Clear binder and uses thereof

Abstract

The invention relates to a clear binder composition, comprising: (i) a plasticiser comprising at least one oil of plant origin comprising an ester compound derived from tall oil, said oil of plant origin having a solidification temperature, determined according to the method of ASTM D1982, of less than 30°C and an acid value, determined according to the method of ASTM D465, of less than or equal to 150 mg KOH / g; (ii) a structuring agent comprising at least one resin of plant origin selected from natural rosins, modified rosins, rosin esters and any mixture thereof, said resin of plant origin having an acid value, determined according to the method of AQCM 001, of less than 8 mg KOH / g; (iii) at least one polymer based on conjugated diene units and on monovinyl aromatic hydrocarbon units; and (iv) optionally an adhesion dopant.

Description

[0001] Clear binder and its applications

[0002] Technical field

[0003] 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.

[0004] State of the prior art

[0005] Conventional bituminous binders, due to the presence of asphaltenes, are black in color and are therefore difficult to color. Colored coatings are increasingly used because, among other things, they improve the safety of road users by clearly identifying specific routes such as pedestrian paths, cycle paths, and bus lanes. They also make it possible to mark certain danger zones such as city entrances or dangerous bends. Colored coatings improve visibility in low-light conditions, for example at night or in specific locations such as tunnels. Finally, they simply improve the aesthetic appearance of urban roads and can be used for public squares, building and school courtyards, sidewalks, pedestrian streets, garden and park paths, parking and rest areas.

[0006] Therefore, for all the above applications, it is preferred to use clear synthetic binders, which do not contain asphaltenes and can be colored.

[0007] 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.

[0008] 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.

[0009] Application WO2018 / 115729 discloses a cold-solid binder composition. In particular, the composition may be a clear binder and the plasticizing agent is in particular an oil of petroleum origin. Application WO2018 / 115730 describes a similar composition for the preparation of poured asphalts and the production of coatings.

[0010] Document US2002 / 052431 discloses aqueous emulsions comprising on the one hand a clear synthetic binder and on the other hand a latex. During manufacture, and then in implementation, these binders are subjected to different types of external factors which modify their structure and cause their properties to change.

[0011] 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.

[0012] 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.

[0013] However, these clear binders are not entirely satisfactory. Although they do indeed have a reduced environmental footprint compared to traditional clear binders, they present sustainability issues. Indeed, currently available clear binders incorporating a plasticizing agent and / or a structuring agent of plant origin have significantly reduced resistance to aging compared to traditional clear binders prepared from petroleum-based products. In particular, these binders prepared from plant-based compounds have significantly reduced resistance to aging of cold properties compared to traditional clear binders prepared from petroleum-based products.

[0014] More regular replacement of road surfaces is therefore to be expected, which significantly reduces their environmental value.

[0015] There is therefore still a need for bio-sourced clear binders (prepared from at least one plasticizing agent of plant origin and / or at least one structuring agent of plant origin) with improved mechanical properties, compared to existing bio-sourced clear binders.

[0016] In particular, there remains a need for bio-sourced clear binders (prepared from at least one plasticizing agent of plant origin and / or at least one structuring agent of plant origin) with improved resistance to aging, in particular resistance to aging of cold properties, compared to the bio-sourced clear binders currently available.

[0017] In particular, there remains a need for bio-sourced clear binders (prepared from at least one plasticizing agent of plant origin and / or at least one structuring agent of plant origin) with properties equivalent to traditional clear binders prepared from oil and resin of petroleum origin.

[0018] More particularly, there remains a need for bio-sourced clear binders (prepared from at least one plasticizing agent of plant origin and / or at least one structuring agent of plant origin) having resistance to aging, in particular resistance to aging of cold properties, equivalent to traditional clear binders prepared from oil and resin of petroleum origin.

[0019] Surprisingly, it was found that the combination of (i) a vegetable oil comprising an ester derived from tall oil having a solidification temperature of less than 30°C and whose acidity index, determined according to the ASTM D465 method, is less than or equal to 150 mg KOH / g and (ii) a resin of vegetable origin chosen from natural rosins, modified rosins, rosin esters, and mixtures thereof and whose acidity index, determined according to the ASTM D465 method, is less than 8 mg KOH / g made it possible to obtain a bio-sourced clear binder having improved properties compared to the bio-sourced clear binders of the prior art incorporating an oil of vegetable origin and / or a resin of vegetable origin.In particular, the clear binders of the invention exhibit better resistance to aging of their properties, in particular better resistance to aging of the cold properties, compared to the bio-sourced clear binders of the prior art.

[0020] More specifically, it was found that this particular combination made it possible to obtain a clear binder with properties similar to those of traditional clear binders, obtained from petroleum-based compounds, in particular similar resistance to cold aging properties.

[0021] Summary of the invention

[0022] For the purposes of the invention, the term “bio-sourced clear binder” means a clear binder comprising at least one plasticizing agent of plant origin and / or at least one structuring agent of plant origin.

[0023] In the remainder of the application, any reference to a standard (e.g. ASTM D1982) refers to the version of said standard in force on the date of filing of this application.

