OA19486A - Bitume solide à température ambiante. - Google Patents

Abstract

Granules de matériau utilisable comme liant routier ou comme liant d'étanchéité comprenant un cœur et une couche de revêtement, dans lesquels : le cœur est constitué d'une première composition comprenant au moins un matériau choisi parmi : une base bitume, un brai, un liant clair, et la couche de revêtement est constituée d'une seconde composition qui comprend : • au moins un composé viscosifiant choisi parmi les éthers de cellulose, et • au moins un agent anti-agglomérant. Procédé de fabrication de granules de matériau utilisable comme liant routier ou comme liant d'étanchéité ainsi que leur utilisation comme liant routier, notamment pour la fabrication d'enrobés. Procédé de fabrication d'enrobés à partir de granules de matériau utilisable comme liant routier ou comme liant d'étanchéité ainsi qu'un procédé de transport et/ou de stockage et/ou de manipulation de granules.

Description

The present invention relates to granules of a material which is solid at room temperature, which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a clear binder, a bitumen / polymer composition. The present invention also relates to a process for preparing these granules as well as their use as a road binder, in particular for the manufacture of mixes.

The present invention also relates to a process for manufacturing mixes from the granules according to the invention as well as a process for transporting and / or storing and / or handling these bitumen granules at room temperature, in particular at temperature. high ambient.

State of the art

The vast majority of bitumen is used in construction, primarily for the manufacture of road pavements or in industry, for example for roofing applications. It is generally in the form of a black material that is highly viscous, even solid at room temperature, which becomes fluid on heating.

Typically, bitumen is stored and transported hot, in bulk, in tankers or by ships at elevated temperatures in the range of 120 ° C to 160 ° C. However, the storage and transport of hot bitumen has certain drawbacks. On the one hand, the transport of hot bitumen in liquid form is considered dangerous and it is very regulated from a regulatory point of view. This mode of transport does not present any particular difficulties when the equipment and transport infrastructure are in good condition. Otherwise, it can become problematic: if the tanker is not sufficiently insulated, the viscosity of the bitumen may increase during too long a journey. The bitumen delivery distances are therefore limited. On the other hand, keeping bitumen at high temperatures in tanks or tankers consumes energy. Further, maintaining the bitumen at elevated temperatures for a long time can affect the properties of the bitumen and thus change the final performance of the asphalt.

To overcome the problems of transporting and storing hot bitumen, packaging allowing the transport and storage of bitumens at room temperature have been developed. This mode of transporting bitumen in ambient temperature packaging represents only a small fraction of the quantities transported worldwide,

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As an example of packaging for cold transport currently used, there may be mentioned the packaging of bitumen at room temperature in metal drums. This method is increasingly questionable from an environmental point of view because the bitumen stored in the drums must be heated before its use as a road binder. However, this operation is difficult to implement for this type of packaging and the drums constitute waste after use. On the other hand, the storage of bitumen at room temperature in drums leads to losses because the bitumen is very viscous and part of the product remains on the walls of the drum during the transfer into the tanks of the asphalt production units. Handling and transporting bituminous products in these drums can be difficult and dangerous if specialized drum handling equipment is not available from carriers or where the bitumen is used.

Other examples of packaging include bitumens in the form of granules transported and / or stored in bags, often used in places where the ambient temperature is high. These granules have the advantage of being easy to handle.

The same difficulty is encountered in the handling, packaging and storage of pitches and bituminous compositions comprising, clear binders, bitumen / polymer compositions, in particular stock solutions of bitumen / polymer compositions.

US 3,026,568 describes bitumen granules covered with a powdery material, such as limestone powder. However, this type of granular bitumen does not prevent the bitumen from creeping, especially at high ambient temperature.

Application WO 2009/153324 describes bitumen granules coated with a polymeric anti-caking compound, in particular polyethylene. The disadvantage of this coating is that it changes the properties of the bitumen during its road application.

Application WO 2016/016318 describes bitumen granules comprising a chemical additive. These bitumen granules allow the transport and / or the storage and / or the handling of the bitumen at ambient temperature without the latter creeping, as well as the reduction of their adhesion and agglomeration between them.

Application WO 2016/198782 describes bitumens that are solid at room temperature in the form of granules comprising a core and a coating layer in which:

- the core comprises at least one bitumen base and,

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the coating layer comprises at least 10% by mass of one or more viscosifying compounds relative to the total mass of the coating layer, and at least one anti-caking compound.

The viscosifying compounds illustrated in WO 2016/198782 are based on gelatin. These granules exhibit satisfactory working properties, however, they have the disadvantage of requiring an additional step after the coating of the cores with the coating layer, to allow the formation of a shell around the cores.

Application US 2011/233105 describes asphalt granules which are stable on storage and have a core / shell structure. The core of the granules consists of a mixture of a bituminous material obtained by recycling shingles and a bituminous binder. The envelope, in particular based on fines, minerals or crushed plastics, or even clay, prevents the agglomeration of the granules during their storage.

Continuing with its work, the Applicant has surprisingly discovered a new composition of granules of material which is solid at room temperature, which can be used as a road binder or as a sealing binder, such as a road bitumen, a pitch, a composition. bitumen / polymer, a clear binder, making it possible to avoid and reduce adhesion and agglomeration during their transport and / or storage and / or handling, at high ambient temperature, over long periods and whose properties are retained over time compared to the granules of the prior art.

More precisely, the Applicant has demonstrated that this new composition of granules makes it possible to resist creep under extreme conditions of transport and / or storage and / or handling, under conditions of compression, in particular due to storage, on very long periods.

Summary of the invention

The subject of the invention is granules of material which can be used as a road binder or as a sealing binder comprising a core and a coating layer in which:

- the core consists of a first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder, and

- the coating layer consists of a second composition which comprises:

• at least one viscosifying compound chosen from cellulose ethers, and • at least one anti-caking agent.

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The invention also relates to a process for manufacturing granules of material which can be used as a road binder or as a sealing binder, composed of a core and a coating layer of the core, this process comprising:

i) shaping the heart from a first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder, ii) coating the core over all or part of its surface by a second composition comprising at least one viscosifying compound chosen from cellulose ethers and at least one anti-caking agent.

The invention also relates to granules of material which can be used as a road binder 10 or as a sealing binder, which may be obtained by implementing this process.

According to one embodiment of the invention, the cellulose ether is chosen from: methyl cellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxyethyl methylcellulose (HEMC) ), hydroxypropyl methylcellulose (HPMC), hydroxybutyl methylcellulose (HBMC), carboxymethylcellulose (CMC), sodium carboxymethylcellulose (Na-CMC), carboxymethylsulfoethylcellulose, hydroxyethylmethylcarboxymethylcellulose.

According to a preferred embodiment of the invention, the cellulose ether is selected from: hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose, even more preferably hydroxypropyl methylcellulose.

According to one embodiment of the invention, the second composition comprises at least 10% of one or more anti-caking agents, the percentages being expressed by mass relative to the total mass of the second composition.

According to a preferred embodiment of the invention, the second composition comprises: at least 20% of one or more anti-caking agents, even better at least 30%, advantageously at least 40%, even better at least 50% of one or more anti-caking agents, and optionally one or more plasticizers, the percentages being expressed by mass relative to the total mass of the second composition.

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Preferably, the anti-caking compound is chosen from: talc; fines generally less than 125 µm in diameter, such as siliceous fines, with the exception of limestone fines; sand such as Fontainebleau sand; cement ; carbon; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of cones of conifers, in particular of pine; ash from rice husks; grain powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, fumed silicas, in particular hydrophobic or hydrophilic fumed silicas, silicates, silicon hydroxides and oxides of silicon; plastic powder; lime; hydrated lime; the plaster ; rubber crumb; powder of polymers, such as styrene-butadiene (SB) copolymers, styrene-butadiene-styrene (SBS) copolymers and mixtures of these materials.

According to one embodiment of the invention, the first composition exhibits needle penetrability measured at 25 ° C according to standard EN 1426 of 5 to 330 1/10 mm, preferably 10 to 220 1/10 mm.

According to one embodiment of the invention, the bitumen base further comprises at least one chemical additive chosen from: an organic compound, a paraffin, a polyphosphoric acid, a tackifier, and mixtures thereof.

According to one embodiment of the invention, the first composition comprising at least one chemical additive has a penetrability of 5 to 45 l / 10 mm, measured at 25 ° C according to standard EN 1426 and / or a ball softening temperature and ring greater than or equal to 90 ° C, the ball and ring softening temperature being measured according to standard EN 1427.

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According to a preferred embodiment, the granules of material which can be used as a road binder or as a sealing binder exhibit stability during transport and / or storage and / or handling at a temperature of up to 100 ° C., advantageously. from 20 ° C to 90 ° C, preferably from 20 ° C to 80 ° C, more preferably from 40 ° C to 80 ° C, even more preferably from 40 ° C to 60 ° C, for a period greater than or equal to 2 months, preferably greater than or equal to 3 months.

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According to a preferred embodiment, in the method of the invention, the second composition is applied to the core of the granules in a fluidized air bed device.

The invention also relates to the use of the granules defined above as a road binder.

According to a preferred embodiment, the use relates to the manufacture of mixes.

The invention also relates to a process for manufacturing mixes comprising at least one road binder and aggregates, the road binder being chosen from the granules defined above, this process comprising at least the steps of:

- heating of the aggregates to a temperature ranging from 100 ° C to 180 ° C, preferably from 120 ° C to 160 ° C,

- mixing the aggregates with the road binder in a tank such as a mixer or a mixer drum,

- obtaining of asphalt.

According to a preferred embodiment, the mix manufacturing process does not include a step of heating the road binder before it is mixed with the aggregates.

The invention finally relates to a method for transporting and / or storing and / or handling a material which can be used as a road binder or as a sealing binder, said material being transported and / or stored and / or handled in granular form as defined. above.

detailed description

The objectives which the Applicant has set for itself have been achieved thanks to the development of compositions of material which can be used as a road binder or as a sealing binder, in a divided form, having a core / shell structure, in which the core is based on a first composition and the coating layer gives the overall structure improved properties under extreme conditions of transport and / or storage and / or handling compared to granules of material usable as a road binder or as a binder sealing known from the prior art.

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A first object of the invention relates to granules of material which can be used as a road binder or as a sealing binder comprising a core and a coating layer

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I in which:

- the core consists of a first composition which comprises at least one material chosen from: a bitumen base, a pitch, a clear binder, and,

- the coating layer consists of a second composition which comprises:

• at least one viscosifying compound chosen from cellulose ethers, and • at least one anti-caking agent.

By "high ambient temperature" is meant the temperature resulting from the climatic conditions in which the material which can be used as a road binder or as a waterproofing binder is transported and / or stored and / or handled, in particular road bitumen. More precisely, the high ambient temperature is equivalent to the temperature reached during transport and / or storage of the material which can be used as a road binder or as a waterproofing binder, in particular road bitumen, this temperature being less than 100 ° C. Advantageously, the high ambient temperature is from 20 ° C to 90 ° C, preferably from 20 ° C to 80 ° C, more preferably from 40 ° C to 80 ° C, even more preferably from 40 ° C to 60 ° C, it being understood that the high ambient temperature implies that no heat input is provided other than that resulting from climatic conditions.

The invention relates to materials which can be used as a road binder or as a waterproofing binder, in particular bitumens liable to be solid when subjected to high ambient temperatures, in particular a temperature of up to 100 ° C, advantageously , from 20 ° C to 90 ° C, preferably from 20 ° C to 80 ° C, more preferably from 40 ° C to 80 ° C, even more preferably from 40 ° C to 60 ° C.

For the purposes of the present invention, the term “material usable as a road binder or as a waterproofing binder” means any material capable of being used for this use, and in particular: bitumen bases, bitumen / polymer compositions, compositions bitumen with additives, pitches, bitumen-polymer stock solutions, clear binders, clear binder-polymer stock solutions, mixtures of these materials in all proportions.

The term “material which is solid at elevated ambient temperature” is understood to mean a material exhibiting a solid appearance at elevated ambient temperature under conditions of transport and / or storage and / or handling. More specifically, the term “solid material at high ambient temperature” is understood to mean a material which retains its solid appearance throughout transport and / or storage and / or handling at high ambient temperature, that is to say DUPLICATA

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II ⁸ say a material which does not flow at a temperature of up to 100 ° C, advantageously of

20 ° C to 90 ° C, preferably 20 ° C to 80 ° C, more preferably 40 ° C to 80 ° C, even more preferably 40 ° C to 60 ° C, under its own weight and more, which does not creep when subjected to a temperature of up to 100 ° C, advantageously from 20 ° C to

90 ° C, preferably 20 ° C to 80 ° C, more preferably 40 ° C to 80 ° C, even more preferably 40 ° C to 60 ° C, and to pressure forces resulting from transport conditions and / or storage and / or handling.

The term “bitumen that is solid at room temperature” is understood to mean a bitumen having a solid appearance at room temperature regardless of the transport and / or storage conditions.

More precisely, by solid bitumen at room temperature is meant a bitumen which retains its solid appearance throughout transport and / or storage at room temperature, that is to say a bitumen which does not flow at room temperature under its own weight and moreover, which does not creep when subjected to pressure forces resulting from transport and / or storage conditions.

By “coating layer covering all in part of the surface of the heart” is meant that the coating layer covers at least 90% of the surface of the heart, preferably at least 95% of the surface of the heart, more preferably at least. 99% of the surface of the heart.

