WO2023046595A1

WO2023046595A1 - Clear binder and uses thereof

Info

Publication number: WO2023046595A1
Application number: PCT/EP2022/075810
Authority: WO
Inventors: Pauline ANACLET
Original assignee: Totalenergies Onetech
Priority date: 2021-09-21
Filing date: 2022-09-16
Publication date: 2023-03-30
Also published as: FR3127226A1

Abstract

The present invention relates to a clear binder composition comprising an oil of petroleum origin of the TDAE type and its uses in road and/or industrial applications. The present invention also relates to the use of a TDAE-type oil as a plasticiser in a clear binder base in order to improve the ageing resistance of the binder properties in the cold state.

Description

CLEAR BINDER AND ITS APPLICATIONS

The present invention relates to a clear binder and its uses in road and/or industrial applications, in particular for the production of colored compositions for coating surfaces. The present invention also relates to the use of a TDAE-type oil as a plasticizing agent in a clear binder composition to improve the resistance to aging of the properties, in particular the cold properties, of the composition.

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 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 entrances to built-up areas or dangerous bends. The colored coatings promote visibility in low light conditions, for example at night or in special sites such as tunnels. Finally, they simply improve the aesthetic appearance of urban roads and can be used for public squares, building and school yards, sidewalks, pedestrian streets, garden and park alleys. , parking and rest areas.

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

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

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

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

Document FR 2765229 discloses a clear binder composition, comprising a petroleum oil and a polymer such as an SB, SBS, EVA copolymer, etc. This composition also comprises a wax.

Document US2002/052431 discloses aqueous emulsions comprising on the one hand a clear synthetic binder and on the other hand a latex. During manufacture, and then during implementation, these binders are subjected to different types of external factors which modify their structure and change their properties. These are the phenomena of aging, essentially attributable to losses of volatile fractions and phenomena of oxidation by the oxygen in the air.

Application WO2010/055491 describes a clear synthetic binder formulated, in part, from renewable raw materials, which is resistant to ageing. The clear synthetic binder is prepared from a vegetable oil, a resin of petroleum origin and at least one copolymer.

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

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

Summary of the invention

The subject of the invention is a clear binder composition comprising:

(i) a plasticizer comprising at least one oil which has a total aromatic compound content of between 10% and 40%, a total paraffinic compound content of between 35% and 65%, a total naphthenics between 10% and 40%, the contents being given by weight relative to the weight of the oil and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100° C. ranging from 15 mm ² /s to 40 mm ² /s, measured according to the ASTM D445 method, and an aniline point ranging from 50° C. to 80° C., measured by the ASTM D611 method,

(ii) at least one structuring agent,

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

(iv) at least one second polymer of the ethylene-vinyl acetate type, and,

(v) optionally an adhesive dope.

According to a preferred embodiment of the invention, the oil is a synthetic oil obtained from the products of the vacuum distillation of atmospheric residues and resulting from a double extraction of the raffmat by means of a polar solvent (TDAE) .

According to a preferred embodiment of the invention, the oil comprises a total content of aromatic compounds of between 15% and 35% by weight, a total content of paraffinic compounds of between 40% and 60% by weight, and a content total naphthenic compounds of between 15% and 35% by weight, measured according to the ASTM D2140 method, a kinematic viscosity at 100° C. ranging from 16 mm ² /s to 30 mm ² /s, measured according to the ASTM D445 method, and an aniline point ranging from 60°C to 70°C, measured by the ASTM D611 method.

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

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

According to a preferred embodiment of the invention, the first polymer has a weight-average molecular weight of between 10,000 and 700,000 daltons.

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

According to a preferred embodiment of the invention, the composition has the following contents, by weight relative to the total weight of clear binder:

- from 30 to 80% by weight of plasticizer, - from 30 to 60% by weight of structuring agent,

- from 0.5 to 20% by weight of the first polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units,

- from 0.5 to 20% by weight of the second polymer of the ethylene-vinyl acetate type,

- optionally from 0.05% to 0.5% by weight of dope.

A further subject of the invention is a method for preparing a clear binder composition as described above and in detail below, comprising the steps:

- mixing and heating the plasticizer to a temperature between 140 and 200°C,

- adding the structuring agent, mixing and heating to a temperature between 140 and 200°C,

- adding the first and second polymer, mixing and heating to a temperature between 140 and 200°C,

- adding any adhesive agent, mixing and heating between 140 and 200°C.