[0024] The invention firstly relates to a clear binder composition comprising:

[0025] (i) a plasticizing agent comprising at least one oil of vegetable origin comprising an ester compound derived from tall oil, said oil of vegetable origin having a solidification temperature, determined according to the ASTM D1982 method, of less than 30°C and an acidity index, determined according to the ASTM D465 method, of less than or equal to 150 mg KOH / g,

[0026] (ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an acidity index, determined according to the ASTM D465 method, of less than 8 mg KOH / g,

[0027] (iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and

[0028] (iv) possibly an adhesive agent.

[0029] Preferably, the ester compound is selected from derivatives of a tall oil fatty acid.

[0030] More preferably, the ester compound is chosen from the group consisting of: trimethylolpropane tallates, ethylene glycol monomerates, neopentyl glycol monomerates, 2-ethylhexyl monomerates, glycerol monomerates, and any of their mixtures.

[0031] Advantageously, the content of plasticizing agent ranges from 1% to 40% by mass, relative to the total mass of the composition, preferably from 5% to 30% by mass, more preferably from 10% to 20% by mass.

[0032] Preferably, the resin of plant origin is chosen from natural rosin esters, more preferably from pentaerythritol esters of natural rosins, in particular from pentaerythritol esters of tall oil rosins.

[0033] Advantageously, the clear binder composition has a structuring agent content of 50% to 95% by mass, relative to the total mass of the composition, preferably 60% to 90% by mass, more preferably 75% to 85% by mass.

[0034] Preferably, the polymer is a copolymer of styrene and butadiene, preferably selected from a styrene / butadiene / styrene block copolymer of radial structure, a butadiene / styrene block copolymer of radial structure and mixtures thereof.

[0035] According to one embodiment, the clear binder composition further comprises Fischer-Tropsch waxes, preferably from 0.1% to 10% by mass of Fischer-Tropsch waxes, relative to the total mass of the clear binder composition, preferably from 0.5% to 5% by mass, more preferably from 1% to 3% by mass.

[0036] According to a preferred embodiment, the clear binder composition of the invention has a biosourced carbon content, measured according to standard ASTM D6668, of at least 75%, preferably at least 80%, more preferably at least 85%, advantageously at least 90%.

[0037] According to a preferred embodiment, the clear binder composition of the invention has an aerobic biodegradability, measured according to the ISO 17556 standard, at least 2 times higher than the aerobic biodegradability of a clear binder composition prepared from a plasticizing agent of petroleum origin and a structuring agent of petroleum origin, preferably at least 3 times higher, more preferably at least 4 times higher, advantageously at least 5 times higher.

[0038] The invention also relates to a process for preparing a clear binder composition as defined above and in detail below, comprising the steps:

[0039] - bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140°C and 200°C,

[0040] - mixing with stirring the plasticizing agent and the structuring agent at a temperature between 140°C and 200°C,

[0041] - adding the polymer, mixing and heating to a temperature ranging from 140°C to 200°C,

[0042] - adding any adhesive dope, mixing and heating to a temperature ranging from 140°C to 200°C.

[0043] The invention also relates to an emulsion comprising a clear binder composition as defined above and in detail below, water, and an emulsifying agent.

[0044] The invention finally relates to a coating comprising (i) a clear binder composition as defined above and in detail below or an emulsion as defined above and in detail below, (ii) aggregates and / or mineral fillers, and optionally (iii) one or more pigments.

[0045] The expression "consists essentially of" followed by one or more characteristics means that, in addition to the components or steps explicitly listed, components or steps which do not significantly modify the properties and characteristics of the invention may be included in the process or material of the invention.

[0046] The expression "between X and Y" includes the limits, unless explicitly stated otherwise. This expression therefore means that the interval in question includes the values ​​X, Y and all values ​​from X to Y.

[0047] The various embodiments, variations, preferences and advantages described for each of the objects of the invention apply to all of the objects of the invention and may be taken separately or in combination.

[0048] Detailed description

[0049] The essential constituents of a clear binder composition are: - a plasticizing agent, for example an asphaltene-free oil,

[0050] - a structuring agent,

[0051] - at least one polymer,

[0052] - where appropriate, doping agents, or dopes, or adhesive dopes, and / or Fischer-Tropsch waxes.

[0053] The clear binder of the invention is characterized by the combination of a particular oil of plant origin and a specific resin of 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, while having similar properties, particularly in terms of resistance to aging.

[0054] For the purposes of the invention, the terms “clear binder” and “clear binder base” are used equivalently.

[0055] The invention relates to a clear binder comprising:

[0056] (i) a plasticizing agent comprising at least one oil of vegetable origin comprising an ester compound derived from tall oil, said oil of vegetable origin having a solidification temperature, determined according to the ASTM D1982 method, of less than 30°C and an acidity index, determined according to the ASTM D465 method, of less than or equal to 150 mg KOH / g,

[0057] (ii) a structuring agent comprising at least one resin of plant origin chosen from natural rosins, modified rosins, rosin esters, and any of their mixtures, said resin of plant origin having an acidity index, determined according to the ASTM D465 method, of less than 8 mg KOH / g

[0058] (iii) at least one polymer based on conjugated diene units and monovinyl aromatic hydrocarbon units, and

[0059] (iv) possibly an adhesive dope and / or a Fischer-Tropsch wax.

[0060] The plasticizing agent

[0061] For the purposes of the invention, the term "plasticizing agent" means a chemical constituent making it possible to fluidify and reduce the viscosity and modulus of the binder in which it is incorporated.

