WO2024141521A1 - Clear binder and uses thereof - Google Patents

Abstract

The invention relates to a clear binder composition comprising: (i) a plasticizing agent containing at least one hydrocarbon oil of petroleum or synthetic origin; (ii) a structuring agent containing at least one resin of plant origin, selected from natural rosins, modified rosins, rosin esters, and any mixture of same, said resin of plant origin having an acid number of less than or equal to 40 mg KOH/g, determined according to the ASTM D465 standard test method; (iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units; and (iv) optionally an anti-stripping agent.

Description

CLEAR BINDER AND ITS APPLICATIONS

Technical area

The present invention relates to a clear binder and its uses in road and/or industrial applications, in particular for the production of colored surface coating compositions.

State of the prior art

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

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

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

Application WO2018/046838 discloses a clear binder that is solid when cold. In particular, it describes a clear binder containing a synthetic oil from deasphalting unit cuts (DAO) and a copolymer based on butadiene and styrene units, for example an SB or SBS copolymer.

Application WO2018/115729 discloses a cold solid binder composition. In particular, the composition can be a clear binder and the plasticizing agent is in particular an oil of petroleum origin. Application WO2018/115730 describes a similar composition for the preparation of mastic asphalts and the production of coatings.

Document US2002/052431 discloses aqueous emulsions comprising on the one hand a clear synthetic binder and on the other hand a latex. During manufacturing, and then during implementation, these binders are subject to different types of external factors which modify their structure and cause their properties to evolve.

Clear binders with a reduced environmental footprint compared to the clear binders discussed above have also been developed by seeking to at least partially substitute the plasticizing agent and/or the structuring agent with constituents of plant origin.

Application EP3081599 describes for example in this sense a binder of plant origin based on modified tall oil pitch, a modified resin and possibly a polymer.

However, these clear binders are not entirely satisfactory. Although they do have a reduced environmental footprint compared to traditional clear binders, they present sustainability issues. Indeed, the clear binders currently available incorporating a plasticizing agent and/or a structuring agent of plant origin have significantly reduced resistance to aging, compared to traditional clear binders prepared from products of petroleum origin. In particular, these binders prepared from compounds of plant origin have significantly reduced resistance to aging of cold properties, compared to traditional clear binders prepared from products of petroleum origin.

A more regular replacement of road surfaces is therefore to be expected, which significantly reduces their environmental benefit.

There thus remains a need for clear biosourced binders, in particular prepared from a structuring agent of plant origin, presenting improved mechanical properties, compared to existing clear biosourced binders.

In particular, there remains a need for clear biosourced binders (prepared from at least one structuring agent of plant origin) with resistance to aging, in particular improved resistance to aging of cold properties, compared to currently clear biosourced binders. available.

In particular, there remains a need for biosourced clear binders (prepared from at least one structuring agent of plant origin) with equivalent, or even improved, properties compared to traditional clear binders prepared from a plant oil. petroleum origin and a resin of petroleum origin.

More particularly, there remains a need for clear biosourced binders (prepared from at least one structuring agent of plant origin) exhibiting resistance to aging, in particular resistance to aging of cold properties, equivalent, or even improved, compared to traditional clear binders prepared from an oil of petroleum origin and a resin of petroleum origin.

Surprisingly, it was found that the combination of (i) a hydrocarbon oil of petroleum or synthetic origin and (ii) a resin of plant origin chosen from natural rosins, modified rosins, esters of rosin, and their mixtures and whose acidity index, determined according to the ASTM D465 method, is less than or equal to 40 mg KOH/g made it possible to obtain a clear biosourced binder having improved properties compared to clear biosourced binders of the prior art. In particular, the clear binders of the invention have better resistance to aging of their properties, in particular better resistance to aging of cold properties, compared to the clear biosourced binders of the prior art.

More particularly, it was noted that this particular combination made it possible to obtain a clear binder having similar, or even improved, properties compared to those of traditional clear binders, obtained from compounds of petroleum origin, in particular resistance to aging of similar cold properties.

Summary of the invention

By “biosourced clear binder” is meant within the meaning of the invention a clear binder comprising at least one structuring agent of plant origin.

In the remainder of the application, any reference to a standard (e.g. ASTM D1982) relates to the version of said standard in force on the date of filing of this application.

The invention firstly relates to a clear binder composition comprising:

(i) a plasticizing agent comprising at least one hydrocarbon oil of petroleum or synthetic origin,

(ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an index of acidity, determined according to the ASTM D465 method, less than or equal to 40 mg KOH/g,

(iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and

(iv) possibly an adhesive boost.

Preferably, the hydrocarbon oil has a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds of between 35% and 65%, a total content of naphthenic compounds of between 10% and 40%. , the contents being given by mass, relative to the total mass of the oil present and measured according to the ASTM D2140 method. According to one embodiment, the hydrocarbon oil has a kinematic viscosity at 100°C, measured according to the ASTM D445 method, ranging from 15 mm ² /s to 40 mm ² /s, and an aniline point, measured by the ASTM D611 method, ranging from 50°C to 80°C.

According to an alternative embodiment, the hydrocarbon oil has a kinematic viscosity at 100°C, measured according to the ASTM D445 method, ranging from 40 mm ² /s to 90 mm ² /s, and an aniline point, measured by the ASTM D61 1 method, ranging from 45°C to 95°C.

Preferably, the content of plasticizing agent in the clear binder composition of the invention ranges from 1% to 65% by mass, relative to the total mass of the composition, preferably from 5% to 55% by mass, more preferably from 10% to 50% by mass.