The expression "consists essentially of" followed by one or more characteristics, means that can be included in the process or the material of the invention, in addition to the components or steps explicitly listed, components or steps which do not modify significantly the properties and characteristics of the invention.

The expression "between X and Y" includes the limits. This expression therefore means that the target interval includes the values X, Y and all values from X to Y.

The composition according to the invention makes it possible to obtain granules of solid material which can be used as a road binder or as a sealing binder, in particular of bitumen, comprising a coating layer which is resistant to climatic conditions and to conditions of transport and / or of storage of road binders and / or waterproofing binders, in particular which is resistant to climatic conditions and to the conditions of transport and / or storage of solid road bitumen, which easily breaks under a mechanical shear effect, such as by example under the effect of a mechanical shear applied in a tank such as a mixer or a mixer drum during the production of asphalt mixes.

More particularly, the coating layer is resistant to transport and / or storage of road binders and / or waterproofing binders, in particular bitumen, at room temperature

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The heart of the granules / first composition:

First variant:

According to a first variant, the cores of the granules of material which can be used as a road binder or as a sealing binder are prepared from a first bitumen composition comprising one or more bitumen bases.

Preferably, the bitumen granules are prepared from a first bitumen composition comprising:

- one or more bitumen bases,

- from 0.1% to 5% by mass, preferably from 0.5% to 4% by mass, more preferably from 0.5% to 2.5% by mass of at least one chemical additive, the percentages being by mass relative to the total mass of bitumen base.

The bitumen base and the chemical additive are as described below.

Preferably, the bitumen granules are prepared from a first bitumen composition comprising:

- one or more bitumen bases,

- from 0.1% to 5% by mass, preferably from 0.5% to 4% by mass, more preferably from 0.5% to 2.5% by mass of at least one chemical additive and,

- from 0.5% to 20% by mass, preferably from 2% to 20% by mass, more preferably from 4% to 15% by mass of at least one anti-caking agent, the percentages being by mass relative to the total mass of bitumen base.

According to a second preferred embodiment, the cores of the granules are prepared from a first composition comprising:

- one or more bitumen bases,

- between 0.1% and 5% by mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.5% by mass of at least one chemical additive,

- And between 0.05% and 15% by mass, preferably between 0.1% and 10% by mass, more preferably between 0.5% and 6% by mass of at least one olefinic polymer adjuvant, the percentages being by mass relative to the total mass of bitumen base.

According to a third preferred embodiment, the cores of the granules are prepared from a first composition comprising:

- one or more bitumen bases,

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-between 0.1% and 5% by mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.5% by mass of at least one chemical additive,

- and between 0.05% and 15% by mass, preferably between 0.1% and 10% by mass, more preferably between 0.5% and 6% by mass of at least one polymer, the percentages being by mass relative to the total mass of bitumen base.

Advantageously, the different embodiments described above for the granules can be combined with one another.

Second variant:

According to a second variant, the cores of the granules of material which can be used as a road binder or as a sealing binder are prepared from a first composition comprising at least one pitch.

According to a first embodiment, the cores of the granules consist of a first composition based on pitch.

According to a second embodiment, the cores of the granules consist of a first composition based on pitch and at least one bitumen base.

According to an embodiment of this variant, the first composition comprises at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175. ° C, it being understood that the penetrability is measured according to the standard EN 1426 and that the TBA is measured according to the standard EN 1427.

According to one embodiment of this variant, the first composition comprises:

- at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to the EN 1426 standard and that the TBA is measured according to the EN 1427 standard,

I- at least one bitumen base, and

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- at least one chemical additive.

Third variant:

| According to a third variant, the granules of material which can be used as a road binder or as a sealing binder are prepared from a first composition comprising at least one clear binder.

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Conventional bituminous binders, due to the presence of asphaltenes, are black in color and are therefore difficult to color. Colored coatings are used more and more because they allow, among other things, to improve the safety of road users by clearly identifying specific lanes such as pedestrian lanes, cycle lanes, bus lanes. They also make it possible to materialize certain danger zones such as city entrances or dangerous bends. Colored coatings promote visibility in low light conditions, for example at night or in particular sites such as tunnels. Finally, they simply improve the aesthetic appearance of urban roads and can be used for public places, courtyards of buildings and schools, sidewalks, pedestrian streets, garden and park paths. , parking and rest areas.

Consequently, for all of the aforementioned applications, it is preferred to use clear synthetic binders, which do not contain asphaltenes and which can be colored.

According to this variant, the first composition comprises at least one clear binder.

Advantageously, the first composition comprises at least one clear binder base and at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures.

According to one embodiment of the invention, the first composition comprises from 0.1% to 5% by mass, preferably from 0.5% to 4% by mass, more preferably from 0.5% to 2.5% by mass of said chemical additive relative to the total mass of said additive clear binder.

According to one embodiment of the invention, the first composition comprises

- at least one clear binder base,

- between 5% and 30% by mass, preferably between 6% and 28% by mass, more preferably between 7% and 26% by mass of the chemical additive (s) relative to the total mass of said clear binder base.

In this case, the first composition is said to be a concentrated clear binder.

According to a preferred embodiment, the granules are prepared from a first composition comprising:

- one or more clear binder bases,

- from 30 to 40% of at least one polymer,

- from 4 to 6% of at least one compatibilizer,

- from 3% to 15% of at least one anti-caking agent,

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The term “clear binder solid when cold and in divided form” means a clear binder which is solid at room temperature which is packaged in divided form, that is to say in the form of units which are distinct from each other, which are called granules.

The clear binder according to the invention is designated interchangeably in the present description by "clear binder, solid when cold and in divided form" or by "clear binder with additives".

Preferably, the clear binder is a composition which can be used as a substitute for bitumen-based binders for the preparation, for example, of colored asphalt mix. A clear binder is free of asphaltenes and can therefore retain the natural color of the aggregate it is mixed with or be easily colored with pigments.

Bitumen base

Advantageously, the core or core of the solid bitumen granules according to the invention is prepared from a first composition, which is a road bitumen composition, said first composition being prepared by bringing into contact:

- one or more bitumen bases, and

- optionally at least one chemical additive.

For the purposes of the invention, the terms "bitumen" and "road bitumen" are used equivalently and independently of each other. By "bitumen" or "road bitumen" is meant any bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more chemical additives, said compositions being intended for road application.

Among the bitumen bases that can be used according to the invention, there may be mentioned first of all bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or tar sands and bitumens from the refining of crude oil. . The bitumen bases according to the invention are advantageously chosen from bitumen bases obtained from the refining of crude oil. The bitumen bases can be chosen from bitumen bases or mixtures of bitumen bases originating from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches. Bitumen bases can be obtained by conventional processes for manufacturing bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumen bases can optionally be vis-reduced and / or deasphalted and / or rectified to

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The different bitumen bases obtained by the refining processes can be combined with each other to obtain the best technical compromise. The bitumen base can also be a recycling bitumen base. Bitumen bases can be hard grade or soft grade bitumen bases.

According to the invention, for the conventional methods of manufacturing bitumen bases, the operation is carried out at manufacturing temperatures of between 100 ° C and 200 ° C, preferably between 140 ° C and 200 ° C, more preferably between 140 ° C and 170 ° C, and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours. The term “production temperature” is understood to mean the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and duration of the heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594.

According to the invention, the blown bitumens can be produced in a blowing unit, by passing a flow of air and / or oxygen through a starting bituminous base. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid. Generally, the blowing is carried out at high temperatures, of the order of 200 to 300 ° C., for relatively long periods, typically between 30 minutes and 2 hours, continuously or in batches. The blowing time and temperature are adjusted as a function of the properties targeted for the blown bitumen and as a function of the quality of the starting bitumen.

Preferably, the bitumen base used to manufacture the granules of the invention has a needle penetrability measured at 25 ° C according to standard EN 1426 from 5 to 330 1/10 mm, preferably from 10 to 220 1 / 10 mm.

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As is well known, the so-called "needle penetrability" measurement is carried out by means of a standardized test NF EN 1426 at 25 ° C (P25). This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm). The needle penetrability, measured at 25 ° C, according to the standardized test NF EN 1426, represents the measurement of the penetration in a bitumen sample, after a time of 5 seconds, of a needle whose weight with its support is 100 g. Standard NF EN 1426 replaces approved standard NF T 66-004 of December 1986 with effect from December 20, 1999 (decision of the Director General of AFNOR dated November 20, 1999).

The clear binder base

The term “clear binder base” is understood to mean compositions comprising a plasticizer, for example an oil of petroleum or plant origin, a structuring agent, for example a hydrocarbon resin, and a polymer. The composition of the clear binder bases determines certain essential properties of these binders, in particular the plasticity index, the viscosity of the binder, or the color which must be as light as possible.

According to one embodiment of the invention, the clear binder base comprises:

- a plasticizer, for example a natural or synthetic oil, devoid of asphaltenes,

- a structuring agent, for example a hydrocarbon or vegetable resin,

- a copolymer,

- where appropriate, doping agents, or dopes, or adhesion dopes.

Clear binder compositions are described in the following applications and patents and these clear binder compositions can be used as a clear binder base in the present invention.

It is possible to use as a clear binder base a clear binder comprising hydrogenated white oils comprising at least 60% paraffinic carbons (according to the ASTM D2140 method), and a hydrocarbon resin, optionally mixed with copolymers of the ethylene-acetate type. vinyl (EVA) or low density polyethylene, for example of the EPDM (ethylene-propylene-diene-monomer) type, as described in WO 01/53409.

A clear binder comprising an oil with a naphthenic content between 35% and 80% and a hydrocarbon resin, as described in EP 1783174, can be used as a clear binder base.

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A clear binder comprising an oil can be used as the clear binder base. synthetic, a resin and a polymer of SBS or SIS type, as described in EP 1473327.

| A clear binder comprising:

- at least one oil of petroleum origin, preferably an aromatic oil | 5 comprising aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues from stills of petroleum cuts, | - at least one resin of plant origin, preferably chosen from esters of rosin, esters of glycerol and rosin, esters of pentaerythritol and | rosins, taken alone or as a mixture, and

- at least one latex, preferably chosen from latexes of acrylic polymers, | natural rubber latex, synthetic rubber latex, taken alone or as a mixture, as described in WO 2009/150519.

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A clear synthetic binder comprising:

| 15 - at least one oil of vegetable origin preferably chosen from rapeseed, sunflower, soybean, linseed, olive, palm, castor, wood, corn, squash and pips oils | grape, jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and mixtures thereof ,

I - at least one resin of petroleum origin, preferably chosen from hydrocarbon-based resins of petroleum origin obtained from the copolymerization of aromatic, aliphatic, cyclopentadienic petroleum fractions taken alone or as a mixture and, _ - at least one polymer, preferably chosen from copolymers of styrene and of butadiene, copolymers of styrene and of isoprene, ethylene / propene / diene terpolymers,

Polychloroprene islands, copolymers of ethylene and vinyl acetate, copolymers of ethylene and methyl acrylate, copolymers of ethylene and butyl acrylate, ethylene / methyl acrylate / methacrylate terpolymers. glycidyl, ethylene / butyl acrylate / maleic anhydride terpolymers, atactic polypropylenes, taken alone or in mixtures, the quantity of oil of vegetable origin in the binder being greater than or equal to 10% by weight and the quantity of polymer in the binder being less than or equal to 15% by weight, * as described in WO 2010/055491.

According to another embodiment of the invention, the clear binder base comprises:

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I (i) a plasticizer consisting of an oil containing a total content of paraffinic compounds, measured according to the ASTM D2140 method, of at least 50%, preferably at least 60% by weight, more preferably between 50 % and 90%, preferably between

60% and 80%, and (ii) a copolymer based on conjugated diene units and on aromatic monovinyl hydrocarbon units, for example based on butadiene unit and styrene units.

Preferably, the oil is a synthetic oil obtained from deasphalting unit cuts (or "DAO oil").

Preferably, the oil contains a total content of paraffinic compounds greater than or equal to 50%, preferably greater than or equal to 60% by weight, and a total content of naphthenic compounds less than or equal to 25% by weight, measured according to the ASTM D2140 method.

Preferably, the oil contains a total content of paraffinic compounds greater than or equal to 50%, preferably greater than or equal to 60% by weight, a total content of naphthenic compounds less than or equal to 25% by weight, and a content total aromatic compounds less than or equal to 25% by weight, measured according to the ASTM D2140 method.

For example, the oil contains a total content of paraffinic compounds, measured according to the ASTM D2140 method, of between 50% and 90%, preferably between 60% and 80% by weight, a total content of naphthenic compounds of between 5% and 25% by weight, and a total aromatic content of between 5% and 25% by weight.

Preferably, the oil has an aniline point, measured according to ISO2977: 1997, greater than or equal to 80 ° C, preferably greater than or equal to 90 ° C, for example greater than 100 ° C.

Preferably, the clear binder base preferably comprises (i) 40 to 80 wt% plasticizer, (ii) 18 to 50 wt% resin, (iii) 1 to 7 wt% of copolymer; and, (iv) optionally from 0.05% to 0.5% by weight of tackifier dope, for example amine, based on the basis weight of clear binder.

Advantageously, the clear binder base preferably comprises (i) from 40 to 80% by weight of plasticizer, (ii) from 18 to 50% by weight of resin, (iii) from 1 to 7% by weight of

DUPLICATA ¹⁷ copolymer; and, (iv) from 0.05% to 0.5% by weight of tackifier, eg amine, based on the basis weight of clear binder.