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

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

A further subject of the invention is the use of an oil which has a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds of between 35% and 65%, a total content of naphthenic compounds between 10% and 40%, the contents being given by weight and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100° C. ranging from 15 mm ² /s to 40 mm ² /s, measured according to the method ASTM D445, and an aniline point ranging from 50°C to 80°C, measured by the ASTM D611 method, as a plasticizing agent in a clear binder composition to improve the aging resistance of the clear binder composition, in particular to improve the aging resistance of the cold properties of the clear binder composition. The expression "consists essentially of" followed by one or more characteristics, means that may 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 terminals, unless explicitly stated otherwise. This expression therefore means that the target interval includes the values X, Y and all values 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 plasticizer, for example a natural or synthetic oil, free of asphaltenes,

- a structuring agent, for example a hydrocarbon resin,

- at least one polymer,

- where appropriate, doping agents, or dopes, or dopes of adhesiveness.

The clear binder of the invention is characterized by the specific choice of the plasticizer and of two particular copolymers. This selection of components makes it possible to obtain advantageous properties compared to the clear binders of the prior art.

Within the meaning of the invention, the terms "clear binder" and "clear binder base" are used in an equivalent manner.

The invention relates to a clear binder comprising:

(i) a plasticizer comprising at least one oil which has a total aromatic compound content of between 10% and 40%, a total paraffinic compound content of between 35% and 65%, a total naphthenic compound content of between 10% and 40%, the contents being given by weight and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100° C. ranging from 15 mm ² /s to 40 mm ² /s, measured according to the ASTM D445 method , and an aniline point ranging from 50°C to 80°C, measured by the ASTM D611 method,

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

(iv) at least one second polymer of the ethylene-vinyl acetate type, and,

(v) optionally an adhesive dope.

The plasticizer

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

According to the invention, the plasticizer comprises at least one oil whose characteristics are stated above. Oils having these characteristics are available in particular among the synthetic oils obtained from the products of the vacuum distillation of atmospheric residues. These oils result from a double extraction of the raffmat recoverable in the lubricants, by means of 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 physico-chemical 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 set out in the object of the invention. Other preferred characteristics of these oils are reported below.

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

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

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

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 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 between 20% and 30%.

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 of between 16 and 30 mm ² /s (ASTM D 445 method).

The TDAE oils used in the clear binder composition according to the invention have an aniline point of between 50° C. and 80° C., more advantageously between 60° C. and 70° C. (ASTM D611 method).

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 of between 400 and 550 mm ² /s (ASTM D 445 method ).

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 that can be used in the clear binder compositions according to the invention can be a product marketed by the company TotalEnergies under the name: Plaxolene 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 originate and on the refining process used.

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

- 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 D611 method).

Advantageously, the amount of plasticizer used in the process for preparing the clear binder represents between 30% and 80%, preferably between 40% and 70% by weight, preferably between 45% and 60% relative to the weight. total clear binder composition.

Advantageously, in the clear binder compositions of the invention, the TDAE oils, as defined above, represent at least 90% by mass relative to the total mass of the plasticizer, preferably at least 95%, even more advantageously at least 98%, and even more advantageously at least 99%.

In particular, in a preferred embodiment, the plasticizer according to the invention consists solely of a TDAE oil or of a mixture of TDAE oils.

When the plasticizer comprises another type of oil in addition to the TDAE oil, the latter can be chosen from oils of petroleum origin or oils of vegetable origin.

The structuring agent

By “structuring agent”, is meant any chemical constituent conferring satisfactory mechanical properties and cohesiveness to said binder. The structuring agent is a constituent of clear binder compositions well known to those skilled in the art. The structuring agent used in the composition of the invention is a resin, preferably chosen from resins of hydrocarbon-based petroleum origin or resins of vegetable origin.

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

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

Other examples of resins that can be used as a structuring agent include, without limitation, resins of plant origin obtained from plants and/or plants.

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

Harvest resins include accroid resins, dammar, natural rosins, modified rosins, rosin esters, and metal resinates. These can be taken alone or in a mixture. Among the natural rosins, mention may be made of gem and wood rosins, in particular pine, and/or tall oil rosins. 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.

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 natural rosins, esters of glycerol and hydrogenated rosins, esters of glycerol and dismutated rosins, esters of glycerol and polymerized rosins, esters of glycerol and maleized rosins, esters of pentaerythritol and natural rosins and esters of pentaerythritol and hydrogenated rosins. These rosin esters can be taken alone or as a mixture and come from rosins which have undergone one or more disproportionation, polymerization and/or maleization treatments.

Natural rosin esters of pentaerythritol and hydrogenated rosin esters of pentaerythritol are preferred rosin esters.

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

For more information on the resins of vegetable origin that can be used according to the invention, reference can be made to article K340 by Bernard Delmond published in the “Techniques de l’ingénieur”.

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

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

Preferably, the weight ratio between the structuring agent and the plasticizing agent used for the preparation of the clear binder composition according to the invention is between 0.3 and 2, for example between 0.5 and 1.5.