Advantageously, the resin of plant origin is chosen from esters of natural rosins, more preferably among pentaerythritol esters of natural rosins, in particular among pentaerythritol esters of tall oil rosins.

Preferably, the content of structuring agent ranges from 25% to 90% by mass, relative to the total mass of the composition, preferably from 30% to 80% by mass, more preferably from 35% to 75% by mass.

Preferably, the polymer is a copolymer of styrene and butadiene, preferably is chosen from a styrene/butadiene/styrene block copolymer of radial structure, a butadiene/styrene block copolymer of radial structure and mixtures thereof.

According to a particular embodiment, the clear binder composition of the invention further comprises Fischer-Tropsch waxes, preferably from 0.1% to 10% by mass of Fischer-Tropsch waxes, relative to the mass total of the clear binder composition, preferably from 0.5% to 5% by weight, more preferably from 1% to 3% by weight.

The invention also relates to a process for preparing a clear binder composition as defined above and described in detail below, comprising the steps:

- bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140°C and 200°C,

- stirring mixture of the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C,

- adding the polymer, mixing and heating to a temperature ranging from 140°C to 200°C,

- adding any adhesive dope and/or any Fischer-Tropsch waxes, mixing and heating to a temperature ranging from 140°C to 200°C. The invention also relates to an emulsion comprising a clear binder composition as defined above and described in detail below, water, and an emulsifying agent.

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

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

The expression “between X and Y” includes the limits, unless explicitly stated otherwise. This expression therefore means that the target interval includes the values X, Y and all the values going from X to Y.

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

detailed description

The essential constituents of a clear binder composition are:

- a plasticizing agent,

- a structuring agent,

- at least one polymer,

- where appropriate, doping agents, or dopes, or adhesiveness dopes, or Fischer-Tropsch waxes.

The clear binder of the invention is characterized by the combination of a hydrocarbon oil of petroleum or synthetic origin and a resin of specific plant origin. This selection of components makes it possible to obtain a clear binder with a reduced environmental footprint, compared to clear binders prepared from an oil of petroleum origin and a resin of petroleum origin. The clear binder of the invention has similar, or even improved, properties compared to clear binders prepared from an oil of petroleum origin and a resin of petroleum origin, particularly in terms of resistance to aging.

For the purposes of the invention, the terms “clear binder” and “clear binder base” are used equivalently. The invention relates to a clear binder comprising:

(i) a plasticizing agent comprising at least one hydrocarbon oil of petroleum or synthetic origin,

(ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an index of acidity, determined according to the ASTM D465 method, less than or equal to 40 mg KOH/g

(iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and

(iv) possibly an adhesive boost and/or possibly a Fischer-Tropsch wax.

The plasticizing agent

By “plasticizing agent”, within the meaning of the invention, is meant a chemical constituent making it possible to fluidize and reduce the viscosity and modulus of the binder in which it is incorporated.

The plasticizing agent comprises at least one hydrocarbon oil of petroleum or synthetic origin.

According to one embodiment, the hydrocarbon oil of petroleum or synthetic origin has a content of saturated compounds of between 1% and 30% by mass, advantageously between 5 and 25% by mass, more advantageously between 7 and 23% by mass (SARA method: Saturates/Aromatics/Resins/Asphaltenes, according to ASTM D2007).

Preferably the oil is a hydrocarbon oil of petroleum origin. It can be aromatic or paraffinic.

According to one embodiment, the oil is composed of 90% to 100% by weight of at least one hydrocarbon oil of petroleum origin, advantageously from 95% to 100%, even better from 98% to 100% by weight. at least one hydrocarbon oil of petroleum origin. Even more advantageously, the oil consists of a hydrocarbon oil of petroleum origin or of a mixture of hydrocarbon oils of petroleum origin.

In a preferred embodiment of the invention, the hydrocarbon oil of petroleum origin is chosen from aromatic oils.

More preferably, the aromatic oils have a content of aromatic compounds of between 30% and 95% by mass, advantageously between 50% and 95% by mass, more advantageously between 60 and 95% by mass relative to to the total mass of the aromatic oil (SARA Saturates/Aromatics/Resins/Asphalts method, according to the ASTM D2007 standard).

More preferably, the aromatic oils have a content of saturated compounds of between 1% and 30% by mass, advantageously between 5 and 25% by mass, more advantageously between 7 and 23% by mass (SARA method: Saturated/Aromatic/ Resins/Asphalt cores, according to ASTM D2007).

More preferably, aromatic oils have a resin compound content of between 1 and 10% by mass, advantageously between 3 and 5% by mass, (SARA method: Saturates/Aromatics/Resins/Asphaltenes, according to the ASTM D2007 standard).

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

Preferably, the oil used in the clear binder composition according to the invention has a total content of paraffinic compounds of between 35% and 65%, preferably between 40% and 60%, for example between 45% and 58%. .

Preferably, the oil used in the clear binder composition according to the invention has a total content of naphthenic compounds of between 10% and 40%, and in particular between 15% and 35%, preferably between 20 and 30%. .

Preferably, the oil used in the clear binder composition according to the invention has a total content of aromatic compounds of between 10% and 40%, and in particular between 15% and 35%, for example between 18 and 30%. %.

More preferably, the hydrocarbon oil of the invention has a kinematic viscosity at 100°C of between 0.1 mm ² /s and 150 mm ² /s, advantageously of between 5 mm ² /s and 120 mm ² /s, more advantageously between 7 mm ² /s and 90 mm ² /s (ASTM Method D 445).