[0062] According to the invention, the plasticizing agent comprises, preferably consists of, at least one oil of plant origin whose characteristics are stated above.

[0063] The vegetable-derived oil typically comprises at least one vegetable-derived ester compound derived from tall oil. For the purposes of the invention, the term "tall oil derivative" means a chemical compound obtained at least in part from one of the components of crude tall oil (or CTO). Components of crude tall oil include, for example, tall oil fatty acids (or TOFA), tall oil heads, tall oil rosins, and tall oil pitch (also known as tall oil pitch). Suitable tall oil derivatives of the invention include acid-functional derivatives such as monomeric, dimeric, and trimeric acids made from tall oil fatty acids, dimerized rosin acids, and refined fatty acids obtainable from tall oil.

[0064] The ester compound has a solidification temperature, determined according to the ASTM D1982 method, of less than 30°C.

[0065] Preferably, the ester compound is selected from C4-C36, typically C8-C20, fatty acid esters.

[0066] As is known, an ester compound results from the reaction between a carboxylic acid and an alcohol with elimination of water. In the following application, the ester compound of the invention is described from the carboxylic acid and the alcohol whose esterification reaction would lead to the production of said ester.

[0067] According to one embodiment, the carboxylic acid is in a polymerized form, in particular in the form of dimerized fatty acids.

[0068] Preferably, the fatty acid is selected from the group consisting of: oleic acid, linoleic acid, linolenic acid, palmitic acid and any mixture thereof.

[0069] Alternatively, the fatty acid is selected from monomeric acids (defined below), dimeric acids, tall oil heads, and the like, and mixtures thereof.

[0070] The alcohol can be primary, secondary, or tertiary. In particular, it can be a monool, a diol, or a polyol. The alcohol can also come from polyethers such as triethylene glycol or polyethylene glycols. Phenolic esters are also suitable.

[0071] Preferably, the alcohol is selected from: methanol, ethanol, 1-propanol, isobutyl alcohol, 2-ethylhexanol, octanol, isodecyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol monobutyl ether, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol, sucrose and the like, and any mixture thereof. More preferably, the alcohol is selected from alcohols comprising a quaternary carbon atom located in the beta position relative to the oxygen of any of their hydroxyl groups. Examples include trimethylolpropane, neopentyl glycol, trimethylolethane, pentaerythritol, dipentaerythritol, benzyl alcohols and others.

[0072] As stated above, the ester compound is a derivative of tall oil.

[0073] Preferably, it is obtained from a tall oil fatty acid (also called TOFA for "Tall Oil fatty acid" in English) or from a derivative of a tall oil fatty acid, for example from a dimer acid of tall oil fatty acid. Tall oil fatty acid is obtained from crude tall oil (or CTO for "Crude Tall Oil" in English) by distillation. Crude tall oil is a by-product of the process of converting wood into paper pulp, also called the Kraft process. Distillation of crude tall oil gives, in addition to tall oil fatty acid, a more volatile and highly saturated fraction of long-chain fatty acids (mainly palmitic acid), called "tall oil heads".Tall oil fatty acid is the next cut, which contains mainly C18-C20 fatty acids with varying degrees of unsaturation (e.g., oleic acid, linoleic acid, linolenic acid, and various isomers thereof). Another cut, known as distilled tall oil (DTO), is a mixture composed mainly of tall oil fatty acids and a smaller proportion of tall oil rosin. Tall oil rosin (TOR), isolated next, consists largely of a C19-C20 tricyclic monocarboxylic acid. The bottom cut of the distillation is known as tall oil pitch or simply pitch. In general, any fraction which contains at least one tall oil fatty acid is preferred for the preparation of an ester compound suitable for the invention.

[0074] As previously stated, polymerized fatty acids can be used to make the tall oil-derived ester compounds of the invention. Unsaturated fatty acids are generally polymerized using acidic clay catalysts. Fatty acids with high levels of mono- or polyunsaturation are preferred. In this high-temperature process, the unsaturated fatty acids undergo intermolecular addition reactions, e.g., the "Alder-ene reaction," to form polymerized fatty acids. The mechanism is complex and not well understood. However, the product primarily comprises dimerized fatty acids and a unique mixture of monomeric fatty acids. Distillation yields a fraction highly enriched in dimerized fatty acid, commonly referred to as "dimer acid." These dimer acids can be used to make the ester-functional rejuvenating agents.

[0075] Distillation of the polymerized tall oil fatty acid provides a fraction enriched in monomeric fatty acids, known as the "Monomer" (with a capital "M") or "Monomer Acid". The Monomer, a unique composition, is a preferred starting material for the preparation of the ester compound of the invention. While tall oil fatty acid derived from a natural source consists largely of linear unsaturated C carboxylic acids, primarily oleic and linoleic acids, the Monomer contains relatively small amounts of oleic and linoleic acids, and instead contains significant amounts of branched and cyclic, saturated and unsaturated C carboxylic acids, as well as elaidic acid. The more diverse and significantly branched composition of the Monomer results from the catalytic treatment performed on the tall oil fatty acid during polymerization.It is believed that the reaction of Monomer with alcohols to make "Monomerate" esters will yield unique derivatives that differ from the corresponding tall oil fatty acid esters. The "Monomer" has been assigned CAS No. 68955-98-6. Examples of Monomer are Century® MO5 and MO6 fatty acids, produced by Arizona Chemical Company. Further information on the composition of Monomer and its conversion to various esters is given in US Patent 7,256,162.