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

The first polymer

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

The monovinyl aromatic hydrocarbon is preferably chosen from styrene, o-methyl styrene, p-methyl styrene, p-tert-butyl styrene, 2,3-dimethyl-styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and the like or mixtures thereof, especially styrene.

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

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

Advantageously, the first polymer is chosen from block copolymers.

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

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

Advantageously, the first 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, preferably from 1:99 to 20:80, even more preferably 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 content by weight 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 content by weight of styrene ranging from 20 to 40%, preferably from 25 to 35% by mass relative to the total mass of the copolymer .

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 200,000 to 400,000 daltons.

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

In a preferred embodiment, the total amount of the first polymer used in the process for preparing the clear binder of the invention is between 0.5 and 20% by weight, preferably between 1 and 10%, preferably between 1 and 7%, for example between 1.5% and 5%, by mass based on the total mass of the clear binder composition.

The second polymer

The second polymer used in the process for preparing the clear binder according to the invention is a copolymer of the ethylene-vinyl acetate (EVA) type.

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

Preferably, the second copolymer has a melt index or melt index (melt index in English) of between 10 and 400 g/10 min), preferentially between 50 and 300 g/10 min, even more preferentially between 100 and 200 g/10 min. melt index or fluidity index is measured in a known manner by the ASTMD1238 method or by the ISO 1133 method. In a specific embodiment, the total amount of the second polymer used in the process of the invention is between 0.5 and 20% by weight, preferably between 0.5 and 10%, preferably between 1 and 7%, for example between 1% and 5%, based on the total mass of the clear binder composition.

Adhesiveness boosters

To improve the reciprocal affinity between the binder and the aggregates and ensure their durability, adhesive dopes 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, tackifiers generally represent between 0.05% and 0.5% by weight based on 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 can 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. Use will be made, for example, of metal oxides such as iron oxides, chromium oxides, cobalt oxides, titanium oxides to obtain the colors red, yellow, grey, blue-green or white. The pigments can be added either in the clear binder or in the asphalt (mixed with the aggregates for example) or in an emulsion of the clear binder.

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) mixing the plasticizer, for example TDAE oil or the mixture of TDAE oils, and heating to a temperature between 140-200°C, for example from 10 minutes to 30 minutes,

(ii) addition of the structuring agent, for example the hydrocarbon resin, mixing and heating to a temperature of between 140-200° C., for example from 30 minutes to 2 hours, (iii) addition of the first and of the second polymer, for example SB and/or SBS and EVA, mixing and heating at a temperature of between 140-200° C., for example, from 90 minutes to 3 hours, of preferably from 90 minutes to 2 hours 30,

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

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

Advantageously, a clear binder composition according to the invention comprises, by weight relative to the total weight of clear binder, or better consists essentially of:

- from 30 to 80% by weight, preferably from 40 to 70% by weight of plasticizer, preferably between 45% and 60% by weight of plasticizer, for example a TDAE oil or a mixture of TDAE oils ,

- from 30 to 60% by weight, preferably from 40 to 50% by weight of structuring agent, for example a hydrocarbon resin,

- from 0.5 to 20% by weight, preferably from 1 to 10%, even better from 1 to 7%, advantageously from 1.5 to 5% by weight of the first polymer, for example a copolymer of styrene and butadiene ,

- from 0.5 to 20% by weight, preferably from 0.5 to 10%, even better from 1 to 7%, advantageously from 1 to 5% by weight of the second polymer (EVA),

- optionally from 0.05% to 0.5% by weight of dope, preferably between 0.1% and 0.3% by weight of dope, for example a dope chosen from amines.

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

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

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 1/10mm. A person skilled in the art can modulate the penetrability of the clear binder, in particular by carefully choosing the ratio by weight [structuring agent/plasticizing agent] in the composition of the clear binder. Indeed, it is known that an increase in this ratio makes it possible to reduce the penetrability at 25°C. Advantageously, the clear binder according to the invention has a ring and ball softening temperature (TBA), measured according to the NF EN 1427 method ranging from 40 to 80°C, advantageously from 45 to 70°C.

Clear Binder Applications

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

By hot techniques is meant techniques in which the clear binder composition is brought during its application to relatively high temperatures. Hot techniques lead to coatings, asphalts and so-called "hot" mixes such as gravel-bitumen, high-modulus mixes, sand-bitumen, semi-grained bituminous concretes (BBSG), concretes high modulus bituminous concrete (BBME), flexible bituminous concrete (BBS), thin bituminous concrete (BBM), permeable bituminous concrete (BBDr), very thin bituminous concrete (BBTM), ultra-thin bituminous concrete (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.

A subject of the invention is therefore also asphalt mixes comprising a clear binder composition according to the invention, aggregates, optionally fillers and optionally pigments.