More preferably, the hydrocarbon oil of the invention has a kinematic viscosity at 40°C of between 100 mm ² /s and 2500 mm ² /s, advantageously between 200 mm ² /s and 2400 mm ² /s, more advantageously between 400 mm ² /s and 2,250 mm ² /s (ASTM Method D 445).

More preferably, the hydrocarbon oil of the invention has a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C (EN ISO method 2592). More preferably, the hydrocarbon oil of the invention has an aniline point between 20°C and 120°C, advantageously between 40°C and 120°C (ASTM Method D61 1).

In particular, the hydrocarbon oil of the invention has an aniline point lower than 95°C, preferably ranging from 10°C to 95°C, advantageously from 40°C to 90°C (ASTM Method D61 1).

More preferably, the aromatic oils have a density at 15°C of between 400 kg/m ³ and 1500 kg/m ³ , advantageously between 600 kg/m ³ and 1200 kg/m ³ , more advantageously between 800 kg/m 3 m ³ and 1,100 kg/m ³ (ASTM Method D4052).

According to this advantageous embodiment, the aromatic oil comprises aromatic extracts of petroleum residues, obtained by extraction or dearomatization of residues from distillations of petroleum cuts.

Aromatic extracts are secondary products of the crude oil refining process, obtained in particular from the products of vacuum distillation of atmospheric residues. They result from a simple or double extraction of the valuable raffinate in lubricants, using a polar solvent.

The different extracts are classified into different categories depending on their process of obtaining and are as follows:

- DAE Distillate Aromatic Extracted, or aromatic distillate extract);

- MES Mild Extract Solvate in English or mild extraction solvent),

- TDAE {Treated Distillate Aromatic Extract in English or treated distilled aromatic extract),

- RAE {Residual Aromatic Extract)

- TRAE {Treated Residual Aromatic Extract in English or treated residual aromatic extract)

According to a first embodiment, the plasticizing agent comprises at least one oil having a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds, of between 35% and 65%, a total content of naphthenic compounds between 10% and 40%, the contents being given by mass, relative to the total mass of the oil, and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100 ° C, measured according to the ASTM D445 method, ranging from 40 mm ² /s to 90 mm ² /s, and an aniline point, measured by ASTM D611 method, ranging from 45°C to 95°C. These oils result from a (simple) extraction of the raffinate recoverable in lubricants, using a polar solvent, and are hereinafter referred to as “RAE oil”. However, oils obtained by a process other than the RAE process, but having the same physicochemical characteristics and the same composition, also fall within the scope of the invention.

In the present application, the term “RAE oil” means an oil defined both by its content of aromatic, paraffinic and naphthenic compounds, by its viscosity at 100°C and its aniline point as defined above in the context of this first embodiment. Other preferential characteristics of these oils are reported below.

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

The RAE oils used in the clear binder composition according to the invention have a total content of paraffinic compounds of between 35% and 65%, preferably between 37% and 60%, for example between 40% and 55%.

The RAE oils used in the clear binder composition according to the invention have a total content of naphthenic compounds of between 10% and 40%, and in particular between 15% and 35%, preferably between 20 and 30%.

The RAE oils used in the clear binder composition according to the invention have a total aromatic compound content of between 10% and 40%, and in particular between 15% and 35%, for example between 25 and 30%.

In a preferred embodiment, the RAE oil is chosen from those comprising:

- a total content of paraffinic compounds of between 37% and 60%;

- a total content of naphthenic compounds of between 15% and 35%; And

- a total content of aromatic compounds of between 15% and 35%.

In a more particularly preferred mode, the RAE oil is chosen from those comprising:

- a total content of paraffinic compounds of between 40% and 55%;

- a total content of naphthenic compounds of between 20% and 30%; And

- a total content of aromatic compounds of between 25% and 35%.

The RAE oils used in the clear binder composition according to the invention have a kinematic viscosity at 100°C of between 40 and 90 mm ² /s, more advantageously between 45 and 85 mm ² /s (ASTM Method D 445). Preferably, the RAE oils used in the clear binder composition according to the invention have a kinematic viscosity at 40°C of between 1000 and 2500 mm ² /s, more advantageously between 1200 and 2500 mm ² /s (ASTM Method D 445 ).

The RAE oils used in the clear binder composition according to the invention have an aniline point between 45°C and 95°C, more advantageously between 50°C and 75°C (ASTM Method D61 1).

Preferably, the RAE oils used in the clear binder composition according to the invention have a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C. C, even better, between 200°C and 250°C (ASTM Method D92).

More preferably, the RAE oils used in the clear binder composition according to the invention have a density at 15°C of between 400 kg/m ³ and 1500 kg/m ³ , advantageously between 600 kg/m ³ and 1200 kg /m ³ , more advantageously between 800 kg/m ³ and 1100 kg/m ³ (ASTM D4052 method).

For example, an RAE oil usable in the clear binder compositions according to the invention may be a product marketed by the company TotalEnergies under the name: REGENIS® 50.

The respective contents of paraffinic, naphthenic and aromatic compounds depend to a certain extent on the nature of the crude oil from which the oils are produced and the refining process used.

For example, REGENIS® 50 is an RAE Residual Aromatic Extract) which presents

- a density at 15°C between 980 kg/m ³ and 1010 kg/m ³ (ASTM D4052 method),

- a flash point (Cleveland) of approximately 230°C (EN ISO 2592 method),

- a kinematic viscosity at 100°C of between 60 and 85 mm ² /s (ASTM D 445 method),

- an aniline point between 53 and 65°C (ASTM Method D611).