Advantageously, the clear binder base also comprises (i) from 45% to 70% by weight of plasticizer, (ii) from 25 to 50% by weight of resin, (iii) from 1% to 7% by weight of copolymer; and, (iv) optionally 0.1% and 0.3% by weight of tackifier dope, based on the total base weight of clear binder.

Preferably, the clear binder base consists essentially of (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight of copolymer, based on the total base weight of clear binder.

Advantageously, the clear binder base consists essentially of (i) from 40 to 80% by weight of plasticizer, (ii) from 20 to 50% by weight of resin, (iii) from 1 to 7% by weight of copolymer and (iv) from 0.05% to 0.5% by weight of tackifier dope, based on the total weight of clear binder base.

Advantageously, the clear binder base also consists essentially of (i) from 45% to 70% by weight of plasticizer, (ii) from 25 to 50% by weight of resin (iii) from 1% to 7% by weight of copolymer; and, (iv) 0.1% and 0.3% by weight of tackifier dope, based on the total base weight of clear binder.

Preferably, the copolymer is a copolymer based on styrene and butadiene units which comprises a weight content of butadiene 1-2 ranging from 5 to 70%.

Preferably, the copolymer is advantageously a copolymer based on styrene and butadiene units which comprises a content by weight of 1-2 butadiene ranging from 5 to 70% and a content by weight of 1,2-vinyl group of between 10 and 40. %.

For example, said copolymer based on styrene and butadiene units has an average molecular weight of between 10,000 and 500,000, preferably between 50,000 and 200,000, and more preferably between 50,000 and 150,000 daltons. Preferably, a styrene / butadiene block copolymer or a styrene / butadiene / styrene block copolymer will be used.

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The clear binders according to the invention are advantageously characterized in that they have a color index less than or equal to 4, preferably less than or equal to 3, as determined according to the ASTM DH4 scale.

In addition, they can advantageously have a softening temperature 5 Ball-Ring temperature determined according to standard NF EN1427 of between 55 ° C and 90 ° C.

Preferably, the clear binder that can be used according to the invention has a penetrability at 25 ° C, measured according to standard NF EN 1426, between 10 and 220 1/10 mm, preferably between 30 and 100 1/10 mm, more preferably. between 40 and 80 1/10 mm. A person skilled in the art can modulate the penetrability of the clear binder usable in the invention in particular by judiciously choosing the weight ratio [structuring agent / plasticizer] in the composition of the clear binder base. Indeed, it is known that an increase in this ratio makes it possible to decrease the penetrability at 25 ° C.

The clear binder bases used in the invention can be prepared, for example, according to the following process comprising the steps of:

(i) mixing the plasticizer, for example DAO oil, and heating at a temperature between 140-200 ° C, for example 10 minutes to 30 minutes, (ii) adding the structuring agent, by example the hydrocarbon resin, mixing and heating at a temperature between 140-200 ° C, for example from 30 minutes to 20 hours, (iii) addition of the polymer (s), for example SBS, mixing and heating at a temperature of between 140-200 ° C, for example, 90 minutes to 3 hours, preferably 90 minutes to 2 hours 30 minutes, (iv) optional addition of a tackifier dope, mixing and heating at a temperature between 140 -200 ° C, for example, from 5 minutes to 20 minutes.

The order of steps (i) to (iv) can be changed.

According to one embodiment of the invention, the cores of the clear binder granules further comprise at least one coloring agent as described above, such as, for example, a pigment.

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In these embodiments, the anti-caking agent and / or the coloring agent will be chosen by | the person skilled in the art depending on the color of the desired clear binder.

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The pitch | According to the French dictionary, "pitch" is understood to mean a residue from the distillation of petroleum, petroleum, coal, wood or other organic molecules.

The invention relates here to residues from the distillation of petroleum, also called "petroleum pitch".

For the purposes of the invention, the terms "pitch" will be used independently of one another,

1 “petroleum pitch” and “deasphalting pitch”.

Pitches can be obtained by conventional refinery manufacturing processes. The manufacturing process corresponds to the succession of atmospheric distillation and vacuum distillation. First, the crude oil is subjected to distillation at atmospheric pressure, which results in a gas phase, different distillates and an atmospheric distillate residue. Then, the residue from the atmospheric distillation itself is subjected to reduced pressure distillation, called vacuum distillation, which separates heavy gas oil, various still cuts and a vacuum distillation residue. This vacuum distillation residue contains "petroleum pitch" in varying concentration.

It is possible to obtain "petroleum pitch" using two methods:

® 1 ^st process:

The vacuum distillation residue is dealphated with the addition of a suitable solvent, such as propane, thereby precipitating the pitch and | 25 separate it from light fractions such as deasphalted oil.

2 ^nd method:

| The vacuum distillation residue is subjected to extraction with solvent, and more precisely with furfuraldehyde. This heterocyclic aldehyde has the particularity of dissolving | selectively aromatic and polycyclic compounds. This process thus makes it possible to eliminate the aromatic extracts and to recover the "petroleum pitch".

According to one embodiment, the pitch is an oxidized pitch.

| Preferably, the oxidized pitch according to the invention is obtained by oxidizing a mixture comprising pitch and a diluent, such as a light gasoline, also called

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For example, oxidized pitches can be made in a blowing unit, by passing a flow of air and / or oxygen through a starting pitch. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid. Generally, the oxidation is carried out at high temperatures, of the order of 200 to 300 ° C, for relatively long times, typically between 30 minutes and 2 hours, continuously or in batches. The oxidation time and temperature are adjusted depending on the desired properties of the oxidized pitch and depending on the quality of the starting pitch.

The mechanical qualities of pitches are generally assessed by determining a series of mechanical characteristics by standardized tests, the most widely used of which are the needle penetrability expressed in 1/10 mm and the softening point determined by the ball test and ring, also called ring and ball softening temperature (TBA).

According to one embodiment of the invention, the pitch exhibits needle penetrability at 25 ° C from 0 to 20 1/10 mm, preferably from 0 to 15 1/10 mm, more preferably from 0 to 10 1 / 10 mm, it being understood that the penetrability is measured according to standard EN 1426.

According to one embodiment of the invention, the pitch has a softening point of between 115 ° C and 175 ° C. Among examples of pitches used in the invention, there are pitches having respectively a softening point of between 115 ° C and 125 ° C, between 135 and 145 ° C or also between 165 and 175 ° C.

The plasticizer

For the purposes of the invention, the term "plasticizer" is understood to mean a chemical constituent which makes it possible to thin and reduce the viscosity and the modulus of the binder obtained.

In one embodiment of the invention, the plasticizer is chosen from oils of petroleum origin, oils of vegetable origin and mixtures thereof.

In a preferred embodiment of the invention, the oils of vegetable origin are chosen from rapeseed, sunflower, soybean, linseed, olive, palm, castor, wood and corn oils, squash, grape seeds, jojoba, sesame, walnut, hazelnut,

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I almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and mixtures thereof.

Preferably, the oils of plant origin are chosen from rapeseed, sunflower, linseed, coconut and soybean oils, and mixtures thereof.

In a preferred embodiment of the invention, the oils of petroleum origin are chosen from aromatic oils or oils of synthetic origin.

Preferably, the aromatic oils comprise aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues from the distillation of petroleum cuts.

More preferably, the aromatic oils have an aromatic compound content of between 30 and 95% by weight, advantageously between 50 and 90% by weight, more advantageously between 60 and 85% by weight (SARA method: Saturates / Aromatics / Resins / Asphaltenes).

More preferably, the aromatic oils have a saturated compound content of between 1 and 20% by weight, advantageously between 3 and 15% by weight, more advantageously between 5 and 10% by weight (SARA method: Saturates / Aromatics / Resins / Asphaltenes).

More preferably, the aromatic oils have a content of resin compounds of between 1 and 10% by weight, advantageously between 3 and 5% by weight, (SARA method: Saturates / Aromatics / Resins / Asphaltenes).

In a preferred embodiment of the invention, the oils of synthetic origin are obtained from deasphalting cuts from the distillation under reduced pressure (vacuum residue, RSV) of crude oil (hereinafter referred to as "DAO oil").

In particular, in a preferred embodiment, the plasticizer consists only of a DAO oil.

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

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In a specific embodiment, the plasticizer is an oil, for example a DAO oil, containing a total content of paraffinic compounds of at least 50% by weight, preferably at least 60% by weight, for example between 50% and 90%, preferably between 60% and 90%, more preferably between 50% and 80% and in particular between 55% and 70% or in particular between 60% and 75%.

In a more specific embodiment, the plasticizer is an oil, for example a DAO oil, further containing a total content of naphthenic compounds which does not exceed 25%, for example between 5% and 25%, and in particular between 10% and 25%.

In a more specific embodiment, the plasticizer is an oil, for example a DAO oil, further containing a total aromatics content which does not exceed 25%, for example between 5% and 25%, and in particular between 8% and 18%.

In a particularly preferred embodiment, the plasticizer is an oil, for example a DAO oil, comprising the respective contents:

(i) a total content of paraffinic compounds of between 50% and 90%;

(ii) a total content of naphthenic compounds of between 5% and 25%, for example between 15% and 25%; and (iii) a total content of aromatic compounds of between 5% and 25%, for example between 10% and 15%.

In a more particularly preferred embodiment, the plasticizer is an oil, for example a DAO oil, comprising the respective contents:

(i) a total content of paraffinic compounds of between 60% and 75%;

(ii) a total content of naphthenic compounds of between 5% and 25%, for example between 15% and 25%; and (iii) a total content of aromatic compounds of between 5% and 25%, for example between 10% and 15%.

Oils meeting the above characteristics and which can be used for the preparation of the clear binder according to the invention are obtained by the processes for deasphalting the vacuum residues (RSV) resulting from petroleum refining, for example by deasphalting using 'a

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I C3 to Ce solvent, preferably propane. These deasphalting processes are well known to those skilled in the art and are described for example in Lee et al 2014, Fuel Processing Technology 119: 204-210: The residues resulting from the vacuum distillation (RSV) are separated according to their molecular weight. in the presence of C3 to Ce solvent (for example propane). The so-called DAO ("deasphalted oil") oil thus obtained is rich in paraffin, has a very low asphaltene content, has an evaporation temperature of between 440 ° C and 750 ° C, and an API gravity much higher than that. vacuum residue.

The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil from which the DAO oil originates and on the refining process used. Those skilled in the art know how to determine the respective contents of paraffinic, naphthenic and aromatic compounds in a DAO oil, for example using the SARA fractionation method also described in Lee et al 2014, Fuel Processing Technology 119: 204-210 and thus select the appropriate DAO oil for the preparation of the clear binder according to the invention.

In one embodiment, the amount of plasticizer used in the process for preparing the clear binder base is 40% to 80%, preferably 45% to 70% by weight relative to the total weight of clear binder base.

The structuring agent

The term “structuring agent” is understood to mean any chemical constituent conferring mechanical properties and satisfactory cohesiveness to said binder.

The structuring agent used in the context of the invention is a resin, preferably chosen from resins of hydrocarbon-based petroleum origin, for example obtained from the copolymerization of aromatic, aliphatic or cyclopentadienic petroleum fractions, taken alone or as a mixture, preferably obtained from aromatic petroleum fractions. For example, it may be a polycycloaliphatic thermoplastic resin, for example of the hydrogenated cyclopentadiene homopolymer type, low molecular weight.

More particularly, the hydrocarbon resin of the cyclopentane type has a softening point (or Ball-Ring temperature, TBA, 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 1.

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Other examples of resins which can be used as a structuring agent include, without being limiting, resins of plant origin obtained from plants and / or plants. They can be said to be harvested, that is to say harvested from living plants. They can be used as they are, one then speaks of natural resins or they can be chemically transformed, one then speaks of modified natural resins.

Among the harvest resins are additive resins, dammar, natural rosins, modified rosins, rosin esters and metal resins. These can be taken alone or as a mixture.

Among the natural rosins, mention may be made of rosins from gemstones and wood, in particular from pine, and / or tall oil or tall oil. These natural rosins can be taken alone or as a mixture.

Among the modified rosins, mention may be made of hydrogenated rosins, dismutated rosins, polymerized rosins and / or maleized rosins. These modified natural rosins can be taken alone or as a mixture, and undergo one or more disproportionation, polymerization and / or maleization treatments.

Among the rosin esters, mention may be made of the methyl esters of natural rosins, the methyl esters of hydrogenated rosins, the esters of glycerol and of natural rosins, the esters of glycerol and of hydrogenated rosins, the esters of glycerol and of dismutated rosins, esters of glycerol and polymerized rosins, esters of glycerol and maleized rosins, esters of pentaerythntol and natural rosins and esters of pentaerythritol and hydrogenated rosins. These rosin esters can be taken alone or as a mixture and come from rosin which has undergone one or more disproportionation, polymerization and / or maleization treatments.

Esters of pentaerythritol and natural rosins and esters of pentaerythritol and hydrogenated rosins are preferred rosin esters.

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

The weight ratio between the structuring agent and the plasticizer used for the preparation of the clear binder is generally from 0.3 to 1.5, for example from 0.5 to 1.

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In a specific embodiment, the amount of structuring agent used in the process for preparing the clear binder base is 25 to 50% by weight relative to the total weight of clear binder base.