[0076] For the purposes of the invention, the term "Monomerate of an alcohol" means the product of the reaction between the "Monomer" (defined above) and said alcohol. More particularly, the "Monomerate of an alcohol" is obtained by esterification of the monomeric fatty acids obtained by distillation of the polymerized tall oil fatty acid and said alcohol.

[0077] The ester compounds of the invention include, for example, ethylene glycol tallate (i.e., tall oil fatty acid ethylene glycol ester), propylene glycol tallate, trimethylolpropane tallate, neopentyl glycol tallate, methyl tallate, ethyl tallate, glycerol tallate, oleyl tallate, octyl tallate, benzyl tallate, 2-ethylhexyl tallate, polyethylene glycol tallates, tall oil pitch esters, ethylene glycol monomerate, glycerol monomerate, trimethylolpropane monomerate, neopentyl glycol monomerate, 2-ethylhexyl monomerate, ethylene glycol dimerate, 2-ethylhexyl dimerate, 2-ethylhexyl trimerate, and derivatives thereof. Particularly preferred ester compounds are tallates and monomerates, including trimethylolpropane tallate, ethylene glycol monomerate, glycerol monomerate, and any mixtures thereof.The ester compounds are typically non-crystalline, i.e., they have a solidification temperature, determined according to the ASTM D1982 method, of less than 30°C, preferably less than 20°C, more preferably less than 10°C, and most preferably less than 0°C.

[0078] Preferably, the ester compounds have a cloud point below 0°C, more preferably below -10°C, even more preferably below -20°C, and most preferably below -25°C. The cloud point is determined by gradually cooling a pure, molten sample and observing the temperature at which the clear sample just becomes cloudy.

[0079] Preferably, the plasticizing agent has a Gardner color index, determined according to standard ASTM D6166, of less than or equal to 10, more preferably less than or equal to 8.

[0080] Preferably, the plasticizing agent has a flash point, determined according to the ASTM D92 method, greater than or equal to 200°C, preferably greater than or equal to 250°C, even more preferably greater than or equal to 280°C.

[0081] Preferably, the plasticizing agent has an acidity index, determined according to the ASTM D465 method, less than or equal to 150 mg KOH / g, more preferably less than or equal to 100 mg KOH / g, even more preferably less than or equal to 50 mg KOH / g.

[0082] Advantageously, the plasticizing agent has an acidity index, determined according to the ASTM D465 method, less than or equal to 20 mg KOH / g, preferably less than or equal to 15 mg KOH / g, typically between 0.1 mg KOH / g and 15 mg KOH / g.

[0083] Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 40°C, measured according to the ASTM D445 method, greater than or equal to 30 cSt, more preferably between 30 cSt and 100 cSt, even more preferably between 35 cSt and 50 cSt.

[0084] Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at -20°C, measured according to the ASTM D445 method, greater than or equal to 1000 cSt, more preferably between 1000 cSt and 2000 cSt, even more preferably between 1500 cSt and 1800 cSt, typically 1600 cSt.

[0085] Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 0°C, measured according to the ASTM D445 method, greater than or equal to 200 cSt, more preferably between 200 cSt and 500 cSt, even more preferably between 300 cSt and 400 cSt, typically 350 cSt.

[0086] Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 20°C, measured according to the ASTM D445 method, greater than or equal to 50 cSt, more preferably between 50 cSt and 200 cSt, even more preferably between 75 cSt and 150 cSt, typically 100 cSt.

[0087] Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 40°C, measured according to the ASTM D445 method, greater than or equal to 10 cSt, more preferably between 10 cSt and 100 cSt, even more preferably between 15 cSt and 50 cSt, typically 40 cSt.

[0088] Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 60°C, measured according to the ASTM D445 method, greater than or equal to 10 cSt, more preferably between 15 cSt and 50 cSt, even more preferably between 20 cSt and 30 cSt, typically 23 cSt.

[0089] Preferably, the plasticizing agent has a Cannon-Fenske kinematic viscosity at 100°C, measured according to the ASTM D445 method, greater than or equal to 5 cSt, more preferably between 5 cSt and 50 cSt, even more preferably between 5 cSt and 20 cSt, typically 10 cSt.

[0090] In particular, in a preferred embodiment, the plasticizing agent according to the invention consists solely of one or more ester compound(s) derived from tall oil.

[0091] For example, an oil that can be used in the clear binder compositions according to the invention may be a product marketed by the company KRATON under the name: SYLVAROAD® RP1000.

[0092] Advantageously, the clear binder of the invention has a plasticizing agent content ranging from 1% to 40% by mass, relative to the total mass of the clear binder, preferably from 5% to 30% by mass, more preferably from 10% to 20% by mass.

[0093] Advantageously, in the clear binder compositions of the invention, the oils of plant origin, as defined above, represent at least 90% by mass relative to the total mass of the plasticizing agent, preferably at least 95%, even more advantageously at least 98%, and even more advantageously at least 99%.

[0094] The structuring agent

[0095] By “structuring agent” we mean any chemical constituent conferring mechanical properties and satisfactory cohesiveness to said binder.