According to a second embodiment, the plasticizing agent comprises at least one oil having a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds, of between 35% and 65%, a total content of naphthenic compounds between 10% and 40%, the contents being given by mass, relative to the total mass of the oil, and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100 ° C, measured according to the ASTM method D445, ranging from 15 mm ² /s to 40 mm ² /s, and an aniline point, measured by the ASTM D61 1 method, ranging from 50°C to 80°C.

These oils result from a double extraction of the raffinate recoverable in lubricants, using a polar solvent, and are hereinafter referred to as “TDAE oil”. However, oils obtained by a process other than the TDAE process, but having the same physicochemical characteristics and the same composition, also fall within the scope of the invention.

In the present application, the term “TDAE oil” means an oil defined both by its content of aromatic, paraffinic and naphthenic compounds, by its viscosity at 100°C and its aniline point as defined above in the context of this first embodiment. Other preferential characteristics of these oils are reported below.

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

The TDAE oils used in the clear binder composition according to the invention have a total content of paraffinic compounds of between 35% and 65%, preferably between 40% and 60%, for example between 45% and 55%.

The TDAE oils used in the clear binder composition according to the invention have a total content of naphthenic compounds of between 10% and 40%, and in particular between 15% and 35%, preferably between 20 and 30%.

The TDAE oils used in the clear binder composition according to the invention have a total aromatic compound content of between 10% and 40%, and in particular between 15% and 35%, for example between 20 and 25%.

In a preferred embodiment, the TDAE oil is chosen from those comprising:

- a total content of paraffinic compounds of between 40% and 60%;

- a total content of naphthenic compounds of between 15% and 35%; And

- a total content of aromatic compounds of between 15% and 35%.

In a more particularly preferred mode, the TDAE oil is chosen from those comprising:

- a total content of paraffinic compounds of between 45% and 55%;

- a total content of naphthenic compounds of between 20% and 30%; And

- a total content of aromatic compounds of between 20% and 25%. The TDAE oils used in the clear binder composition according to the invention have a kinematic viscosity at 100°C of between 15 and 40 mm ² /s, more advantageously between 16 and 30 mm ² /s (ASTM Method D 445).

Preferably, the TDAE oils used in the clear binder composition according to the invention have a kinematic viscosity at 40°C of between 300 and 600 mm ² /s, more advantageously between 400 and 550 mm ² /s (ASTM Method D 445 ).

The TDAE oils used in the clear binder composition according to the invention have an aniline point between 50°C and 80°C, more advantageously between 60°C and 70°C (ASTM Method D61 1).

Preferably, the TDAE oils used in the clear binder composition according to the invention have a Cleveland flash point greater than or equal to 150°C, advantageously between 150°C and 600°C, more advantageously between 200°C and 400°C. C, even better, between 250°C and 300°C (ASTM Method D92).

More preferably, the TDAE oils used in the clear binder composition according to the invention have a density at 15°C of between 400 kg/m ³ and 1500 kg/m ³ , advantageously between 600 kg/m ³ and 1200 kg /m ³ , more advantageously between 800 kg/m ³ and 1100 kg/m ³ (ASTM D4052 method).

For example, a TDAE oil usable in the clear binder compositions according to the invention can be a product marketed by the company TotalEnergies under the name: Plaxolène TD346 ®.

The respective contents of paraffinic, naphthenic and aromatic compounds depend to a certain extent on the nature of the crude oil from which the oils are produced and the refining process used.

For example, Plaxolène TD346 ® is a TDAE (Treated Distillate Aromatic Extract) oil which presents:

- a density at 15°C of between 940 kg/m ³ and 970 kg/m ³ (ASTM D4052 method),

- a flash point (Cleveland) of approximately 260 to 280°C (ASTM D92 method),

- a kinematic viscosity at 100°C of between 16 and 23 mm ² /s (ASTM D 445 method),

- an aniline point between 64 and 72°C (ASTM Method D611).

Advantageously, the clear binder of the invention has a plasticizing agent content ranging from 1% to 65% by mass, relative to the total mass of the clear binder, preferably from 5% to 55% by mass, more preferably from 10 % to 50% by mass. Advantageously, in the clear binder compositions of the invention, the oils as defined above represent at least 90% by mass relative to the total mass of the plasticizing agent, preferably at least 95%. , even more advantageously at least 98%, and still advantageously at least 99%.

The structuring agent

By “structuring agent” is meant any chemical constituent conferring mechanical properties and satisfactory cohesiveness to said binder.

The structuring agent used in the composition of the invention is a resin chosen from resins of plant origin.

Resins of plant origin can be called harvested, that is to say harvested from the living plant. They can be used as is, we then speak of natural resins, or they can be chemically transformed, we then speak of modified natural resins.

Harvest resins include natural rosins, modified rosins, and rosin esters. These can be taken alone or in a mixture. Among natural rosins, we can cite gem and wood rosins, in particular pine, and/or tall oil. These natural rosins can be taken alone or in 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 in a mixture, and undergo one or more disproportionation, polymerization and/or maleization treatments.

Preferably, the resin is chosen from rosin esters, optionally modified.

More preferably, the resin is chosen from modified rosin esters.

Even more preferably, the resin is chosen from tall oil rosin esters, optionally modified.

Advantageously, the resin is chosen from modified tall oil rosin esters.

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

Advantageously, the resin is chosen from pentaerythritol esters of natural rosins, pentaerythritol esters of hydrogenated rosins and any of their mixtures, more advantageously from pentaerythritol esters of natural rosins.