The polymer

The polymer used in the first composition is a copolymer based on conjugated diene units and on aromatic monovinyl hydrocarbon units. The conjugated diene is preferably chosen from those comprising from 4 to 8 carbon atoms per monomer, for example butadiene, 2-methyl-l, 3-butadiene (isoprene), 2,3-dimethyl-l, 3- butadiene, 1,3-pentadiene and 1,2-hexadiene, chloroprene, carboxylated butadiene, carboxylated isoprene, especially butadiene and isoprene, and mixtures thereof.

The monovinyl aromatic hydrocarbon is preferably chosen from styrene, Γοmethyl 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.

More particularly, the polymer consists of one or more copolymers chosen from block copolymers of styrene and butadiene, of styrene and of isoprene, of styrene and of chloroprene, of styrene and of carboxylated butadiene or of styrene and of isoprene. carboxylated. A preferred copolymer is a copolymer based on butadiene units and on styrene units, such as the styrene / butadiene SB block copolymer or the styrene / butadiene / styrene SBS block copolymer.

The copolymer of styrene and of conjugated diene, in particular the copolymer of styrene and of butadiene, advantageously has a styrene content by weight ranging from 5 to 50%, preferably from 20 to 50%.

The copolymer of styrene and of conjugated diene, in particular the copolymer of styrene and of butadiene, advantageously has a content by weight of butadiene (1-2 and 1-4) ranging from 50 to 95%. The copolymer of styrene and of conjugated diene, in particular the copolymer of styrene and of butadiene, advantageously has a weight content of butadiene 1-2 ranging from 5 to 70%, preferably from 5 to 50%. The 1-2 butadiene units are the units which result from the polymerization via the 1-2 addition of the butadiene units.

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The weight average molecular weight of the copolymer of styrene and of conjugated diene, and in particular that of the copolymer of styrene and of butadiene, can be between, for example, between 10,000 and 500,000, preferably between 50,000 and 200,000 and more. preferably from 50,000 to 150,000 daltons.

In a specific embodiment, the total amount of polymer used in the process of the invention is 0.5 to 20% by mass, preferably 1 to 10%, preferably 1 to 7%, per example from 2% to 5% relative to the total mass of bitumen base, or of clear binder.

In another specific embodiment, the total amount of polymer used in the process of the invention is 20% to 50% by mass, relative to the total mass of bitumen base, or relative to the mass. total clear binder base.

In this case, the first composition is called a stock solution of bitumen / polymer composition or stock solution of clear binder / polymer composition. It is intended to be transported and stored in concentrated form, then diluted with the desired amount of bitumen base or clear binder base just before its use as a road binder or as a coating binder. According to the invention, it is possible to form granules of bitumen stock solution or of clear binder, so as to facilitate their transport and storage as well as their handling at high ambient temperature.

According to a variant of the invention, the polymer is chosen from micronized polymers. Preferably, according to this variant, the polymer has particles with a diameter ranging from 250 to 1000 μm, preferably with a diameter ranging from 400 to 600 μm.

Compatibilizing agent

Preferably, the compatibilizer is chosen from waxes, for example animal waxes, vegetable waxes, mineral waxes and mixtures thereof.

Animal and vegetable waxes are mainly composed of mixtures of fatty acid derivatives (fatty acid esters) while mineral waxes are paraffinic derivatives.

Stickiness dopes

In order to improve the reciprocal affinity between the binder and the aggregates and to ensure their durability, adhesiveness dopes can also be used in the first.

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I composition, as a mixture with the other components, in particular the clear binder, or the bitumen base or the pitch. These are, for example, nitrogenous surfactant compounds derived from fatty acids (amines, polyamines, alkyl-polymane, etc.).

When they are added to the first composition, the stickiness dopes generally represent between 0.05% and 0.5% by weight relative to the weight of clear binder or bitumen base or pitch. For example, in a specific embodiment, from 0.05% to 0.5% of amine will be added, preferably from 0.1% to 0.3% of amine relative to the total base mass of clear binder or bitumen base or pitch.

Coloring agents

The clear synthetic binder can also include one or more coloring agents, such as inorganic pigments or organic dyes. The pigments are selected according to the shade, the color desired for the coating. Metal oxides such as iron oxides, chromium oxides, cobalt oxides, titanium oxides will be used, for example, to obtain the colors red, yellow, gray, blue green or white. The pigments 15 can be added, either in the clear binder or in the mix (mixed with the aggregates, for example) or in an emulsion of the clear binder.

The chemical additive

The bitumen base, the pitch or the clear binder can further comprise at least one chemical additive chosen from: an organic compound, a paraffin, a polyphosphoric acid and their mixtures.

In particular, when the solid material comprises at least one chemical additive, it is in an amount suitable so that its penetrability is preferably 5 to 50 1 / 10mm and / or that the ball and ring softening temperature (TBA) is, preferably greater than or equal to 60 ° C, it being understood that the penetrability is measured at 25 ° C according to standard EN 1426 and TBA according to standard EN 1427.

According to a first embodiment of the invention, the chemical additive is an organic compound. Advantageously, the organic compound has a molar mass of less than or equal to 2000 gmol ′ ¹ , preferably a molar mass of less than or equal to 1000 gmol ′ ¹ .

In this first embodiment, according to a first variant, the organic compound is a compound of general formula (I):

Arl-R-Ar2 (I), in which:

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DUPLICATA • Arl and Ar2 represent, independently of one another, a benzene ring or a system of condensed aromatic rings of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and • R represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from amide, ester, hydrazide, urea, carbamate and anhydride functions.

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Preferably, Arl and / or Ar2 are substituted by at least one alkyl group of 1 to 10 carbon atoms, advantageously in one or more positions ortho with respect to the hydroxyl group (s), more preferably Arl and Ar2 are 3,5-dialkyl-4hydroxyphenyl groups, advantageously 3,5-di- / er / -butyl-4-hydroxyphenyl groups.

Preferably, R is in the para position with respect to a hydroxyl group of Ar1 and / or Ar2.

Advantageously, the compound of formula (I) is 2 ’, 3-bis [(3- [3, 5-di-teri-butyl-4hydroxyphenyl] propionyl)] propionohydrazide.

According to a second variant of this first embodiment, the organic compound is a compound of general formula (II):

R '- (NH) _n CONH- (X) m- (NHCO) p (NH) _n -R''(II), in which,

- the groups R 'and R ", identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, and optionally comprising heteroatoms such as N, O, S, C5-C24 hydrocarbon rings and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S, and R ”may be H;

- the group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms, such as N, O, S, C5 hydrocarbon rings -C24 and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

- n, m and p are integers having a value of 0 or 1 independently of each other.

According to this variant, when the integer m has a value of 0 and when the integer pa has a value of 1, then the groups R '- (NH) _n CONH and NHCO (NH) _n -R ”are covalently linked by a CONH-NHCO hydrazide bond. The R ′ group, or the R ″ group,

DUPLICATA then comprises at least one group chosen from: a hydrocarbon chain of at least carbon atoms, an aliphatic ring of 3 to 8 atoms, an aliphatic, partially aromatic or fully aromatic condensed polycyclic system, each ring comprising 5 or 6 atoms.

Still according to this variant, when the integer m has a value of 1, then the group R ', the group R ”and / or the group X, comprises at least one group chosen from: a hydrocarbon chain of at least 4 atoms of carbon, an aliphatic ring of 3 to 8 atoms, an aliphatic, partially aromatic or fully aromatic condensed polycyclic system, each ring comprising 5 or 6 atoms.

Preferably, the R ’and / or R” group comprises an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, in particular chosen from the groups C4H9, C5H11, C9H19, C11H23, C12H25, C17H35, C18H37, C21H43, C22H45.

Preferably, the group X represents a linear, saturated hydrocarbon chain comprising from 1 to 22 carbon atoms, advantageously X represents a linear, saturated hydrocarbon chain comprising from 1 to 12 carbon atoms, even better still from 1 to 4 carbon atoms. Preferably, the group X is chosen from the groups C2H4, C ₃ H ₆ .

Preferably, the group X can also be a cyclohexyl group or a phenyl group, the radicals R '- (NH) _n CONH- and -NHCO (NH) _n -R ”can then be in the ortho, meta or para position. On the other hand, the radicals R '- (NH) _n CONH- and -NHCO (NH) _n -R ”may be in the cis or trans position with respect to each other. In addition, when the radical X is cyclic, this ring can be substituted by groups other than the two main groups R '- (NH) _n CONH- and -NHCO (NH) _n -R ”.

Preferably, the X group comprises two rings of 6 carbon atoms linked by a CH 2 group, these rings being aliphatic or aromatic. In this case, the group X is a group comprising two aliphatic rings linked by an optionally substituted CH2 group, for example:

Advantageously, according to this variant, the organic compound is a compound of general formula (II) chosen from:

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- hydrazide derivatives such as the compounds C5HU-CONH-NHCO-C5H11, C9H19CONH-NHCO-C9H19, C11H23-CONH-NHCO-C11H23, C17H35-CONH-NHCO-C17H35, or

C21H43-CONH-NHCO-C21H43;

- diamides such as N, N'-ethylenedi (laurylamide) of formula C11H23-CONH-CH25 CH2-NHCO-C11H31, N, N'-ethylenedi (myristylamide) of formula C13H27-CONH-CH2-CH2NHCO-C13H27, N, N'-ethylenedi (palmitamide) of formula C15H31-CONH-CH2-CH2-NHCOC15H31, N, N'-ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35;

- monoamides such as laurylamide of formula C11H23-CONH2, myristylamide of formula C13H27-CONH2, palmitamide of formula C15H31-CONH2, stearamide of formula C17H35-CONH2;

- ureid derivatives such as 4,4'-bis (dodecylaminocarbonylamino) diphenylmethane of formula C12H25-NHCONH-C6H4-CH2-C6H4-NHCONH-C12H25.

Preferably, the compound of general formula (II) is chosen from those which satisfy the condition n = 0.

Preferably, the compound of general formula (II) is chosen from those which satisfy the condition: the sum of the numbers of the carbon atoms of R ', X and R ”is greater than or equal to 10, advantageously greater than or equal to 14 , preferably greater than or equal to 18.

Preferably, the compound of general formula (II) is chosen from those which satisfy the condition: the number of carbon atoms of at least one of R ′ and R ″ is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.

Preferably, according to a first variant, the compound of general formula (II) is chosen from those of formula (IIA):

R'-CONH- (X) _m -NHCO-R ”(IIA) where R ', R”, m and X have the same definition as above.

Preferably, in formula (IIA) when m = 1, the group X represents a linear, saturated hydrocarbon chain comprising from 1 to 22 carbon atoms, advantageously X represents a linear, saturated hydrocarbon chain comprising from 1 to 12 carbon atoms , even better from 1 to 4 carbon atoms. Preferably, the group X is chosen from the groups C2H4, C3H6.

Preferably, the compound of general formula (IIA) is chosen from those which satisfy the condition: the sum of the numbers of the carbon atoms of R ', X and R ”is greater than or equal to 10, advantageously greater than or equal to 14 , preferably greater than or equal to 18.

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Preferably, the compound of general formula (IIA) is chosen from those which satisfy the condition: the number of carbon atoms of at least one of R ′ and R ″ is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.

More preferably, according to this variant, the compound of general formula (IIA) is chosen from hydrazide derivatives such as the compounds C5H11-CONH-NHCO-C5H11, C ₉ Hi9-CONH-NHCO-C ₉ Hi9, Ci 1H23-CONH -NHCO-C11H23, C17H35-CONH-NHCO-C17H35, or C21H43-CONH-NHCO-C21H43; diamides such as N, N'-ethylenedi (laurylamide) of formula C11H23-CONH-CH2-CH2-NHCO-C11H31, N, N'-ethylenedi (myristylamide) of formula C13H27-CONH-CH2-CH2-NHCO- C13H27, N, N'-ethylenedi (palmitamide) of formula C15H31-CONH-CH2-CH2-NHCO-C15H31, N, N'-ethylenedi (stearamide) of formula C17H35CONH-CH2-CH2-NHCO-C17H35; mono amides such as laurylamide of formula C11H23-CONH2, myristylamide of formula C13H27-CONH2, palmitamide of formula C15H31-CONH2, stearamide of formula C17H35-CONH2.

Even more advantageously, the compound of general formula (IIA) is N, N'15 ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35.

Preferably, according to a second variant, the compound of general formula (II) is chosen from those of formula (IIB):

R’-CONH-R ”(IIB) where R’ and R ”have the same definition as above.

Advantageously, according to this variant, the sum of the numbers of the carbon atoms of R ’and R” is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.

Even more advantageously, according to this variant, the number of carbon atoms of R ′ is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14, and R ”= H.

Advantageously, the compound of general formula (II) is chosen from hydrazide derivatives such as the compounds C5H11-CONH-NHCO-C5H11, C9H19-CONH-NHCO-C9H19, C11H23-CONH-NHCO-C11H23, C17H35-CONH-NHCO- C17H35, or C21H43-CONH-NHCOC21H43; diamides such as N, N'-ethylenedi (laurylamide) of formula C11H23-CONH30 CH2-CH2-NHCO-C11H31, N, N'-ethylenedi (myristylamide) of formula C13H27-CONH-CH2CH2-NHCO-C13H27, N, N'-ethylenedi (palmitamide) of formula C15H31-CONH-CH2-CH2NHCO-C15H31, N, N'-ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCOC17H35; mono amides such as laurylamide of formula C11H23-CONH2,

DUPLICATE

I

I I

I

I

I

I I

I

I myristylamide of formula C13H27-CONH2, palmitamide of formula C15H31-CONH2, stearamide of formula C17H35-CONH2.

