the following contents, by weight relative to the total weight of clear binder: - from 30 to 80% by weight of plasticizing agent, - from 30 to 60% by weight of structuring agent, - from 0.5 to 20% by weight of the first polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, - from 0.5 to 20% by weight of the second ethylene-vinyl acetate polymer, - optionally from 0.05% to 0.5% by weight of dope.

9. A process for preparing a clear binder composition according to any one of the preceding claims, comprising the steps of: - mixing and heating the plasticizing agent to a temperature of between 140 and 200°C, - adding the structuring agent, mixing and heating to a temperature of between 140 and 200°C, - adding the first and second polymers, mixing and heating to a temperature of between 140 and 200°C, - adding the optional adhesive dope, mixing and heating to between 140 and 200°C.

10. An emulsion comprising a clear binder composition according to any one of claims 1 to 8, water, and an emulsifying agent.

11. Coated material comprising (i) a clear binder composition according to any one of claims 1 to 8 or an emulsion according to claim 10, (ii) aggregates and / or mineral fillers, and optionally (iii) one or more pigments.

12. Use of an oil which has 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 weight and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100°C ranging from 15 mm2 / s to 40 mm2 / s, measured according to the ASTM D445 method, and an aniline point ranging from 50°C to 80°C, measured by ASTM D611 method, as a plasticizing agent in a clear binder composition to improve the aging resistance of the clear binder composition, particularly to improve the aging resistance of the cold properties of the clear binder composition.