Clear link and its applications

Abstract

Clear binder and its applications. 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 method ASTM D1982, of less than 30°C and an acidity index, determined according to method ASTM D465, of less than or equal to 150 mg KOH / g, (ii) a structuring agent comprising at least one vegetable resin selected from natural rosins, modified rosins, rosin esters, and any mixture thereof, said vegetable resin having an acidity index, determined according to method AQCM 001, of less than 8 mg KOH / g, (iii) at least one polymer based on conjugated diene motifs and aromatic monovinyl hydrocarbon motifs, and (iv) optionally an adhesion enhancer. Figure for the abridged version: None

Description

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

[0001] The present invention relates to a clear binder and its uses in road and / or industrial applications, in particular for the production of colored surface coating compositions. Prior art

[0002] Conventional bituminous binders, due to the presence of asphaltenes, are black and therefore difficult to color. Colored pavements are increasingly used because, among other things, they improve road user safety by clearly identifying specific lanes such as pedestrian walkways, cycle paths, and bus lanes. They also make it possible to mark certain danger zones such as town entrances or sharp curves. Colored pavements enhance 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 lots, and rest areas.

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

[0004] Clear binders of the prior art are generally made up of a plasticizing agent, for example a petroleum-derived oil, a structuring agent, for example a hydrocarbon resin, and a polymer.

[0005] Application WO2018 / 046838 discloses a cold-solid clear binder. In particular, it describes a clear binder containing a synthetic oil from deasphalting unit cuts (DAO) and a copolymer based on butadiene and styrene motifs, for example an SB or SBS copolymer.

[0006] Application WO2018 / 115729 discloses a cold-setting solid binder composition. In particular, the composition may be a clear binder and the plasticizing agent may be, in particular, a petroleum-derived oil. Application WO2018 / 115730 describes a similar composition for the preparation of mastic asphalt and the application of pavements.

[0007] US2002 / 052431 discloses aqueous emulsions comprising, on the one hand, a clear synthetic binder and, on the other hand, a latex. During manufacturing and subsequent use, these binders are subjected to various types of external factors that modify their structure and alter their properties.

[0008] Clear binders exhibiting a reduced environmental footprint compared to The clear binders discussed above have also been developed by seeking to substitute at least partially the plasticizing agent and / or the structuring agent with constituents of plant origin.

[0009] Application EP3081599 describes, for example, in this sense a binder of vegetable origin based on modified tall oil pitch, a modified resin and possibly a polymer.

[0010] These clear binders, however, are not entirely satisfactory. Although they do have a reduced environmental footprint compared to traditional clear binders, they present durability problems. Indeed, currently available clear binders incorporating a plasticizer and / or a structuring agent of plant origin exhibit significantly reduced resistance to aging compared to traditional clear binders prepared from petroleum-based products. In particular, these binders prepared from plant-based compounds exhibit significantly reduced resistance to aging of their cold-weather properties compared to traditional clear binders prepared from petroleum-based products.

[0011] More regular replacement of road surfaces is therefore to be expected, which significantly reduces their environmental value.

[0012] There therefore remains a need for bio-based clear binders (prepared from at least one plant-based plasticizing agent and / or at least one plant-based structuring agent) with improved mechanical properties, compared to existing bio-based clear binders.

[0013] In particular, there remains a need for bio-based clear binders (prepared from at least one plant-based plasticizing agent and / or at least one plant-based structuring agent) exhibiting resistance to aging, in particular improved resistance to aging of cold properties, compared to currently available bio-based clear binders.

[0014] In particular, there remains a need for bio-based clear binders (prepared from at least one plant-based plasticizing agent and / or at least one plant-based structuring agent) with properties equivalent to traditional clear binders prepared from petroleum-based oil and resin.

[0015] In particular, there remains a need for bio-based clear binders (prepared from at least one plant-based plasticizing agent and / or at least one plant-based structuring agent) exhibiting resistance to aging, in particular resistance to aging of cold properties, equivalent to traditional clear binders prepared from petroleum-based oil and resin.

[0016] Surprisingly, it was found that the association (i) of a vegetable oil comprising an ester derived from tall oil having a solidi (i) a calcification below 30°C and having an acidity index, determined according to ASTM D465, of 150 mg KOH / g or less, and (ii) a resin of vegetable origin selected from natural rosins, modified rosins, rosin esters, and mixtures thereof, and having an acidity index, determined according to ASTM D465, of less than 8 mg KOH / g, made it possible to obtain a bio-based clear binder with improved properties compared to prior art bio-based clear binders incorporating a vegetable oil and / or a vegetable resin. In particular, the clear binders of the invention exhibit better resistance to aging of their properties, especially better resistance to aging of cold-weather properties, compared to prior art bio-based clear binders.

[0017] More specifically, it was found that this particular association made it possible to obtain a clear binder with properties similar to those of traditional clear binders obtained from petroleum-based compounds, in particular a similar resistance to aging of cold properties. Summary of the invention

[0018] For the purposes of this invention, "clear bio-based binder" means a clear binder comprising at least one plant-based plasticizing agent and / or at least one plant-based structuring agent.

[0019] 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.

[0020] The invention relates firstly to a clear binder composition comprising:

[0021] (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, of less than 30°C and an acidity index, determined according to ASTM D465, of less than or equal to 150 mg KOH / g,

[0022] (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 acidity index, determined according to ASTM D465, of less than 8 mg KOH / g,

[0023] (iii) at least one polymer based on conjugated diene units and aromatic monovinyl hydrocarbon units, and

[0024] (iv) possibly an adhesiveness enhancer.