Even more advantageously, the compound of general formula (II) is N, N'ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH ₂ -NHCO-C17H35.

Preferably, when the chemical additive is chosen from organic compounds of formula (II), it is used in combination with at least one other chemical additive chosen from organic compounds of formula (I), (III), (V) , (VI) and (VII) and / or the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV).

According to a third variant of this embodiment, the organic compound is a compound of formula (III):

(R-NHCO) _X -Z- (NHCO-R ') _y (III), in which,

- R and R ’, identical or different, contain a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms, rings and / or heterocycles,

- Z represents a tri-functionalized group chosen from the following groups:

AA fS

ΥΛ _χ λ _ν λ Q - „WW“ T

Z1 Z ₂ IZ

- x and y are different integers of value varying from 0 to 3 and such that x + y = 3.

Preferably, when x is 0 and Z represents Z2, the compound of formula (III) is N2, N4, N6-tridecylmelamine having the following formula with R ’representing the group C9H19:

DUPLICATE

Other preferred compounds corresponding to formula (III) are such that x is equal to 0, Z represents Z ₂ and R ′ represents a saturated, linear hydrocarbon chain, from 1 to 22 carbon atoms, preferably from 2 to 18 carbon atoms, preferably 5 to 12 carbon atoms.

Other preferred compounds corresponding to formula (III) are such that: y is equal to 0 and Z represents Zi, the compounds then have the formula:

O HN

R with R chosen from the following groups, taken alone or as mixtures:

. , I I I

Other preferred compounds corresponding to formula (III) are such that: y is equal to 0, Z represents Zi and R represents a saturated, linear hydrocarbon chain, from 1 to 22 carbon atoms, preferably from 8 to 12 atoms. of carbon.

According to a fourth variant of this embodiment, the organic compound is a reaction product of at least one Cj-Cn polyol and at least one C2-C12 aldehyde. Among the polyols which can be used, mention may be made of sorbitol, xylitol, mannitol and / or ribitol. Preferably, the polyol is sorbitol.

Advantageously, according to this variant, the organic compound is a compound which comprises at least one function of general formula (IV):

DUPLICATE

With:

- x is an integer,

-R is chosen from an alkyl, alkenyl, aryl or C1-Cn aralkyl radical optionally substituted by one or more halogen atoms, one or more Cj-C6 alkoxy groups.

The organic compound is advantageously a derivative of sorbitol. By “sorbitol derivative” is meant any reaction product obtained from sorbitol. In particular, any reaction product obtained by reacting an aldehyde with D-sorbitol. By this condensation reaction, sorbitol acetals, which are sorbitol derivatives, are obtained. 1,3: 2,4-Di-O-benzylidene-D-sorbitol is obtained by reacting 1 mole of D-sorbitol and 2 moles of benzaldehyde and has the formula:

The sorbitol derivatives can thus be all the condensation products of aldehydes, in particular of aromatic aldehydes with sorbitol. We will then obtain 20 sorbitol derivatives of general formula: θ

O ---- ((---- Ar ₂

Ar, ---- Ç \ O ⁰ \ y — oh

HO 'where An and Ar ₂ are optionally substituted aromatic rings.

Among the sorbitol derivatives, other than 1,3: 2,4-Di-O-benzylidene-D-sorbitol, we can find, for example, 1,3: 2,4: 5,6-tri-O-benzylidene- D-sorbitol, 2,4-mono-O-benzylidene D-sorbitol, l, 3: 2,4-bis (p-methylbenzylidene) sorbitol, l, 3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol, l, 3: 2,4-bis (p-ethylbenzylidene) sorbitol, l, 3: 2,4-bis (p-propylbenzylidene) sorbitol, 30 l, 3: 2,4-bis (p-butylbenzylidene) sorbitol , l, 3: 2,4-bis (p-ethoxylbenzylidene) sorbitol, 1,3: 2,4DUPLICATA .35 bis (p-chlorobenzylidene) sorbitol, l, 3: 2,4-bis (p-bromobenzylidene) sorbitol, 1,3: 2,4-Di-Omethylbenzylidene-D-sorbitol, l, 3: 2,4-Di-O-dimethylbenzylidene-D-sorbitol, 1,3: 2,4-Di-O (4-methylbenzylidene) -D-sorbitol, 1,3: 2,4-Di-O- (4,3-dimethylbenzylidene) -D-sorbitol. Preferably, according to this variant, the organic compound is 1,3: 2,4-Di-O-benzylidene-Dsorbitol.

ΙΟ

According to a fifth variant of this embodiment, the organic compound is a compound of general formula (V):

R ”- (COOH) _Z (V), in which R” represents a linear or branched, saturated or unsaturated chain comprising from 4 to 68 carbon atoms, preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 carbon atoms and z is an integer ranging from 2 to 4.

Preferably, the group R ”is a saturated linear chain of formula C _w H2w with w an integer varying from 4 to 22, preferably from 4 to 1.2.

According to this variant of the invention, the organic compounds corresponding to formula (V) can be diacids (z = 2), triacids (z = 3) or tetracids (z = 4). The preferred organic compounds according to this variant are diacids with z = 2.

Preferably, according to this variant, the diacids have the general formula HOOCC _w H _2w -COOH with w an integer varying from 4 to 22, preferably from 4 to 12 and where z = 2 and R = CwH2w ·

Advantageously, according to this variant, the organic compound is a diacid chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8-octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10decanedioic acid with w = 8, undecanedioic acid with w = 9 , 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

Advantageously, the diacid is sebacic acid.

The diacids can also be diacid dimers of unsaturated fatty acid (s), that is to say dimers formed from at least one unsaturated fatty acid, for example from a single unsaturated fatty acid or from two different unsaturated fatty acids. The diacid dimers of unsaturated fatty acid (s) are conventionally obtained by intermolecular dimerization reaction of at least one unsaturated fatty acid (Diels Aider reaction, for example). Preferably, only one type of unsaturated fatty acid is dimerized. They derive in particular from the dimerization of an unsaturated fatty acid in particular of Cs to C34, in particular of C12 to C22, in particular of C16 to C20, and more particularly of Cis. A preferred fatty acid dimer is

DUPLICATA obtained by dimerization of linoleic acid, which can then be partially or totally hydrogenated. Another preferred fatty acid dimer has the formula HOOC- (CH2) 7CH = CH- (CH2) 7-COOH. Another preferred fatty acid dimer is obtained by dimerization of methyl linoleate. Likewise, one can find fatty acid triacids and fatty acid tetracids, obtained respectively by trimerization and tetramerization of at least one fatty acid.

According to a sixth variant of this embodiment, the organic compound is a compound of general formula (VI):

(CH ₂ ) _p

(VI) in which,

- the groups Y and Y 'represent, independently of one another, an atom or group chosen from: H, - (CH2) _q -CH3, - (CH2) _q -NH2, - (CH2) _q -OH, - (CH2) _q -COOH or

- (CH ₂ ) _q -NH- (CH ₂ ) _q - N (CH ₂ ) _p -γ

O with q an integer varying from 2 to 18, preferably from 2 to 10, preferably from 2 to 4 and p an integer greater than or equal to 2, preferably having a value of 2 or 3.

Among the preferred organic compounds corresponding to formula (VI), mention may be made of the following compounds:

HN NH

HN. .NH

o

HN. .N nh ₂ o

nh ₂

O h ₂ n

N N

O nh ₂

HN N

N. .NH

DUPLICATE

Preferably, according to this variant, the organic compound of general formula (VI) is:

According to a seventh variant of this embodiment, the organic compound is a compound of general formula (VII):

R-NH-CO-CO-NH-R '(VII) in which, R and R', identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, optionally substituted, and optionally comprising heteroatoms, rings and / or heterocycles.

According to another embodiment of the invention, the chemical additive is a paraffin.

Paraffins have chain lengths of 30 to 120 carbon atoms (C30 to C120). The paraffins are advantageously chosen from polyalkylenes. Preferably, polymethylene paraffins and polyethylene paraffins will be used according to the invention. These paraffins may be of petroleum origin or from the chemical industry. Advantageously, the paraffins used are synthetic paraffins resulting from the conversion of biomass and / or natural gas.

Preferably, these paraffins contain a large proportion of so-called “normal” paraffins, that is to say straight-chain, unbranched linear paraffins (saturated hydrocarbons). Thus, paraffins can comprise from 50 to 100% normal paraffins and from 25 to 50% isoparaffins and / or branched paraffins. More preferably, the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins and / or branched paraffins. Advantageously, the paraffins comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins. Even more preferably, the paraffins comprise 85-95% normal paraffins and 5-15% isoparaffins.

Preferably, the paraffins are polymethylene paraffins. More particularly, the paraffins are synthetic polymethylene paraffins, for example paraffins obtained from the conversion of synthesis gas by the FischerTropsch process. In the Fischer-Tropsch process, paraffins are obtained by reaction of

DUPLICATE hydrogen with carbon monoxide over a metal catalyst. Fischer-Tropsch synthesis methods are described for example in the publications EP 1 432 778, EP

328 607 or EP0 199 475.

According to another embodiment of the invention, the chemical additive is a polyphosphoric acid. The polyphosphoric acids (PPA) which can be used in the invention are described in WO 97/14753. They are compounds of the crude formula P _q H _r O _s in which q, r and s are positive numbers such as:

q> 2 and in particular q ranges from 3 to 20 or more and that 5q + r-2s = 0.

In particular, said polyphosphoric acids can be linear compounds of the crude formula PqH ( _q +2) O (3q + i) corresponding to the structural formula:

HO

Where q has the definition given above. They can also be products of two-dimensional or three-dimensional structure.

All of these polyphosphoric acids can be considered as polycondensation products by heating aqueous metaphosphoric acid.

It will not be departing from the scope of the invention by combining several different chemical additives such as different organic compounds of formula (I), (II), (III), (V), (VI) and (VII), the products of reaction of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), and / or different paraffins and / or different polyphosphoric acids in the material which can be used as road binder or as a waterproofing binder.

Advantageously, when a chemical additive is used in the material which can be used as a road binder or as a sealing binder, it is chosen from the compounds of formula (I), the compounds of formula (II), the compounds of formula (V) and mixtures of these compounds.

Even more advantageously, when a chemical additive is used in the material which can be used as a road binder or as a sealing binder, it is chosen from:

- 2 ’, 3-bis [(3- [3, 5-di- / erributyl-4-hydroxyphenyl] propionyl)] propionohydrazide,

- sebacic acid,

DUPLICATE

-hydrazide derivatives such as: C5H11-CONH-NHCO-C5H1], C9H19-CONH-NHCOC9H19, C11H23-CONH-NHCO-C11H23, C17H35-CONH-NHCO-C17H35, or C21H43-CONHNHCO-C21H43;

- diamides such as N, N'-ethylenedi (laurylamide) of formula C11H23-CONH-CH2CH2-NHCO-C11H31, N, N'-ethylenedi (myristylamide) of formula C13H27-CONH-CH2-CH2NHCO-C13H27, N, N'-ethylenedi (palmitamide) of formula C15H31-CONH-CH2-CH2-NHCOC15H31, N, N'-ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35;

- monoamides such as laurylamide of formula C11H23-CONH2, myristylamide of formula C13H27-CONH2, palmitamide of formula C15H31-CONH2, stearamide of formula C17H35-CONH2, and mixtures of these compounds.

Even more preferably, when a chemical additive is used in the material which can be used as a road binder or as a sealing binder, it is chosen from:

- 2 ’, 3-bis [(3- [3, 5-di- / er / -butyl-4-hydroxyphenyl] propionyl)] propionohydrazide,

- sebacic acid,

- and mixtures of these compounds.

According to another preferred embodiment, when a chemical additive is used in the material which can be used as a road binder or as a sealing binder, it is chosen from:

- diamides, such as N, N'-ethylenedi (laurylamide) of formula C11H23-CONH-CH2CH2-NHCO-C11H31, N, N'-ethylenedi (myristylamide) of formula C13H27-CONH-CH2-CH2NHCO-C13H27, N, N'-ethylenedi (palmitamide) of formula C15H31-CONH-CH2-CH2-NHCOC15H31, N, N'-ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35

- sebacic acid,

- and mixtures of these compounds.

According to one embodiment of the invention, the first composition, comprising for example a bitumen base, of which the core of the granules is composed, comprises from 0.1% to 10% by mass, preferably from 0.5% to 5% by mass, more preferably from 0.5% to 2.5% by mass of chemical additive relative to the total mass of the first composition.

According to an advantageous embodiment, the first composition comprises at least two chemical additives.

According to a first variant of this embodiment, the first composition comprises at least a first chemical additive of formula (V) and at least a second additive

Chemical DUPLICATE chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); the chemical additives of formula (VII) and the reaction products of at least one C ₃ -Ci2 polyol and of at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second additive chemical being distinct from the first chemical additive.

Preferably, and according to this first variant, the first composition comprises at least one first chemical additive of formula (V) and at least one second chemical additive of formula (II).

More preferably, and according to this first variant, the first composition comprises at least a first additive of formula (V) and at least one second chemical additive of formula (IIA).

Preferably, and still according to this first variant, the first chemical additive of formula (V) is chosen from diacids (z = 2), triacids (z = 3) and tetracids (z = 4), preferably from diacids (z = 2).

More preferably, and still according to this first variant, the first chemical additive of formula (V) is chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

Advantageously, and according to this first variant, the first chemical additive of formula (V) is sebacic acid or 1,10-decanedioic acid with w = 8.