According to a preferred embodiment, the resin is chosen from pentaerythritol esters of tall oil rosins.

For more information on the resins of plant origin that can be used according to the invention, one can refer to article K340 by Bernard Delmond published in “Engineering Techniques”.

Preferably, the resin of plant origin has a softening temperature, determined according to the AQCM 003 method, of between 60°C and 200°C, preferably between 80°C and 150°C, more preferably between 90°C and 110°C.

The resin of plant origin typically has an acidity index, determined according to the ASTM D465 method, less than or equal to 40 mg KOH/g, preferably ranging from 0.1 to 40 mg KOH/g, more preferably ranging from 0 .5 to 40 mg KOH/g.

According to a preferred embodiment, the resin of plant origin typically has an acidity index, determined according to the ASTM D465 method, less than 8 mg KOH/g, preferably less than or equal to 5 mg KOH/g.

Preferably, according to this preferred embodiment, the resin of plant origin has an acidity index, determined according to the ASTM D465 method, of between 0.1 and 8 mg KOH/g, preferably between 0.2 and 7 mg KOH/g, more preferably between 0.5 mg and 6 mg KOH/g.

Preferably, the resin has a Gardner color index, determined according to standard ASTM D6166, less than or equal to 10, more preferably less than or equal to 5, even more preferably less than or equal to 1, typically 0.9.

Preferably, the resin of plant origin has a glass transition temperature, measured according to the AQCM 218 method, of between 10°C and 80°C, preferably between 20°C and 60°C, more preferably between 40°C. and 50°C.

Preferably, the resin of plant origin has a Brookfield viscosity at 125°C, measured according to the AQCM 004 method, greater than or equal to 5,000 mPa.s, preferably between 7,500 mPa.s and 15,000 mPa.s, more preferably between 10,000 mPa.s and 11,000 mPa.s. Preferably, the resin of plant origin has a Brookfield viscosity at 150°C, measured according to the AQCM 004 method, greater than or equal to 500 mPa.s, preferably between 750 mPa.s and 1500 mPa.s, more preferably between 900 mPa.s and 1000 mPa.s.

Preferably, the resin of plant origin has a Brookfield viscosity at 177°C, measured according to the AQCM 004 method, greater than or equal to 80 mPa.s, preferably between 100 mPa.s and 500 mPa.s, more preferably between 150 mPa.s and 200 mPa.s.

For example, a resin usable in the clear binder compositions according to the invention may be a product marketed by the company KRATON under the name: SYLVALITE® 2100 Rosin Ester.

Preferably, the weight ratio between the structuring agent and the plasticizing agent used for the preparation of the clear binder composition according to the invention is between 0.5 and 10, for example between 1 and 5.

In a specific embodiment, the content of structuring agent in the clear binder composition of the invention ranges from 25% to 90% by mass, relative to the total mass of the composition, preferably from 30% to 80% by mass, more preferably from 35% to 75% by mass.

The polymer

The polymer used in the process for preparing the clear binder according to the invention is a copolymer based on conjugated diene units and monovinyl aromatic hydrocarbon units. The conjugated diene is preferably chosen from those containing 4 to 8 carbon atoms per monomer, for example butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3- butadiene, 1,3-pentadiene and 1,2-hexadiene, chloroprene, carboxylated butadiene, carboxylated isoprene, in particular butadiene and isoprene, and mixtures thereof.

The monovinyl aromatic hydrocarbon is preferably chosen from styrene, o-methyl styrene, p-methyl styrene, p-tert-butylstyrene, 2,3 dimethyl-styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and analogues or mixtures thereof, in particular styrene.

Advantageously, the polymer is chosen from copolymers of styrene and conjugated diene. More particularly, the polymer consists of one or more copolymers chosen from block copolymers of styrene and butadiene, styrene and isoprene, styrene and chloroprene, styrene and carboxylated butadiene or even styrene and carboxylated isoprene. Preferably, the polymer consists of one or more copolymers chosen from copolymers of styrene and butadiene.

For example, the polymer can be chosen from one or more of the following copolymers: SB copolymers (block copolymers of styrene and butadiene), SBS (styrene-butadiene-styrene block copolymers), SIS (styrene-isoprene-styrene), SBS* (styrene-butadiene-styrene star block copolymer), SBR (styrene-b-butadiene-rubber).

Advantageously, the polymer is chosen from block copolymers.

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

More preferably, the polymer is a mixture of a styrene/butadiene/styrene SBS block copolymer and a styrene/butadiene SB block copolymer.

Advantageously, the polymer is a mixture of a styrene/butadiene/styrene SBS block copolymer and a styrene/butadiene SB block copolymer in an SB/SBS mass ratio ranging from 0.1:99.9 to 30:70 , advantageously from 1:99 to 20:80, even more advantageously from 5:95 to 15:85.

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

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

According to one embodiment, the average molecular mass of the copolymer of styrene and conjugated diene, and in particular that of the copolymer of styrene and butadiene, can be comprised, for example, between 10,000 and 700,000, preferably between 50,000 and 500,000 and more preferably from 200,000 to 400,000 daltons.

According to a variant, the average molecular mass of the copolymer of styrene and conjugated diene, and in particular that of the copolymer of styrene and butadiene, can be comprised, for example, between 10,000 and 500,000, preferably between 20,000 and 100,000. , more preferably from 30,000 to 75,000 daltons, advantageously between 50,000 and 60,000.

The polymer can be of linear, branched or radial structure. Preferably, the copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, used in the clear binder composition according to the invention, has a radial structure.