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

The mix generally comprises from 1 to 10% by weight of clear binder, relative to the total weight of the mix, preferably from 4 to 8% by weight, the remainder being made up of aggregates, optionally fillers and optionally the pigments. Usually, the pigments represent an amount by weight of 0 to 1% of the mix, the fillers represent an amount by weight of 0 to 2% of the mix.

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

By cold techniques, we mean techniques based on the use of clear binder emulsions in aqueous phase, at lower temperatures. Cold techniques lead to surface dressings, grouts, cold-poured mixes, cold mixes, cold bituminous concretes, gravel-emulsions, 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 plasticizer, at least one structuring agent and at least one mixture of a first and a second polymer, as defined above.

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

(i) the preparation of a clear binder composition by mixing at least one plasticizer, at least one structuring agent and at least one mixture of a first and a second polymer, as defined above,

(ii) preparing an emulsifying solution by mixing 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.

Use of a TDAE oil as a plasticizer in a clear binder base

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

As described above, the clear binder base includes:

- a plasticizer,

- a structuring agent, for example a hydrocarbon resin, - at least one mixture of a first and a second polymer,

- where appropriate, doping agents, or dopes, or dopes of adhesiveness.

TDAE, or the mixture of TDAE oils, for use as a plasticizer in a clear binder base is described above in the chapter “the plasticizer”.

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

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

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

Examples

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

Materials and methods:

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

Table 1:

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

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

Copolymer of styrene and butadiene: a mixture of block copolymers SB and SB S, thermoplastics, having a content of constituent units resulting from monomers 70/30 Butadiene/Styrene, of radial structure, obtained by polymerization in solution, of molecular mass of about 330,000 daltons equivalent polystyrene (PS), commercially available under the name Calprene ® 411 from the company Dynasol.

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

Adhesiveness booster: amine-type compound (Cecabase® 200 commercially available from ARKEMA).

Preparation of a clear binder composition according to the invention (Cl) and comparative compositions

The clear binders are prepared according to the following process:

- The oil is heated to 170°C;

- The resin is added, and the mixture is mixed for 1 to 2 hours at 170°C with a stirring speed of 300 rpm;

- The copolymer based on styrene and butadiene, in powder form, and the EVA copolymer are added, and the mixture is mixed for 2 h at 170° C. with a stirring speed of 250 rpm;

- The adhesive agent is added in liquid form and then mixed for 15 minutes at 170°C. Methods for determining the properties of clear binder compositions

Table 2

Clear binder compositions The clear binder compositions according to the invention Cl and comparative Tl are prepared according to the 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 3.

Table 3:

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

Results

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

Claims

1. Clear binder composition comprising:

(i) a plasticizer comprising at least one oil which has a total content of aromatic compounds of between 10% and 40%, a total content of paraffinic compounds of between 35% and 65%, a total content of naphthenic compounds of between 10 % and 40%, the contents being given by weight relative to the weight of the oil and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100° C. ranging from 15 mm ² /s to 40 mm ² /s , measured according to the ASTM D445 method, and an aniline point ranging from 50° C. to 80° C., measured by the ASTM D611 method,

(ii) at least one structuring agent,

(iv) at least one second polymer of the ethylene-vinyl acetate type, and,

(v) optionally an adhesive dope.

2. Composition according to claim 1, in which the oil is a synthetic oil obtained from the products of the vacuum distillation of atmospheric residues and resulting from a double extraction of the raffmat by means of a polar solvent (TDAE).

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

4. Composition according to any one of the preceding claims, in which the first polymer is a copolymer of styrene and butadiene.

5. Composition according to any one of the preceding claims, in which the first polymer comprises a content by weight of styrene ranging from 20 to 40%.

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

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

8. Composition according to any one of the preceding claims, which has the following contents, by weight relative to the total weight of clear binder:

- from 30 to 80% by weight of plasticizer,

- from 30 to 60% by weight of structuring agent,

- optionally from 0.05% to 0.5% by weight of dope.

9. Process for the preparation of a clear binder composition according to any one of the preceding claims, comprising the steps:

- mixing and heating the plasticizer to a temperature between 140 and 200°C,

- adding any adhesive agent, mixing and heating between 140 and 200°C.

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

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

12. Use of an oil which has a total content of aromatic compounds between 10% and 40%, a total content of paraffinic compounds between 35% and 65%, a total content of naphthenic compounds between 10% and

40%, the contents being given by weight and measured according to the ASTM D2140 method, said oil having a kinematic viscosity at 100° C. ranging from 15 mm ² /s to 40 mm ² /s, measured according to the ASTM D445 method, and a aniline point ranging from 50°C to 80°C, measured by the ASTM D611 method, as a plasticizing agent in a clear binder composition to improve the aging resistance of the clear binder composition, in particular to improve the resistance to cold aging properties of the clear binder composition.