According to a second variant of this embodiment, the first composition comprises at least a first chemical additive of formula (II) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); chemical additives of formula (VII) and the reaction products of at least one C ₃ -Ci2 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second additive chemical being distinct from the first chemical additive.

Preferably, and according to this second variant, the first chemical additive of formula (II) is chosen from chemical additives of formula (IIA).

DUPLICATE

I I I I I I I I I I

I I I I I I I I I I

More preferably, and according to this second variant, the first composition comprises at least a first chemical additive of formula (IIA) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (IIB); chemical additives of formula (III); chemical additives of formula 5 (V); chemical additives of formula (VI); chemical additives of formula (VII) and the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.

Even more preferably, and according to this second variant, the first composition 10 comprises at least a first additive of formula (IIA) and at least one second chemical additive of formula (V).

Advantageously, and according to this second variant, the first chemical additive of formula (II) is N, N’-ethylenedi (stearamide).

Preferably, and according to this second variant, the second chemical additive of formula (V) is chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8-octanedioic acid with w =

6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

According to a third preferred variant of this embodiment, the first composition comprises at least sebacic acid or 1,10-decanedioic acid and at least N, Nethylenedi (stearamide).

According to a fourth variant of this embodiment, the first composition comprises at least a first additive of formula (I) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); chemical additives of formula (VII) and the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.

Preferably, and according to this fourth variant, the second chemical additive is chosen from chemical additives of formula (II) and chemical additives of formula (V).

Preferably, and according to this fourth variant, the second chemical additive of formula (II) is chosen from chemical additives of formula (IIA).

DUPLICATE

I I I

I I I I I I

I

I I I I I I

I I

More preferably, and according to this fourth variant, the second chemical additive of formula (II) is N, N’-ethylenedi (stearamide).

Preferably, and still according to this fourth variant, the second chemical additive of formula (V) is chosen from diacids (z = 2), triacids (z = 3) and tetracids (z = 4), preferably from diacids (z = 2).

Even more preferably, and still according to this fourth variant, the second chemical additive of formula (V) is chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8-octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, 10 sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

Advantageously, and still according to this fourth variant, the second chemical additive of formula (V) is sebacic acid or 1,10-decanedioic acid.

Preferably, and according to this fourth variant, the first chemical additive of formula 15 (I) is 2 ’, 3-bis [(3- [3, 5-di-ierAbutyl-4-hydroxyphcnyl] propionyl)] propionohydrazide.

Preferably, and according to this embodiment, the mass ratio of the first chemical additive relative to the second chemical additive is from 1: 99 to 99: 1, preferably from 1: 9 to 9: 1, even more preferably from 1: 5 to 5: 1.

Olefinic polymer builder

According to one embodiment of the invention, the first composition may further comprise at least one olefinic polymer adjuvant.

The olefinic polymer builder is preferably selected from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers; (b) ethylene / monomer A / monomer B terpolymers and (c) copolymers resulting from the grafting of a monomer B onto a polymeric substrate.

(a) The ethylene / (meth) acrylate copolymers are advantageously chosen from random or block copolymers, preferably random, of ethylene and of a monomer chosen from glycidyl acrylate and glycidyl methacrylate , comprising from 50% to 99.7% by mass, preferably from 60% to 95% by mass, more preferably from 60% to 90% by mass of ethylene.

DUPLICATE

I I

I

I I

I .0 (b) The terpolymers are advantageously chosen from random or block terpolymers, preferably random, of ethylene, of a monomer A and of a B monomer.

Monomer A is chosen from vinyl acetate and C 1 to C 6 alkyl acrylates or methacrylates.

Monomer B is chosen from glycidyl acrylate and glycidyl methacrylate.

The ethylene / monomer A / monomer B terpolymers comprise from 0.5% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0.5% to 15% by mass, preferably from 2.5% to 15% by mass of units derived from monomer B, the remainder being formed from units derived from ethylene.

(c) The copolymers result from the grafting of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, on a polymer substrate. The polymer substrate consists of a polymer selected from polyethylenes, in particular low density polyethylenes, polypropylenes, random or block copolymers, preferably random, of ethylene and vinyl acetate and random or block copolymers, preferably. statistics, of ethylene and of C 1 -C 6 alkyl acrylate or methacrylate, comprising from 40% to 99.7% by mass, preferably from 50% to 99% by mass of ethylene. Said graft copolymers comprise from 0.5% to 15% by mass, preferably from 2.5% to

15% by mass of grafted units derived from monomer B.

Advantageously, the olefinic polymer adjuvant is chosen from random terpolymers of ethylene (b), of a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and of a B monomer chosen from acrylate. glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0 5% to 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.

According to one embodiment of the invention, the first composition, comprising for example a bitumen base, of which the core of the granules is composed, comprises from 0.05% to 15% by mass, preferably from 0.1% to 10% by mass, more preferably from 0.5% to 6% by mass of the olefinic polymer adjuvant, relative to the total mass of the first composition.

DUPLICATE

According to one embodiment of the invention, the first composition can also comprise other known additives or other known elastomers for bitumen such as copolymers SB (block copolymer of styrene and butadiene), SBS (block copolymer styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), SBS * (styrene-butadiene-styrene star block copolymer), SBR (styrene-b-butadiene-rubber), EPDM (modified ethylene propylene diene). These elastomers can also be crosslinked according to any known process, for example with sulfur. Mention may also be made of elastomers made from styrene monomers and butadiene monomers allowing crosslinking without a crosslinking agent, as described in documents WO 2007/058994, WO 2008/137394 and by the applicant in patent application WO 11/013073. .

According to a particular preferred embodiment, the first composition comprises a combination of the chemical additive of formula (II) and the olefinic polymer adjuvant described above.

We prefer the combination in which the chemical additive is of formula (II) where m = 0, more preferably where m = 0 and n = 0.

Preference will also be given to the combination in which the olefinic polymer adjuvant is chosen from the terpolymers (b) ethylene / monomer A / monomer B described above.

More preferably, the first composition, for example road bitumen, comprises the chemical additive of formula (II) where m = 0, more preferably where m = 0 and n = 0 and the olefinic polymer additive chosen from terpolymers (b ) ethylene / monomer A / monomer B described above.

- The coating layer / second composition:

According to the invention, the coating layer is obtained by applying a composition comprising:

• at least one viscosifying compound chosen from cellulose ethers, and • at least one anti-caking agent on all or part of the surface of the bitumen core.

The precursor composition of the coating layer may comprise at least one solvent to facilitate its application.

The terms "viscosifier" and "viscosifier compound" are used within the meaning of the invention, equivalently and independently of each other. By "viscosifier" or "viscosifier compound" is meant a compound which has the property of reducing the fluidity of a liquid or of a composition and therefore of increasing its viscosity.

DUPLICATE

The viscosifier within the meaning of the invention is a material which has a dynamic viscosity greater than or equal to 50 mPa.s ′ ¹ , preferably from 50 mPa.s ′ ¹ to 550 mPa.s ′ ¹ , more preferably from 80 mPa.s ′ 1. s ^-1 to 450 mPa.s' ¹ , the viscosity being a Brookfield viscosity measured at 65 ° C. The viscosity of a viscosifier according to the invention is measured at 65 ° C. using a Brookfield CAP 2000+ viscometer and at a speed of rotation of 750 rpm. The measurement is read after 30 seconds for each temperature.

The coating layer is solid at elevated ambient temperature, especially at a temperature above 60 ° C.

According to one embodiment of the invention, the average thickness of the coating layer is preferably greater than or equal to 20 μm, more preferably from 20 to 200 μm, and even more preferably from 40 to 150 μm, and even more preferably from 50 to 100 μm. The coating layer must be thick enough for it to be continuous.

In addition to the cellulose ether compound and the anti-caking agent, the coating layer may optionally comprise one or more compounds chosen from: other viscosifying compounds, chemical additives which have been described above, polymers, plasticizing agents , surfactants, ...

The coating composition preferably comprises, based on its final composition, from 5 to 40% by weight of plasticizer, in particular from 5 to 25% by weight, with a content by weight of 5 to 20% more preferably . For this, it is possible to use a plasticizer customary in film coating compositions.

Among the plasticizers, mention may be made of fatty acids, such as, for example, stearic acid, or mixtures of fatty acids such as the product marketed under the trademark Miglyol ®.

According to a preferred embodiment, the coating layer consists essentially of:

• one or more viscosifying compounds chosen from cellulose ethers, and • at least one anti-caking agent.

Advantageously, according to this embodiment, the coating layer comprises, or better consists essentially of:

• one or more cellulose ethers and

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Even more advantageously, according to this embodiment, the coating layer comprises, or better still consists essentially of:

• one or more cellulose ethers and • at least 20%, even better at least 30%, advantageously at least 40% and even more advantageously at least 50% of one or more anti-caking agents, the percentages being expressed by mass relative to the total mass of the coating layer.

According to another preferred embodiment, the coating layer consists essentially of:

• one or more viscosifying compounds chosen from cellulose ethers, · at least one anti-caking agent, and • at least one plasticizing agent.

Advantageously, according to this embodiment, the coating layer comprises, or better consists essentially of:

· One or more cellulose ethers, • at least 10% of one or more anti-caking agents, • at least one plasticizer, the percentages being expressed by mass relative to the total mass of the coating layer.

Even more advantageously, according to this embodiment, the coating layer comprises, or better still consists essentially of:

° one or more cellulose ethers and ° at least 20%, even better at least 30%, advantageously at least 40% and even more advantageously at least 50% of one or more anti-caking agents, at least one plasticizer , the percentages being expressed by mass relative to the total mass of the coating layer.

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Advantageously, the second composition is in the form of a solution or a dispersion in a solvent.

The solvent is advantageously chosen from water and mixtures of water and organic solvents miscible with water such as alcohols, for example ethanol, methanol, glycerol.

Preferably, the concentration of material other than the solvent in said solutions and / or dispersions is from 50 g / L to 500 g / L, preferably from 75 g / L to 300 g / L and even more preferably from 100 g / L at 250 g / L.

♦ cellulose ether

Cellulose ether is a derivative of cellulose in which all or part of the hydroxyl functions of cellulose have reacted with a chemical reagent to form an ether. Other functionalizations of cellulose are possible in addition to the ether functions. Cellulose ether can be in the form of a salt.

Among the cellulose ethers, mention may be made of: methyl cellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxyethyl methylcellulose (HEMC), hydroxypropyl methylcellulose (HPMC), hydroxybutyl methylcellulose (HBMC), carboxymethylcellulose (CMC), sodium carboxymethylcellulose (Na-CMC), carboxymethylsulfoethylcellulose, rhydroxyethylmethylcarboxymethylcellulose.

Advantageously, the cellulose ethers are chosen from cellulose ethers with a hydrophilic nature.

Advantageously, the cellulose ether (s) are chosen from: hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose, even more advantageously hydroxypropyl methylcellulose.

Preferably, the coating layer comprises at least 10% by mass of one or more viscosifying compounds chosen from cellulose ethers, relative to the mass of the coating layer, more preferably at least 20% by mass, and again more preferably at least 30% by mass.

Advantageously, the coating layer comprises at least 40% by mass of one or more viscosifying compounds chosen from cellulose ethers, more advantageously at least 50% by mass, relative to the total mass of the coating layer.

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Even more advantageously, the coating layer comprises from 10% to 90% by weight of one or more viscosifying compounds chosen from cellulose ethers, preferably from 25% to 75% by weight, even more preferably from 40% to 60 % by mass, based on the total mass of coating layer.

ΙΟ * other viscosifying compounds:

Preferably, in addition to cellulose ethers, the viscosifiers are chosen from:

- gelling compounds, preferably of plant or animal origin, such as: gelatin, agar-agar, alginates, starches, modified starches, or gellan gums;

- polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 g.mol · ¹ and 8000 g.mol ' ¹ , such as for example a PEG having a molecular weight of 800 g.mol ¹ (PEG-800 ), a PEG having a molecular weight of 1000 g.mol ' ¹ (PEG-1000), a PEG having a molecular weight of 1500 g.mol · ¹ (PEG-1500), a PEG having a molecular weight of 4000 g. mol ' ¹ (PEG-4000) or a PEG having a molecular weight of 6000 g.mol' ¹ (PEG-6000);

- mixtures of such compounds.

Advantageously, in addition to cellulose ethers, the viscosifiers are chosen from:

- gelling compounds preferably of plant or animal origin, such as: gelatin, agar-agar, alginates, gellan gums;

- Polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 g.mol ' ¹ and 8000 g.mol' ¹ , such as for example a PEG having a molecular weight of 800 g.mol ' ¹ (PEG- 800), a PEG having a molecular weight of 1000 g.mol ' ¹ (PEG-1000), a PEG having a molecular weight of 1500 g.mol' ¹ (PEG-1500), a PEG having a molecular weight of 4000 g .mol ' ¹ (PEG-4000) or a PEG having a molecular weight of 6000 g.mol' ¹ (PEG-6000);

- mixtures of such compounds.

• Anti-caking compounds:

The anti-caking compound is of mineral or organic origin. By "anti-caking agent" or "anti-caking compound" is meant any compound which limits, reduces, inhibits, delays the agglomeration and / or adhesion of the granules to each other during their transport.

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ΙΟ and / or their storage at room temperature and which ensures their fluidity during handling.