[0096] The structuring agent used in the composition of the invention is a resin chosen from resins of plant origin.

[0097] Resins of plant origin can be said to be harvested, that is, harvested from the living plant. They can be used as is, in which case we speak of natural resins, or they can be chemically transformed, in which case we speak of modified natural resins.

[0098] Harvested resins include natural rosins, modified rosins, and rosin esters. These can be used alone or in a mixture. Natural rosins include gem and wood rosins, especially pine rosins, and / or tall oil rosins. These natural rosins can be used alone or in a mixture.

[0099] Modified rosins include hydrogenated rosins, disproportionated rosins, polymerized rosins, and / or maleated rosins. These modified natural rosins may be taken alone or in a mixture, and may undergo one or more disproportionation, polymerization, and / or maleization treatments.

[0100] Preferably, the resin is chosen from rosin esters, optionally modified.

[0101] More preferably, the resin is chosen from modified rosin esters.

[0102] Even more preferably, the resin is chosen from tall oil rosin esters, possibly modified.

[0103] Advantageously, the resin is chosen from modified tall oil rosin esters.

[0104] Rosin esters include natural rosin methyl esters, hydrogenated rosin methyl esters, natural rosin glycerol esters, hydrogenated rosin glycerol esters, disproportionated rosin glycerol esters, polymerized rosin glycerol esters, maleated rosin glycerol esters, natural rosin pentaerythritol esters, and hydrogenated rosin pentaerythritol esters. These rosin esters may be taken alone or as a mixture and may be derived from rosins that have undergone one or more disproportionation, polymerization, and / or maleization treatments.

[0105] 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.

[0106] According to a preferred embodiment, the resin is chosen from pentaerythritol esters of tall oil rosins. For further information on the resins of plant origin that can be used according to the invention, reference may be made to article K340 by Bernard Delmond published in “Techniques de l'ingénieur”.

[0107] 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.

[0108] Plant-based resin typically has an acidity index, determined according to ASTM D465, of less than 8 mg KOH / g.

[0109] Preferably, 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.

[0110] Advantageously, the plant-based resin has an acidity index, determined according to the ASTM D465 method, less than or equal to 5 mg KOH / g.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] For example, a resin that can be used 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 2 and 10, for example between 4 and 6.

[0117] In a specific embodiment, the content of structuring agent in the clear binder composition of the invention ranges from 50% to 95% by mass, relative to the total mass of the composition, preferably from 60% to 90% by mass, more preferably from 75% to 85% by mass.

[0118] The polymer

[0119] The polymer used in the process for preparing the clear binder according to the invention is a copolymer based on conjugated diene units and monovinyl aromatic hydrocarbon units. The conjugated diene is preferably chosen from those comprising 4 to 8 carbon atoms per monomer, for example butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,2-hexadiene, chloroprene, carboxylated butadiene, carboxylated isoprene, in particular butadiene and isoprene, and mixtures thereof.

[0120] The monovinyl aromatic hydrocarbon is preferably selected from styrene, o-methyl styrene, p-methyl styrene, p-tert-butylstyrene, 2,3 dimethyl styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and the like or mixtures thereof, in particular styrene.

[0121] Advantageously, the polymer is chosen from copolymers of styrene and conjugated diene. More particularly, the polymer consists of one or more copolymers chosen from block copolymers of styrene and butadiene, of styrene and isoprene, of styrene and chloroprene, of styrene and carboxylated butadiene or of styrene and carboxylated isoprene. Preferably, the polymer consists of one or more copolymers chosen from copolymers of styrene and butadiene.

[0122] For example, the polymer may be selected from one or more of the following copolymers: SB copolymers (styrene and butadiene block copolymers), SBS (styrene-butadiene-styrene block copolymers), SIS (styrene-isoprene-styrene), SBS* (styrene-butadiene-styrene star block copolymer), SBR (styrene-b-butadiene-rubber).

[0123] Advantageously, the polymer is chosen from block copolymers.

[0124] A preferred polymer is a copolymer based on butadiene units and styrene units, in particular such as a styrene / butadiene SB block copolymer or a styrene / butadiene / styrene SBS block copolymer, 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.

[0125] Advantageously, the polymer is a blend of a styrene / butadiene / styrene SBS block copolymer and a styrene / butadiene SB block copolymer in a SB / SBS mass ratio ranging from 0.1:99.9 to 30:70, advantageously from 1:99 to 20:80, even more advantageously from 5:95 to 15:85.

[0126] The styrene-conjugated diene block copolymer, in particular the styrene-butadiene copolymer, advantageously has a styrene content by weight ranging from 5 to 50%, preferably from 20 to 40%, even better from 25 to 35%.

[0127] The copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, advantageously has a weight content of styrene ranging from 20 to 40%, preferably from 25 to 35% by mass relative to the total mass of the copolymer.

[0128] According to one embodiment, the average molecular mass of the copolymer of styrene and conjugated diene, and in particular that of the copolymer of styrene and butadiene, may be, for example, between 10,000 and 700,000, preferably between 50,000 and 500,000 and more preferably from 200,000 to 400,000 daltons.

[0129] According to one variant, the average molecular mass of the copolymer of styrene and conjugated diene, and in particular that of the copolymer of styrene and butadiene, may be, for example, between 10,000 and 500,000, preferably between 20,000 and 100,000, more preferably from 30,000 to 75,000 daltons, advantageously between 50,000 and 60,000.