In a preferred embodiment, the total quantity of the polymer used in the process for preparing the clear binder of the invention is between 0.5 and 20% by mass, preferably between 1 and 10%, preferably between 1.5 and 7.5%, for example between 2.5% and 5%, by mass relative to the total mass of the clear binder composition.

Adhesiveness boosts

To improve the reciprocal affinity between the binder and the aggregates and ensure their durability, adhesive additives can also be used. These are, for example, nitrogen-containing surfactant compounds derived from fatty acids (amines, polyamines, alkyl-polymanne, etc.).

When added to the clear binder, the adhesiveness dopes generally represent between 0.05% and 0.5% by weight relative to the total weight of the clear binder composition. For example, in a specific embodiment, between 0.05% and 0.5% of amine will be added, preferably between 0.1% and 0.3% of amine, by weight relative to the total weight of the clear binder composition.

Coloring agents

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

Optional additive(s)

According to one embodiment, the clear binder composition of the invention further comprises at least one Fischer-Tropsch wax.

The waxes (or paraffins) used are synthetic waxes from the Fischer-Tropsch synthesis process. These Fischer-Tropsch waxes are generally prepared by reacting carbon monoxide with hydrogen, typically at high pressures over a metal catalyst.

The preferred Fischer-Tropsch waxes are the Fischer-Tropsch waxes described in application WO991 1737. The Fischer-Tropsch waxes described in this document are Fischer-Tropsch waxes comprising a mixture of paraffins. Fischer-Tropsch waxes comprise a majority of n-paraffins, often more than 90%, the remainder being made up of iso-paraffins.

The average length of the paraffin chains of Fischer-Tropsch waxes is between 30 and 15 carbon atoms, preferably between 40 and 100, more preferably between 60 and 90.

Fischer-Tropsch waxes have a melting point (freezing point) between 65 and 105°C, preferably between 68 and 100°C.

The Fischer-Tropsch waxes used in the invention can be partially oxidized or fully oxidized.

A preferred example of Fischer-Tropsch wax is that sold under the brand name Sasobit®, which has a freezing point of 100°C (ASTM D 938), penetrability at 25°C less than 1 1/10 mm (ASTM D 1321) and a penetrability at 65°C of 7 1/10 mm (ASTM 1321).

Another type of Fischer-Tropsch waxes which can be used are the Fischer-Tropsch waxes described in patent EP1951818. These Fischer-Tropsch waxes include a slightly larger quantity of isomerized paraffins than classic Fischer-Tropsch waxes. These Fischer-Tropsch waxes comprising more iso-paraffins are characterized by a freezing point (ISO 2207) between 85 and 120°C and a PEN value at 43°C, expressed in 0.1 mm, determined according to IP 376, greater than 5.

Preferably, when present, the quantity of Fischer-Tropsch waxes is between 0.1% and 10% by mass, relative to the total mass of the clear binder composition, preferably between 0.5% and 5%, more preferably between 1% and 3%.

Clear binder composition

Advantageously, a clear binder composition according to the invention comprises, preferably essentially consists of, more preferably consists of:

- from 1% to 65% by mass of plasticizing agent, in particular a hydrocarbon oil of petroleum or synthetic origin, preferably from 5% to 55% by mass, more preferably between 10% and 50% by mass,

- from 25% to 90% by mass of structuring agent, in particular resin of plant origin, preferably from 30% to 80% by mass, more preferably from 35% to 75% by mass,

- from 0.5% to 20% by mass of polymer, in particular copolymer of styrene and butadiene, preferably from 1% to 10% by mass, even better from 1.5% to 7.5% by mass, advantageously from 2.5% to 5% by mass, - optionally, from 0.05% to 0.5% by mass of dope(s), for example chosen from amines, preferably between 0.1% and 0.3% by mass,

- optionally, from 0.1% to 10% by mass of Fischer-Tropsch wax(es), preferably from 0.5% to 5% by mass, more preferably from 1% and 3% by mass, relative to the total mass of the clear binder composition.

Preferably, the clear binder according to the invention has a penetrability at 25°C, measured according to standard NF EN 1426, of between 10 and 220 1/10 mm, preferably between 20 and 160 1/10 mm, more preferably between 30 and 100 1/10 mm. Those skilled in the art can modulate the penetrability of the clear binder in particular by judiciously choosing the weight ratio [structuring agent/plasticizing agent] in the composition of the clear binder. Indeed, it is known that an increase in this ratio makes it possible to reduce the penetrability at 25°C.

Advantageously, the clear binder according to the invention has a ball and ring softening temperature (TBA), measured according to the NF EN 1427 method ranging from 40 to 80°C, advantageously from 45 to 70°C.

According to one embodiment, the composition of the invention comprises a significant portion of biosourced materials, recycled or from waste. It can therefore have a high eco-material index. The eco-material index is defined by the following equation:

Eco-material index = 100% - [% of non-biosourced, non-biodegradable, non-recycled or non-waste materials], the percentages being expressed by mass, relative to the total mass of the composition.

According to one embodiment, the composition has an eco-material content of at least 5%, preferably at least 10%, preferably at least 15%.

Advantageously, the composition of the invention has a content of biosourced compounds, measured according to standard ASTM D6866, greater than or equal to 5% by mass, relative to the total mass of the composition, preferably greater than or equal to 10% by mass, more preferably greater than or equal to 15% by mass.