More preferably, the anti-caking compound is chosen from: talc; fines, also called fillers, generally less than 125 µm in diameter, such as siliceous fines, with the exception of limestone fines; sand such as Fontainebleau sand; cement ; carbon; wood residues such as lignin, lignosulphonate, powders of coniferous needles, powders of cones of conifers, in particular of pine; ash from rice husks; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, fumed silicas, in particular hydrophobic or hydrophilic fumed silicas, silicates, silicon hydroxides and oxides of silicon ; plastic powder; lime; hydrated lime; the plaster ; rubber crumb; powder of polymers, such as styrene-butadiene (SB) copolymers, styrene-butadiene-styrene (SBS) copolymers and mixtures of these materials.

Advantageously, the anti-caking agent is chosen from talc; fines generally less than 125 µm in diameter with the exception of limestone fines, such as siliceous fines; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of cones of conifers, in particular of pine; glass powder; sand such as Fontainebleau sand; silica fumes, in particular hydrophobic or hydrophilic silica fumes; and their mixtures.

Preferably, the coating layer comprises at least 10% by mass of one or more anti-caking agents, relative to the mass of the coating layer, more preferably at least 20% by mass, and even more preferably at least 20% by mass. less 30% by mass.

Advantageously, the coating layer comprises at least 40% by mass of one or more anti-caking agents, more preferably at least 50% by mass, relative to the total mass of the coating layer.

Even more advantageously, the coating layer comprises from 10% to 90% by mass of one or more anti-caking agents, preferably from 25% to 75% by mass, even more preferably from 40% to 60% by mass, relative to the total mass of coating layer.

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- The granules:

For the purposes of the invention, the term "granules of material which can be used as a road binder or as a sealing binder" can also be defined as a material which can be used as a road binder or as a sealing binder which is solid at room temperature packaged in a form. divided, i.e. in the form of small units called granules or particles, comprising a core based on a material usable as a road binder or as a sealing binder and a shell or shell or coating or coating layer or coating.

Preferably, the coating layer covering the granules of material which can be used as a road binder or as a sealing binder according to the invention is continuous.

Preferably, the coating layer is applied so that at least 90% of the surface of the core of said granules is covered with the coating layer, preferably at least 95%, more preferably at least 99%.

According to one embodiment of the invention, the coating layer covering at least part of the surface of the core of the granules represents from 0.2% to 20% by mass, preferably from 0.5% to 15% by mass. mass, more preferably from 1% to 10% relative to the total mass of the core of the granules.

Preferably, the granules of material which can be used as a road binder or as a sealing binder, advantageously of bitumen, according to the invention, may have, within the same population of granules, one or more shapes chosen from a cylindrical shape, spherical or semi-spherical or ovoid, preferably in a semi-spherical shape. The size of the granules is such that the longest average dimension is preferably less than or equal to 50 mm, more preferably from 2 to 30 mm, even more preferably comprised from 3 to 20 mm. The size and shape of the granules can vary depending on the manufacturing process employed. For example, the use of a die makes it possible to control the production of granules of a chosen size. A sieving makes it possible to select granules according to their size.

Preferably, the granules of material which can be used as a road binder or as a sealing binder, advantageously the bitumen granules, according to the invention have a weight of between 0.1 g and 50 g, preferably between 0.2 g and 10 g, more preferably between 0.2 g and 5 g.

Without being bound by theory, the Applicant has unexpectedly discovered that the use of a viscosifying compound of cellulose ether type and of at least one anti-caking agent according to the invention makes it possible to obtain a coating layer:

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- which is resistant to climatic and transport conditions and / or | extreme storage of the solid material usable as a road binder or as a waterproofing binder, | - which breaks easily under a mechanical shearing effect, such as for example under the effect of mechanical shearing applied in a tank such as a mixer or a mixing drum during the production of asphalt, _ - which does not requires no additional step after its application.

More particularly, the coating layer is resistant to transport and / or storage of the material which can be used as a road binder or as a sealing binder, in particular bitumen, at high ambient temperature, in particular at a temperature above 60 ° C, in "Big

IBags "while being brittle under the effect of mechanical shear. It thus allows the release of the core during the production of asphalt.

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According to one embodiment of the invention, the bitumen granules may further comprise one or more other coating layers covering all or part of the coating layer of the solid material which can be used as a road binder or as a sealing binder, in particular of bitumen, according to the invention.

- Granule manufacturing process:

Another subject of the invention relates to a process for manufacturing granules of solid material which can be used as a road binder or as a sealing binder, in particular bitumen, composed of a core and a coating layer of the core, this process comprising :

i) shaping the heart from at least a first composition, ii) coating the core over all or part of its surface with at least one second composition comprising at least one viscosifying compound chosen from cellulose ethers and at least one anti-caking compound.

Step ii) can be carried out by dipping, spraying, co-extrusion, etc. Preferably, step ii) is carried out by a method using a fluidized air bed device.

The shaping of the heart of the granules from a solid material which can be used as a road binder or as a sealing binder, in particular bitumen, can be carried out according to any known process, for example according to the manufacturing process described in document US Pat. 3,026,568, WO 2009/153324 or WO 2012/168380. According to a mode

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Other techniques can be used in the manufacturing process of the solid material core, in particular molding, pelletizing, extrusion ...

The coating of the granules of solid material which can be used as a road binder or as a sealing binder, in particular bitumen, can be done by any known technique, in particular by applying the second material in a fluidized bed process, as described for example in US 5,236,503 or in EP 1 407 814.

Preferably, the core particles of solid material have a longest average dimension ranging from 1 to 30 mm, advantageously from 2 to 20 mm, even more advantageously from 2 to 10 mm.

Preferably, during the implementation of the method of the invention, the ratio by mass of the coating layer relative to the mass of the core, optionally with additives, is from 0.05 to 1, advantageously from 0.1 to 0.9, even more advantageously from 0.1 to 0.5.

Another object of the invention consists of granules of solid material which can be used as a road binder or as a sealing binder, in particular bitumen, which can be obtained by implementing the method according to the invention as described above. above. Such granules advantageously exhibit the properties described above.

- Uses of granules:

Another object of the invention also relates to the use of the granules according to the invention as a road binder.

The road binder can be used to manufacture mixes, in combination with aggregates according to any known process.

Preferably, the granules of solid material which can be used as a road binder or as a sealing binder, in particular of bitumen, according to the invention, are used for the manufacture of mixes.

Bituminous or non-bituminous mixes are used as materials for the construction and maintenance of pavement bodies and their coating, as well as for carrying out all road works. These include, for example, surface plasters, hot mixes, cold mixes, cold-cast mixes, severe emulsions, base, tie, bond and rolling coats, and other combinations of coatings. '' a bituminous or non-bituminous binder and road aggregate having particular properties,

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I I such as anti-omiérantes layers, draining mixes, or asphalts (mixture between a bituminous binder and aggregates of the sand type).

Another object of the invention relates to a process for the production of mixes comprising at least one road binder and aggregates, the road binder being chosen from the granules of solid material according to the invention, this method comprising at least the steps of :

- heating of the aggregates to a temperature ranging from 100 ° C to 180 ° C, preferably from 120 ° C to 160 ° C,

- mixing the aggregates with the road binder in a tank such as a mixer or a mixer drum,

- obtaining of asphalt.

The method of the invention has the advantage of being able to be implemented without a prior step of heating the granules of solid material.

The process for the production of mixes according to the invention does not require a step of heating the granules before mixing with the aggregates because on contact with the hot aggregates, the granules melt.

The granules of solid material which can be used as a road binder or as a sealing binder, in particular of bitumen, according to the invention as described above have the advantage of being able to be added directly to the hot aggregates, without having to be melted beforehand. mix with hot aggregates.

Preferably, the step of mixing the aggregates and the road binder is carried out with stirring, then the stirring is maintained for at most 5 minutes, preferably at most 2 minutes to allow a homogeneous mixture to be obtained.

The granules according to the present invention are remarkable in that they allow the transport and / or the storage and / or the handling of road bitumen at high ambient temperature under extreme conditions, in particular without any agglomeration and / or. or adhesion of the granules of solid material during their transport and / or their storage and / or their handling. On the other hand, the coating layer of the granules breaks under the effect of contact with the hot aggregates and of shearing and it releases the core composition. Finally, the presence of the coating layer in the mixture of road binder and aggregates does not degrade the properties of said road bitumen for road application, compared to an uncoated core composition.

- Method of transport and / or storage and / or handling of solid material which can be used as a road binder or as a coating binder

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The granules obtained by the process of the invention can be transported and / or stored and / or handled in the form of granules of solid material, in particular bitumen, which are solid at room temperature.

The solid material, in particular road bitumen, can be transported and / or stored at elevated ambient temperature for a period greater than or equal to 2 months, preferably 3 months.

Preferably, the elevated ambient temperature is 20 ° C to 90 ° C, preferably 20 ° C to 80 ° C, more preferably 40 ° C to 80 ° C, even more preferably 40 ° C to 60 ° C .

The granules of solid material, in particular bitumen, obtained by the process according to the invention have the advantage of retaining their divided shape, and therefore of being able to be handled, after storage and / or transport at high ambient temperature. In particular, they have the ability to flow under their own weight without boiling, which allows them to be stored in packaging in bags, drums or in containers of all shapes and all volumes and then to be transferred from this packaging to equipment. , such as site equipment (tank, mixer, etc.).

The granules of solid material, in particular bitumen, are preferably transported and / or stored in bulk in bags of 1 kg to 100 kg or 500 kg to 1000 kg commonly called in the field of road bitumens “Big Bag”. ", Said bags preferably being of hot-melt material. They can also be transported and / or stored in bulk in boxes of 5 kg to 30 kg or in drums of 100 kg to 200 kg.

The different embodiments, variations, preferences and advantages described above for each of the objects of the invention apply to all the objects of the invention and can be taken separately or in combination.

Figures:

Figure 1: Sectional view of the fluidized air bed installation

Referring to Figure 1, the fluidized air bed (12) plant (10) (also called a granulator) comprises a fluidized air bed (12) process chamber (II) in which the 30 cores in bituminous material (14) are placed and in which an air stream (16) is supplied from below to the fluidized bed (12) and through a perforated grid (13) in order to maintain the fluidized bed and in order to dry and / or cool the shells formed around the bituminous material cores (14). A precursor composition of the coating layer (18) is then supplied to the fluidized bed by means of a spray nozzle (20) opening at the bottom into

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I I I I I the fluidized bed (12). The fluidized bed process chamber (II) (12) also includes an insert (22) located above the spray nozzle (20) and in the form of a cylindrical installation part adjustable in height and diameter. and the lower ridges (15) of which are adjustable apart from the perforated grid (13) of the bottom of the fluidized bed (12).

The filtration chamber (IV) comprises several filters (24) making it possible to recycle the fine particles emitted during the implementation of the method.

The air stream (16) supplied to the fluidized bed (12) is guided by an incoming air box (I) comprising an incoming air chamber (26).

The fluidized air bed granulator (12) thus comprises 4 distinct zones: (I) the incoming air box, (II) the process chamber, (III) the expansion chamber and (IV) the chamber. filtration.

The fluidized bed area formed by the incoming air chamber (26) has an area (28) with a higher flow velocity of the air stream (16) applied to the bituminous material cores (14).

The precursor composition of the coating layer (18) is supplied to the zone (28) operating at a higher flow rate.

The bituminous material cores (14) from the higher flow velocity zone (28) are returned to the fluidized bed (12).

A portion of the bituminous material cores (14) present in the fluidized bed (12) is returned to the zone (28) at higher flow velocity, so that a circulation of bituminous material cores (14) appears. ) between the fluidized bed (12) and the higher flow velocity zone (28).

The invention is illustrated by the following examples given without limitation.

Experimental part :

In these Examples, the parts and percentages are expressed by weight unless otherwise indicated.

Equipment • Fluidized air bed device:

Installation 1:

Plant 1 is a fluidized air bed plant used in the process for manufacturing granules according to the invention.

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The following Examples 1 to 6 were carried out in a fluidized air bed granulator marketed by the company Glatt® under the trade name ProCell® and whose sectional view is shown in Figure 1.

ΙΟ • Raw materials:

The bituminous material cores used as raw material in the examples below are composed of:

Bitumen base (B): a grade 50/70 bitumen base, noted Bi, having a P25 penetrability of 58 1/10 mm and a TBA of 49.6 ° C and available commercially from the TOTAL group under the brand AZALT®

Addendum:

- Al additive of formula (I): sebacic acid

- Additive A2 of formula (II): N, N'-ethylenedi (stearamide) sold by the company Croda under the name Crodawax 140®.

• Heart composition

Table 1: composition of the bituminous binder constituting the core of the granules

Cl Bitumen base B1 Al 1.5% A2 2.5%

The amounts are expressed as a percentage by mass of additive compound relative to the total mass of the composition.

The coating composition used for coating the granule cores is prepared from the following compounds:

Viscosifying agent:

- Viscosifying agent VI: hydroxypropylmethylcellulose introduced in the form of SEPIFILM ® LP 010 available commercially from the company SEPPIC,

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- Viscosifying agent V2: Cellulose (CAS 9004-34-6) commercially available from the company Sigma-Aldrich,

- V3 viscosifier: 280 Bloom 6 Mesh-Pig Skin type gelatin available commercially from the company Weishardt International.

Anti-caking agent:

- AGI anti-caking agent: siliceous fines from La Noubleau • Processes and methods:

I - Preparation of the cores of the granules

1. Preparation of the core composition

The bitumen base (Bi) is introduced into a reactor maintained at 160 ° C. with stirring at 300 revolutions / min for two hours. The additives are then introduced into the reactor. The contents of the reactor are maintained at 160 ° C. with stirring at 300 revolutions / min for 1 hour.