[0130] The polymer may have a linear, branched or radial structure. Preferably, the copolymer of styrene and conjugated diene, in particular the copolymer of styrene and butadiene, used in the clear binder composition according to the invention, has a radial structure.

[0131] In a preferred embodiment, the total amount of polymer used in the process for preparing the clear binder of the invention is between 0.5 and 20% by mass, preferably between 1 and 10%, preferably between 1.5 and 7.5%, for example between 2.5% and 5%, by mass relative to the total mass of the clear binder composition.

[0132] Stickiness drugs

[0133] To improve the mutual affinity between the binder and the aggregates and ensure their durability, adhesive dopes can also be used. These include, for example, nitrogenous surfactant compounds derived from fatty acids (amines, polyamines, alkylpolymannan, etc.).

[0134] When added to the clear binder, the tackifiers generally represent between 0.05% and 0.5% by weight relative to the total weight of the clear binder composition. For example, in a specific embodiment, between 0.05% and 0.5% of amine, preferably between 0.1% and 0.3% of amine, will be added by weight relative to the total weight of the clear binder composition.

[0135] Coloring agents

[0136] The clear binder may also include one or more coloring agents, such as mineral pigments or organic dyes. The pigments are selected according to the desired shade or color for the coating. For example, metal oxides such as iron oxides, chromium oxides, cobalt oxides, titanium oxides will be used to obtain the colors red, yellow, gray, blue-green or white. The pigments can be added, indifferently in the clear binder or in the asphalt (mixed with aggregates for example) or in an emulsion of the clear binder.

[0137] Optional additive(s)

[0138] According to one embodiment, the clear binder composition of the invention further comprises at least one Fischer-Tropsch wax.

[0139] The waxes (or paraffins) used are synthetic waxes derived from the Fischer-Tropsch synthesis process. These Fischer-Tropsch waxes are generally prepared by reacting carbon monoxide with hydrogen, typically at high pressures over a metal catalyst.

[0140] Preferred Fischer-Tropsch waxes are the Fischer-Tropsch waxes described in application WO9911737. The Fischer-Tropsch waxes described in this document are Fischer-Tropsch waxes comprising a mixture of paraffins. Fischer-Tropsch waxes comprise a majority of n-paraffins, often more than 90%, with the remainder being iso-paraffins.

[0141] The average length of the paraffinic chains of Fischer-Tropsch waxes is between 30 and 115 carbon atoms, preferably between 40 and 100, more preferably between 60 and 90.

[0142] Fischer-Tropsch waxes have a melting point (freezing point) between 65 and 105°C, preferably between 68 and 100°C. The Fischer-Tropsch waxes used in the invention may be partially oxidized or fully oxidized.

[0143] A preferred example of Fischer-Tropsch wax is that sold under the brand name Sasobit®, which has a freezing point of 100°C (ASTM D 938), a penetrability at 25°C of less than 1 1 / 10 mm (ASTM D 1321), and a penetrability at 65°C of 7 1 / 10 mm (ASTM 1321).

[0144] Another type of Fischer-Tropsch waxes that can be used are the Fischer-Tropsch waxes described in patent EP1951818. These Fischer-Tropsch waxes contain a slightly higher quantity of isomerized paraffins than conventional Fischer-Tropsch waxes. These Fischer-Tropsch waxes, which contain more iso-paraffins, are characterized by a freezing point (ISO 2207) between 85 and 120°C and a FEN value at 43°C, expressed in 0.1 mm, determined according to IP 376, greater than 5.

[0145] Preferably, when present, the amount of Fischer-Tropsch waxes is between 0.1% and 10% by mass, relative to the total mass of the clear binder composition, preferably between 0.5% and 5%, more preferably between 1% and 3%.

[0146] The composition of clear binder

[0147] Advantageously, a clear binder composition according to the invention comprises, by weight relative to the total weight of clear binder, or better still consists essentially of:

[0148] - from 1% to 40% by weight of plasticizing agent, in particular of the ester compound derived from tall oil, preferably from 5 to 30% by weight, more preferably between 10% and 20% by weight,

[0149] - from 50 to 90% by weight of structuring agent, in particular resin of plant origin, preferably from 60 to 85% by weight, more preferably from 70 to 85% by weight,

[0150] - from 0.5 to 20% by weight of polymer, in particular copolymer of styrene and butadiene, preferably from 1 to 10%, even better from 1 to 7.5%, advantageously from 1.5 to 5% by weight,

[0151] - 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,

[0152] - optionally from 0.1% to 10% by mass of Fischer-Tropsch wax(es), preferably from 0.5% to 5% by mass, more preferably from 1% to 3% by mass.

[0153] Preferably, the clear binder according to the invention has a penetrability at 25°C, measured according to standard NF EN 1426, of between 10 and 220 1 / 10 mm, preferably between 20 and 160 1 / 10 mm, more preferably between 30 and 100 1 / 10 mm. A person skilled in the art can modulate the penetrability of the clear binder, in particular by judiciously choosing the weight ratio [structuring agent / plasticizing agent] in the composition of the clear binder. Indeed, it is known that an increase in this ratio makes it possible to reduce the penetrability at 25°C.