By “biosourced compounds”, within the meaning of the invention is meant a material derived at least in part from biomass resources. Biomass resources are organic materials available on a renewable or recurring basis, such as crop residues, wood residues, grasses and aquatic plants. Corn ethanol is a well-known example of a biobased material derived from biomass resources. Clear binder preparation process

The present invention also relates to a process for preparing the clear binder composition which has been described above. This process includes the following steps:

(i) bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140-200°C, for example from 10 minutes to 1 hour,

(ii) mixing with stirring the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C, for example from 30 minutes to 2 hours,

(iii) addition of the polymer, for example SB and/or SBS, mixing and heating at a temperature between 140-200°C, for example, from 90 minutes to 3 hours, preferably from 90 minutes to 2 hours 30 minutes ,

(iv) possible addition of an adhesive boost, mixing and heating at a temperature between 140-200°C, for example, from 5 minutes to 30 minutes,

(v) possible addition of one or more Fischer-Tropsch wax(es), mixing and heating at a temperature between 140-200°C, for example, from 5 minutes to 30 minutes.

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

Certain steps can also be carried out together or separately, in particular steps (iii) and/or (iv) and/or (v).

Preferably, step (iii) is carried out separately, before steps (iv) and (v), steps (iv) and (v) being able to be carried out together or separately.

Applications of clear binder

The clear binder composition according to the invention can be used and applied indifferently via so-called “hot”, “warm” techniques or so-called “cold” techniques well known to those skilled in the art.

By hot techniques we mean techniques in which the clear binder composition is brought to relatively high temperatures during its application. Hot techniques lead to coatings, asphalts and so-called “hot” mixes such as bitumen gravels, high modulus mixes, bitumen sands, semi-grained bituminous concretes (BBSG), concretes high modulus bituminous concrete (BBME), flexible bituminous concretes (BBS), thin bituminous concretes (BBM), pervious bituminous concretes (BBDr), very thin bituminous concretes (BBTM), ultra-thin bituminous concretes (BBUM) . The clear binder composition according to the invention is suitable for the preparation of mixes, asphalts and coatings of all types, and in particular those mentioned above.

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

Fillers (or fines) are particles with dimensions less than 0.063 mm. The aggregates include particles of dimensions 0/2 (sand), 2/4 (gravel), 4/6 and 6/10.

The coating generally comprises from 1 to 10% by weight of clear binder, relative to the total weight of the coating, preferably from 4 to 8% by mass, the remainder consisting of the aggregates, possibly the fillers and optionally the pigments. Usually, the pigments represent a quantity by weight of 0 to 1% of the coating, the fillers represent a quantity by weight of 0 to 2% of the coating.

Another subject of the invention is cast asphalts comprising a clear binder composition according to the invention, mineral fillers and possibly pigments. The asphalt comprises from 1 to 20% by weight of clear binder, relative to the total weight of the asphalt, preferably from 5 to 10% by weight, the remainder consisting of the fillers and possibly the pigments (the pigments representing a mass quantity of 0 to 1% of the asphalt).

By cold techniques, we mean techniques based on the use of clear binder emulsions in the aqueous phase, at lower temperatures. Cold techniques lead to surface coatings, grouts, cold poured mixes, cold mixes, cold bituminous concretes, emulsion gravels, storable cold mixes. The clear binder composition according to the invention is suitable for the preparation of the products mentioned above.

The invention therefore also relates to a clear binder emulsion comprising a clear binder composition according to the invention, water and an emulsifying agent. The clear binder comprises at least one plasticizing agent, at least one structuring agent and at least one polymer, as defined above.

The invention therefore also relates to a process for preparing a clear binder emulsion comprising:

(i) the preparation of a clear binder composition by mixing at least one plasticizing agent, at least one structuring agent and at least one polymer, as defined above, (ii) the preparation of an emulsifying solution by mixing water and the emulsifying agent,

(iii) dispersing the clear binder from step (i) in the emulsifying solution from step (ii).

The clear binder emulsion according to the invention preferably comprises from 50% to 80% by weight of the clear binder composition, preferably from 60% to 70%, relative to the total weight of the clear binder emulsion.

The present invention also relates to the use, in a clear binder composition, of the combination of at least:

(i) a plasticizing agent comprising at least one hydrocarbon oil of petroleum or synthetic origin, in which the content of saturated compounds is between 1% and 30% by mass, advantageously between 5 and 25% by mass, more advantageously included between 7 and 23% by mass,

(ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an index of acidity, determined according to the ASTM D465 method, less than or equal to 40 mg KOH/g,

(iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and

(iv) optionally an adhesive boost, to reduce the carbon footprint of said clear binder composition.

By “carbon footprint” of a product, we mean for the purposes of the invention the quantity of carbon (generally expressed in kg of CO2 equivalent per kg of product) necessary for the preparation of said product, this quantity of carbon equivalent taking into account both energy consumption, particularly linked to heating, and raw materials.

The carbon footprint of a product is typically determined according to any of the ISO 14040 and ISO 14044 standards.

The different embodiments, variants, preferences and advantages described above for the plasticizing agent, the structuring agent and the other components of the clear binder composition apply to the use according to the invention.

Surprisingly, in fact, it has been observed that the combination of a hydrocarbon oil of petroleum or synthetic origin and a particular rosin resin in a clear binder composition makes it possible to obtain improved properties of resistance to aging cold properties. This better resistance to aging of cold properties makes it possible to formulate surface coatings, particularly in the field of roads, which degrade less under the effect of time and/or climatic conditions.

EXAMPLES

In the examples below, parts and percentages are by weight unless otherwise noted.

Materials and methods

Plasticizer 1: the petroleum oil used is RAE, it is a residue obtained on the dearomatization unit of the oil chain. This oil has a saturates content (ASTM D2007) of 7%.