2. Preparation of the cores of the solid binder granules

a) General method for the preparation of hearts by binding granules according to the invention

The core composition is heated to 160 ° C for two hours in an oven before being poured into a silicone mold having various spherically shaped holes so as to form the solid binder cores. After observing the solidification of the binder in the mold, the surplus is leveled with a blade heated with a bunsen burner. After 30 minutes, the solid binder in the form of uncoated granules is removed from the mold and stored in a tray covered with silicone paper. The hearts are then allowed to cool by binding at room temperature for 10 to 15 minutes.

b) General method for the preparation of the bitumen cores of the granules according to the invention with an industrial process

For the implementation of this method, it is possible to use a device and a method as described in great detail in US Pat. No. 4,279,579. Various models of this device are available commercially from the company Sandvik under the trade name of. Rotoform ®.

Bitumen granules can also be obtained from the bituminous composition according to the invention poured into the tank of such a device and maintained at a temperature between 130 and 160 ° C.

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One or more injection nozzles allow (tent) the transfer of the bitumen composition according to the invention inside the double pastillation drum comprising a rotating external drum, the two drums being equipped with slots, nozzles and 'orifices allowing the pastillation of drops of bitumen through the first fixed drum and orifices having a diameter of between 2 and 8 mm of the rotating outer drum. The bitumen drops are deposited on the upper face of a horizontal tread driven by rollers.

Bitumen granules were obtained from the bituminous composition C1 poured into the tank of such a device and maintained at a temperature between 130 and 160 ° C.

One or more injection nozzles allow (tent) the transfer of the bituminous composition C1 inside the double pastillation drum comprising a rotating external drum, the two drums being equipped with slots, nozzles and orifices allowing the pastillation of drops of bitumen through the first fixed drum and orifices having a diameter of between 2 and 8 mm of the rotating outer drum. The bitumen drops are deposited on the upper face of a horizontal tread driven by rollers.

II - Coating of the granule cores

1. Preparation of the coating layer

The precursor composition of the coating layer is an aqueous composition comprising at least:

- a viscosifying agent, and

- an anti-caking agent.

It is prepared by mixing the components at room temperature in water.

2. Coating of the granules:

a) General method for coating the granule cores according to the invention (first embodiment)

The bitumen cores obtained in I- are poured into the coating composition. They are then stirred manually in the solution for a few minutes and then they are removed to be placed on a plate and left to dry at room temperature (approximately 30 ° C.).

Solid bitumen granules with a core / shell structure are thus obtained.

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b) General method for coating the granule cores according to an industrial process (second embodiment)

The bituminous material cores are loaded into the process chamber of the device of Figure 1, the air flow being in operation. The bituminous material cores are thus fluidized by the air flow injected into the process chamber. Finally, the precursor composition of the coating layer is sprayed into the process chamber through the spray nozzle.

III - Test of resistance to load of the granules

This test is carried out in order to assess the resistance to load of the granules under a compressive force. In fact, this test makes it possible to simulate the temperature and compression conditions of the granules on top of each other to which they are subjected during transport and / or storage in bulk in bags of 10 to 100 kg or in Big Bags. from 500 to 1000 kg or in drums of 200 kg and assess their resistance under these conditions.

The load resistance test is carried out according to the following protocol: 5 mL of granules are placed in a 20 mL syringe then the plunger is placed on the granules together with a mass of 208 g, representing a force applied as in a Big Bag. The whole is then placed in the oven either at a temperature of 25 ° C for at least 24 hours (load resistance tests at room temperature) or at a temperature of 65 ° C for at least 4 hours (resistance tests. load at high ambient temperature).

IV - Evaluation of the sticky appearance of the granules

The stickiness of the granules is assessed by touch by a manipulator directly after the core coating step (without a drying step).

For each type of granule, the handler takes about ten granules and assesses the stickiness of each of them by first placing them between two fingers and then trying to move the fingers away from the surface of the granule.

Results

1. Bitumen granules coated by means of a fluidized air bed device (second embodiment)

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a) Preparation of bitumen granules

Experiments 1 to 6 are carried out in the device 10 shown in Figure 1 according to the coating method described in II- 2. b).

The parameters for carrying out the various experiments are given in Table 2 below. The spray pressure (in bars) is 1 to 3 bars.

The coating composition used in Experiments 1 to 6 is prepared from:

- hydroxypropylmethylcellulose as viscosifying agent (agent VI), and

- siliceous fines from La Noubleau as an anti-caking agent (AGI agent).

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Examples 1 2 U) 3 (*) 4 (*) 5 6 Precursor composition of the coating layer % viscosifier - 10 10 10 7.5 10 % anti-caking agent 20 - - - 12.5 10 Conditions for implementing the process Quantity of fluidized hearts (in g) 1050 937 1305 1107 1123 Quantity of precursor composition sprayed (in g) 1003 407 194 224 1060 1000 Fluidization flow rate (in m ³ / h) 300 300 280 280 250 250 Product temperature (in ° C) 35 35 35 35 17 17 Spray rate (in 25.1 22.6 10.8 3.3 15.4 14.1

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g / min)

(*) following the agglomeration of the granules during the process, it was interrupted before having sprayed all of the precursor composition.

Examples 1 to 4 are counter-examples.

Examples 5 and 6 are examples according to the invention.

b) Evaluation of the bitumen granules obtained

The granules obtained in Examples 1 to 6 are then evaluated according to several criteria:

1) obtaining bitumen granules comprising a core and a coating layer,

2) the homogeneity of the coating layer formed,

3) the deformation of the granules,

4) the presence of agglomerates, and

5) their resistance to high temperature (load resistance evaluated at 65 ° C for 4 hours).

The results are shown in Table 3 below.

Table 3

Examples 1 2 3 4 5 6 Granule formation Yes no no no Yes Yes Held at room temperature at 65 ° C - - - - ++ +++

+++: the granules retain their original shape and do not adhere to each other.

++: the granules do not adhere to each other but no longer have their rounded shape.

+: the granules adhere slightly to each other.

-: the granules are agglomerated.

• Coating layer comprising exclusively an anti-caking agent (example 1)

In Example 1, the precursor composition of the coating layer comprises only an anti-caking agent.

It is found that the bitumen granules obtained according to Example 1 are not stable at high temperature.

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The mere presence of an anti-caking agent in the precursor composition of the coating layer does not allow the production of stable bitumen granules at high temperature.

• Coating layer comprising only a viscosifying agent chosen from cellulose ethers (examples 2, 3, 4)

In Examples 2, 3, and 4, the precursor composition of the coating layer exclusively comprises a viscosifying agent chosen from cellulose ethers.

The cores and the precursor composition of the coating layer sprayed into the process chamber stick together without forming granules. The cores clump together and make it impossible to form granules of bitumen.

The mere presence of a viscosifying agent chosen from cellulose ethers in the precursor composition of the coating layer does not allow the production of well-individualized bitumen granules.

• Coating layer comprising both a viscosifying agent chosen from cellulose ethers and an anti-caking agent (examples 5 and 6)

In Examples 5 and 6, the precursor composition of the coating layer comprises both a viscosifying agent chosen from cellulose ethers and an anti-caking agent.

The bitumen granules formed in Examples 5 and 6 exhibit good resistance to conditioning at an ambient temperature of 65 ° C. insofar as they hardly adhere to each other.

The granules formed in Example 6 are particularly advantageous in that they retain their initial shape.

Thus, the handling and transport / storage of said granules formed in Examples 5 and 6 will be easy insofar as the granules do not agglomerate with one another at high ambient temperature.

2. Bitumen granules coated by dipping (first embodiment)

a) Preparation of bitumen granules

For experiments 7, 8 and 9, the coating of the bitumen cores is carried out by soaking in the coating composition according to the method described in II- 2. a).

The nature of the coating composition used for each of experiments 7, 8 and 9 is given in Table 4 below.

DUPLICATE

Table 4

Examples 7 8 9 Viscosifying agent % Agent V1 14.3 - - % Agent V2 - 14.3 - % Agent V3 - - 14.3 Anti-caking agent % AGI Agent 14.3 14.3 14.3

Experiment 7 is according to the invention.

Experiments 8 and 9 are comparative.

b) Evaluation of the bitumen granules obtained

The granules obtained in Examples 7 to 9 are then evaluated according to several criteria:

1) the tackiness of the coating layer, and

2) their resistance at ambient temperature (resistance to the load evaluated at 25 ° C. for 10 24 hours).

The results are shown in Table 5 below.

Table 5

Examples 7 8 9 Sticky appearance no Yes Yes Held at room temperature at 25 ° C +++ + +

+++: the granules retain their original shape and do not adhere to each other.

++: the granules do not adhere to each other but no longer have their rounded shape.

+: the granules adhere slightly to each other.

: the granules are agglomerated.

^ Sticky appearance of the granules

The granules prepared in Example 7 are advantageous in that they do not stick. The latter can then be bagged and stored directly after the coating step without requiring an additional drying step.

DUPLICATE

Conversely, the granules prepared in Examples 8 and 9 are sticky. It is therefore necessary for these granules to carry out an additional step of drying the coating layer before they can be bagged.

* Held at room temperature at 25 ° C

The granules prepared in Examples 8 and 9 adhere slightly to each other.

The granules prepared in Example 7 are advantageous in that they retain their initial shape and exhibit no adhesion.

Therefore, the handling and transportation / storage of the granules formed in Example 7 are easy to measure and do not cause any deterioration in the condition of the granules.

Claims (15)

1. Granules of material usable as a road binder or as a waterproofing binder comprising a core and a coating layer, in which: 5 - the core consists of a first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder, and - the coating layer consists of a second composition which comprises: • at least one viscosifying compound chosen from cellulose ethers, and 10 “at least one anti-caking agent. 2. Granules according to claim 1 in which the cellulose ether is chosen from: methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxyethyl methyl cellulose (HEMC) ), hydroxypropyl 15 methylcellulose (HPMC), hydroxybutyl methylcellulose (HBMC), carboxymethylcellulose (CMC), sodium carboxymethylcellulose (Na-CMC), carboxymethylsulfoethylcellulose, hydroxyethylmethylcarboxymethylcellulose. 3. Granules according to claim 2 wherein the cellulose ether is selected from: hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose, even more preferably hydroxypropyl methylcellulose. 4. Granules according to any one of the preceding claims wherein the second composition comprises at least 10% of one or more anti-caking agents, the percentages being expressed by mass relative to the total mass of the second composition. 5. Granules according to any one of the preceding claims, in which the anti-caking compound is chosen from: talc; fines generally with a diameter of less than 125 µm, such as siliceous fines, with the exception of limestone fines; sand such as Fontainebleau sand; cement ; carbon; wood residues such as lignin, lignosulphonate, powders of coniferous needles, powders of cones of conifers, in particular of pine; ash from rice husks; glass powder; clays such as DUPLICATE kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, fumed silicas, in particular hydrophobic or hydrophilic fumed silicas, silicates, silicon hydroxides and Silicon oxides; plastic powder; lime; hydrated lime; the plaster ; rubber crumb; powder of polymers, such as styrene-butadiene (SB) copolymers, styrene-butadiene-styrene (SBS) copolymers and mixtures of these materials. 10 6. Granules according to any one of the preceding claims wherein the first composition has needle penetrability measured at 25 ° C according to standard EN 1426 from 5 to 330 1/10 mm, preferably from 10 to 220 1 / 10 mm. 7. Granules according to any one of the preceding claims wherein the The first composition further comprises at least one chemical additive selected from: an organic compound, a paraffin, a polyphosphoric acid, a tackifier and mixtures thereof. 8. A process for manufacturing granules of material which can be used as a road binder or as a 20 sealing binder composed of a core and a core coating layer according to any one of the preceding claims, this method comprising: i) shaping the heart from a first composition comprising at least one material chosen from: a bitumen base, a pitch, a clear binder, ii) coating the core over all or part of its surface with a second composition comprising at least one viscosifying compound chosen from cellulose ethers and at least one anti-caking agent. 9. The method of claim 8 wherein the second composition is applied to the core of the granules in a fluidized air bed device. 10. Granules according to any one of claims 1 to 7 which exhibit stability during transport and / or storage and / or handling at a temperature of up to 100 ° C, advantageously from 20 ° C to 90 ° C. , preferably from 20 ° C to 80 ° C, more preferably from DUPLICATE 40 ° C to 80 ° C, even more preferably from 40 ° C to 60 ° C, for a period greater than or equal to 2 months, preferably greater than or equal to 3 months. 11. Use of the granules according to any one of claims 1 to 7 and 10 as a road binder. 12. Use according to claim 11 for the manufacture of mixes. 13. A method of manufacturing mixes comprising at least one road binder and aggregates, the road binder being chosen from the granules according to any one of claims 1 to 7 and 10, this method comprising at least the steps of: - heating of the aggregates to a temperature ranging from 100 ° C to 180 ° C, preferably from 120 ° C to 160 ° C, - mixing the aggregates with the road binder in a tank such as a mixer or a mixer drum, - obtaining of asphalt. 14. The method of claim 13, which does not include a step of heating the road binder before mixing it with the aggregates. 15. A method of transporting and / or storing and / or handling a material which can be used as a road binder or as a sealing binder, said material being transported and / or stored and / or handled in granular form according to any one of the claims. 1 to 7 and 10.