[0154] Advantageously, the clear binder according to the invention has a ring and ball softening temperature (RBT), measured according to the NF EN 1427 method, ranging from 40 to 80°C, advantageously from 45 to 70°C.

[0155] The clear binder composition of the invention is advantageous in that it has a significantly higher bio-sourced carbon content compared to the clear binder compositions of petroleum origin of the prior art.

[0156] For the purposes of the invention, "bio-sourced carbon" means carbon supplied by materials derived from renewable organic matter (or biomass), of plant or animal origin, preferably plant-based. Bio-sourced carbon is thus distinguished from fossil carbon present in the Earth's crust, particularly in the form of coal, oil or natural gas.

[0157] According to a preferred embodiment, the clear binder composition according to the invention has a biosourced carbon content, measured according to standard ASTM D6668, greater than or equal to 75%, preferably greater than or equal to 80%, more preferably greater than or equal to 85%, advantageously greater than or equal to 90%.

[0158] The clear binder composition of the invention is also advantageous in that it exhibits improved biodegradability, particularly aerobic biodegradability, compared to prior art clear binder compositions of petroleum origin.

[0159] For the purposes of the invention, "biodegradability" means the capacity of a material to deteriorate once placed in a particular environment, in particular under the effect of microorganisms such as bacteria, fungi or algae. Biodegradability can be measured in an aerobic environment, i.e. in the presence of oxygen, or in an anaerobic environment, i.e. in the absence of oxygen.

[0160] According to a preferred embodiment, the clear binder composition according to the invention has an aerobic biodegradability, measured according to the ISO 17556 standard, at least 2 times higher than the biodegradability of a clear binder composition of petroleum origin of the prior art, preferably at least 3 times higher, more preferably at least 4 times higher, advantageously at least 5 times higher. Process for preparing the clear binder

[0161] The present invention also relates to a process for preparing the clear binder composition which has been described above. This process comprises the following steps:

[0162] (i) bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature of between 140-200°C, for example for 10 minutes to 1 hour,

[0163] (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,

[0164] (iii) adding the polymer, for example SB and / or SBS, mixing and heating at a temperature between 140-200°C, for example, from 90 minutes to 3 hours, preferably from 90 minutes to 2 hours 30,

[0165] (iv) optionally adding an adhesive dope, mixing and heating to a temperature between 140-200°C, for example, from 5 minutes to 30 minutes,

[0166] (v) optional addition of one or more Fischer-Tropsch wax(es), mixing and heating to a temperature between 140-200°C, for example, from 5 minutes to 30 minutes.

[0167] The order of steps (i) to (iv), including steps (i) to (v), may be changed.

[0168] Certain steps may also be carried out together or separately, in particular steps (iii) and / or (iv) and / or (v).

[0169] Preferably, step (iii) is carried out separately, before steps (iv) and (v), and steps (iv) and (v) may be carried out together or separately.

[0170] Applications of clear binder

[0171] The clear binder composition according to the invention can be used and applied indifferently via the so-called “hot”, “warm” or “cold” techniques well known to those skilled in the art.

[0172] Hot techniques are understood to mean techniques in which the clear binder composition is brought to relatively high temperatures during its application. Hot techniques lead to coatings, asphalts and so-called "hot" mixes such as bitumen gravels, high modulus mixes, bitumen sands, semi-granular bituminous concretes (BBSG), high modulus bituminous concretes (BBME), flexible bituminous concretes (BBS), thin bituminous concretes (BBM), permeable bituminous concretes (BBDr), very thin bituminous concretes (BBTM), ultra-thin bituminous concretes (BBUM). The clear binder composition according to the invention is suitable for the preparation of mixes, asphalts and coatings of all types, and in particular those mentioned above.

[0173] The invention therefore also relates to coatings comprising a clear binder composition according to the invention, aggregates, optionally fillers and optionally pigments.

[0174] 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.

[0175] The mix generally comprises from 1 to 10% by weight of clear binder, relative to the total weight of the mix, preferably from 4 to 8% by mass, the remainder being made up of aggregates, possibly fillers and possibly pigments. Usually, the pigments represent a quantity by mass of 0 to 1% of the mix, the fillers represent a quantity by weight of 0 to 2% of the mix.

[0176] Another subject of the invention is poured asphalts comprising a clear binder composition according to the invention, mineral fillers and optionally pigments. The asphalt comprises from 1 to 20% by weight of clear binder, relative to the total weight of the asphalt, preferably from 5 to 10% by weight, the remainder being made up of the fillers and optionally the pigments (the pigments representing a quantity by mass of 0 to 1% of the asphalt).

[0177] Cold techniques are understood to mean techniques based on the use of clear binder emulsions in aqueous phase, at lower temperatures. Cold techniques lead to surface coatings, grouts, cold-cast asphalt mixes, cold asphalt mixes, cold bituminous concretes, emulsion-gravel, storable cold asphalt mixes. The clear binder composition according to the invention is suitable for the preparation of the products mentioned above.

[0178] 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.

[0179] The invention therefore also relates to a process for preparing a clear binder emulsion comprising:

[0180] (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,

[0181] (iii) dispersing the clear binder from step (i) in the emulsifying solution from step (ii).

[0182] 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.