Plasticizer 2: the petroleum oil used is PLAXOLENE MS 132 which is a MES (Mild Extract Solvate) oil which has a saturates content (ASTM D2007) of 48%.

Resin: the resin available under the trade name SYLVALITE® 2100 Rosin ester from the company KRATON was used. It is a plant-based resin comprising a blend of tall oil rosin pentaerythritol esters.

Copolymer of styrene and butadiene: a mixture of SB and SBS block copolymers, thermoplastic, having a content of constituent units derived from 70/30 Butadiene/Styrene monomers, of radial structure, obtained by solution polymerization, of mass was used. molecular weight of approximately 330,000 daltons polystyrene equivalent (PS), available commercially under the name Calprene 41 1 from the company Dynasol.

Preparation of a clear binder composition according to the invention

The clear binder is prepared according to the following process:

- The oil and the resin are brought into contact and the whole is heated to a temperature of 170°C;

- The mixture of oil and resin is heated for 2 hours with a stirring speed of 200 rpm, while maintaining a temperature of 170°C;

- The copolymer based on styrene and butadiene, in powder form, is added and the whole is mixed for 2 hours at 170° C. with a stirring speed of 200 rpm. Methods for determining the properties of clear binder compositions

Compositions de liant clair [Table 1]

Clear binder compositions

The clear binder compositions C1 (according to the invention) and C2 (comparative) are prepared according to the protocol described in the previous paragraph with the constituents and proportions (in percentage by weight relative to the total weight of clear binder) reported in Table 2 .

[Table 2]

The composition is formulated at a grade of 50/70. Results

It can be seen that the composition according to the invention C1 has good mechanical properties, suitable for use as a clear binder both for road applications and for industrial applications.

It is also noted that the composition according to the invention C1 has good cold resistance to aging. Indeed, we observe that the FRAASS value after accelerated aging of 48 hours (PAV) is very close to that of the initial composition (before aging). In addition, composition C1 has better cold resistance after accelerated aging of 48 hours (PAV) than composition C2 (comparison).

Claims

1. Clear binder composition comprising: (i) a plasticizing agent comprising at least one hydrocarbon oil of petroleum or synthetic origin, in which the content of saturated compounds is between 1% and 30% by mass, advantageously between 5 and 25% by mass, more advantageously included between 7 and 23% by mass, (ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an index of acidity, determined according to the ASTM D465 method, less than or equal to 40 mg KOH/g, (iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and (iv) possibly an adhesive boost. 2. Composition according to claim 1, in which said hydrocarbon oil has a total content of aromatic compounds between 10% and 40%, a total content of paraffinic compounds, between 35% and 65%, a total content of naphthenic compounds included between 10% and 40%, the contents being given by mass, relative to the total mass of the oil present and measured according to the ASTM D2140 method. 3. Composition according to claim 2, in which said hydrocarbon oil has a kinematic viscosity at 100°C, measured according to the ASTM D445 method, ranging from 15 mm ² /s to 40 mm ² /s, and an aniline point, measured by the ASTM D61 1 method, ranging from 50°C to 80°C. 4. Composition according to claim 2, in which said hydrocarbon oil has a kinematic viscosity at 100 °C, measured according to the ASTM D445 method, ranging from 40 mm ² /s to 90 mm ² /s, and an aniline point, measured by the ASTM D61 1 method, ranging from 45°C to 95°C. 5. Composition according to any one of claims 1 to 4, in which the content of plasticizing agent ranges from 1% to 65% by mass, relative to the mass total of the composition, preferably from 5% to 55% by mass, more preferably from 10% to 50% by mass. 6. Composition according to any one of the preceding claims, in which the resin of plant origin is chosen from esters of natural rosins, more preferably from pentaerythritol esters of natural rosins, in particular from pentaerythritol esters of natural rosins. tall oil. 7. Composition according to any one of the preceding claims, in which the content of structuring agent ranges from 25% to 90% by mass, relative to the total mass of the composition, preferably from 30% to 80% by mass, more preferably from 35% to 75% by mass. 8. Composition according to any one of the preceding claims, in which the polymer is a copolymer of styrene and butadiene, preferably is chosen from a styrene/butadiene/styrene block copolymer of radial structure, a butadiene/styrene block copolymer of structure radial and their mixtures. 9. Composition according to any one of the preceding claims, further comprising Fischer-Tropsch waxes, preferably from 0.1% to 10% by weight of Fischer-Tropsch waxes, relative to the total mass of the composition of clear binder, preferably from 0.5% to 5% by weight, more preferably from 1% to 3% by weight. 10. Composition according to any one of the preceding claims, having a content of biosourced compounds, measured according to the ASTM D6866 standard, greater than or equal to 5% by mass, relative to the total mass of the composition, preferably greater than or equal at 10% by mass, more preferably greater than or equal to 15% by mass. 11. Process for preparing a clear binder composition according to any one of the preceding claims, comprising the steps: - bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140°C and 200°C, - mixing with stirring of the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C, - adding the polymer, mixing and heating to a temperature ranging from 140°C to 200°C, - adding any adhesive dope and/or any Fischer-Tropsch waxes, mixing and heating to a temperature ranging from 140°C to 200°C. 12. Emulsion comprising a clear binder composition according to any one of claims 1 to 10, water, and an emulsifying agent. 13. Coating comprising (i) a clear binder composition according to any one of claims 1 to 10 or an emulsion according to claim 12, (ii) aggregates and/or mineral fillers, and optionally (iii) one or more pigments.