[0183] The various embodiments, variations, preferences and advantages described above for the plasticizing agent, the structuring agent and the other components of the clear binder composition apply to the use according to the invention.

[0184] Surprisingly, it has been observed that the combination of a plant-based oil comprising an ester compound derived from tall oil and a particular rosin resin in a clear binder composition allows, in comparison with other plant-based oils and resins, to obtain improved cold aging resistance properties. This improvement was observed using a standardized test called BBR for determining the flexural rigidity modulus (NF EN14771: 2012), this test being carried out before and after an aging protocol applied to the sample. This improved resistance to cold aging properties makes it possible to formulate surface coatings, particularly in the road sector, which deteriorate less under the effect of time and / or climatic conditions.

[0185] The invention is illustrated by the following examples given without limitation.

[0186] Examples

[0187] In the examples below, parts and percentages are by weight unless otherwise indicated.

[0188] Materials and methods:

[0189] Plasticizer: The oil available under the trade name SYLVAROAD® RP1000 from KRATON was used. This is a plant-based oil obtained from tall oil. Resin: The resin available under the trade name SYLVALITE® 2100 Rosin ester from KRATON was used. This is a plant-based resin comprising a mixture of pentaerythritol esters of tall oil rosin.

[0190] Styrene and butadiene copolymer: a mixture of thermoplastic SB and SBS block copolymers was used, having a content of constituent units derived from 70 / 30 Butadiene / Styrene monomers, of radial structure, obtained by solution polymerization, with a molecular mass of approximately 330,000 daltons polystyrene equivalent (PS), commercially available under the name Calprene 41 1 from the company Dynasol.

[0191] Preparation of a clear binder composition according to the invention (C1)

[0192] The clear binder is prepared according to the following process:

[0193] - The oil and resin are brought into contact and the mixture is heated to a temperature of 175°C;

[0194] - The oil and resin are mixed, heated for 1 to 2 hours, with a stirring speed of 200 rpm, while maintaining the mixture at a temperature of 175°C;

[0195] - The powdered styrene and butadiene copolymer is added and mixed for 2 hours at 175°C with a stirring speed of 250 rpm.

[0196] Methods for determining the properties of clear binder compositions

[0197] Table 1 Clear binder composition

[0198] The clear binder composition according to the invention C1 is 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

[0199] Results

[0200] It is found that the composition according to the invention C1 has good mechanical properties, suitable for use as a clear binder for both road applications and industrial applications.

[0201] It is also noted that the composition according to the invention C1 has good cold resistance to aging. In particular, it is observed that the value of the penetrability, the softening temperature (TBA), the elastic return and the flexural rigidity modulus of the composition, measured after accelerated aging of 25 hours (PAV), are very close to those of the initial composition C1 (before aging).

Claims

DEMANDS 1. Composition of clear binder comprising: (i) a plasticizing agent comprising at least one vegetable oil comprising an ester compound derived from tall oil, said vegetable oil having a solidification temperature, determined according to ASTM D1982, below 30°C and an acidity index, determined according to ASTM D465, less than or equal to 150 mg KOH / g, (ii) a structuring agent comprising at least one resin of vegetable origin selected from natural rosins, modified rosins, rosin esters, and any mixture thereof, said resin of vegetable origin having an acidity index, determined according to ASTM D465 method, of less than 8 mg KOH / g, (iii) at least one polymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs, and (iv) possibly an adhesiveness enhancer.

2. Composition according to claim 1, wherein the ester compound is selected from derivatives of a fatty acid of tall oil.

3. Composition according to claim 2, wherein the ester compound is selected from the group consisting of: trimethylolpropane tallates, ethylene glycol monomerate, neopentyl glycol monomerates, 2-ethylhexyl monomerates, glycerol monomerates, and any mixture thereof.

4. Composition according to any one of claims 1 to 3, wherein the plasticizing agent content ranges from 1% to 40% by mass, relative to the total mass of the composition, preferably from 5% to 30% by mass, more preferably from 10% to 20% by mass.

5. Composition according to any one of the preceding claims, wherein the resin of vegetable origin is selected from natural rosin esters, more preferably from pentaerythritol esters of natural rosins, in particular from pentaerythritol esters of tall oil rosins.

6. Composition according to any one of the preceding claims, wherein the content of structuring agent ranges from 50% to 95% by mass, relative to the total mass of the composition, preferably from 60% to 90% by mass, more preferably from 75% to 85% by mass.

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

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

9. Composition according to any one of the preceding claims, having a bio-based carbon content, measured according to ASTM D6668, of at least 75%, preferably at least 80%, more preferably at least 85%, advantageously at least 90%.

10. Composition according to any one of the preceding claims, having an aerobic biodegradability, measured according to ISO 17556, at least 2 times higher, than the aerobic biodegradability of a clear binder composition prepared from a petroleum-derived plasticizer and a petroleum-derived structuring agent, preferably at least 3 times higher, more preferably at least 4 times higher, advantageously at least 5 times higher.

11. A method 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 of the plasticizing agent and the structuring agent under agitation at a temperature between 140°C and 200°C, - the addition of the polymer, mixing and heating to a temperature ranging from 140°C to 200°C, - the addition of any adhesiveness boost and / or any Fischer-Trospch 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 11, (ii) aggregates and / or mineral fillers, and optionally (iii) one or more pigments.

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