[0025] Preferably, the ester compound is chosen from the derivatives of a fatty acid of tall oil.

[0026] More preferably, the ester compound is chosen from the group consisting of: trimethylolpropane tallates, ethylene glycol monomers, neopentyl glycol monomers, 2-ethylhexyl monomers, glycerol monomers, and any of their mixtures.

[0027] Advantageously, 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.

[0028] Preferably, the resin of vegetable origin is chosen from natural rosin esters, more preferably from pentaerythritol esters of natural rosins, in particular from pentaerythritol esters of tall oil rosins.

[0029] 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.

[0030] Preferably, the polymer is a copolymer of styrene and butadiene, preferably selected from a radial structure styrene / butadiene / styrene block copolymer, a radial structure butadiene / styrene block copolymer and mixtures thereof.

[0031] The invention also relates to a method for preparing a clear binder composition as defined above and in detail below, comprising the steps:

[0032] - bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140°C and 200°C,

[0033] - mixing the plasticizing agent and the structuring agent under agitation at a temperature temperature between 140°C and 200°C,

[0034] - the addition of the polymer, mixing and heating to a temperature ranging from 140°C to 200°C,

[0035] - the addition of the optional adhesive doping agent, mixing and heating to a temperature temperature ranging from 140°C to 200°C.

[0036] The invention also relates to an emulsion comprising a clear binder composition as defined above and in detail below, water, and an emulsifying agent.

[0037] 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.

[0038] The expression "consists essentially of" followed by one or more characteristics means that components or steps which do not significantly modify the properties and characteristics of the invention may be included in the process or material of the invention, in addition to the components or steps explicitly listed.

[0039] The expression "between X and Y" includes the bounds, 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.

[0040] 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

[0041] The essential constituents of a clear binder composition are:

[0042] - a plasticizing agent, for example an oil free of asphaltenes,

[0043] - a structuring agent,

[0044] - at least one polymer,

[0045] - where appropriate, doping agents, or dopes, or adhesion dopes.

[0046] The clear binder of the invention is characterized by the combination of a specific vegetable oil and a specific vegetable resin. This selection of components makes it possible to obtain a clear binder with a reduced environmental footprint, compared to clear binders prepared from a petroleum oil and a petroleum resin, while exhibiting similar properties, particularly in terms of resistance to aging.

[0047] For the purposes of the invention, the terms "clear binder" and "clear binder base" are used interchangeably.

[0048] The invention relates to a clear binder comprising:

[0049] (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, of less than 30°C and an acidity index, determined according to ASTM D465, of less than or equal to 150 mg KOH / g,

[0050] (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 acidity index, determined according to ASTM D465, of less than 8 mg KOH / g

[0051] (iii) at least one polymer based on conjugated diene units and aromatic monovinyl hydrocarbon units, and

[0052] (iv) possibly an adhesiveness enhancer. The plasticizing agent

[0053] For the purposes of this invention, "plasticizing agent" means a chemical constituent that makes it possible to thin and reduce the viscosity and modulus of the binder in which it is incorporated.

[0054] According to the invention, the plasticizing agent comprises, preferably is made of, at least one vegetable oil whose characteristics are stated above.

[0055] The vegetable-based oil typically comprises at least one vegetable-based ester compound derived from tall oil.

[0056] For the purposes of this invention, "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 rosin, and tall oil pitch. Suitable tall oil derivatives for the purposes of this invention include acid-functionalized derivatives such as monomeric, dimeric, and trimer acids made from tall oil fatty acids, dimerized rosin acids, and refined fatty acids that can be obtained from tall oil.

[0057] The ester compound has a solidification temperature, determined according to the ASTM D1982 method, of less than 30°C.

[0058] Preferably, the ester compound is chosen from C4-C36 fatty acid esters, typically C8-C20.

[0059] As is known, an ester compound results from the reaction between a carboxylic acid and an alcohol with the elimination of water. In the following application, the ester compound of the invention is described as being formed from the carboxylic acid and the alcohol whose esterification reaction would lead to the production of said ester.

[0060] According to one embodiment, the carboxylic acid is in a polymerized form, in particular in the form of dimerized fatty acids.

[0061] Preferably, the fatty acid is chosen from the group consisting of: oleic acid, linoleic acid, linolenic acid, palmitic acid and any of their mixtures.

[0062] According to one variant, the fatty acid is chosen from monomeric acids (defined below), dimeric acids, tall oil heads, and the like, and mixtures thereof.

[0063] The alcohol can be primary, secondary, or tertiary. In particular, it can be a monol, a diol, or a polyol. The alcohol can also be derived from polyethers such as triethylene glycol or polyethylene glycols. Phenolic esters are also suitable.

[0064] 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 similar substances, and any mixture thereof.

[0065] More preferably, the alcohol is chosen from among alcohols comprising a quaternary carbon atom located in the beta position with respect to the oxygen of any of their hydroxyl groups. By way of example, trimethylpropane, neopentyl glycol, trimethyl olethane, pentaerythritol, dipentaerythritol, benzyl alcohols, and others may be cited.

[0066] As stated above, the ester compound is a derivative of tall oil.

[0067] Preferably, it is obtained from a tall oil fatty acid (also called TOFA for "Tall Oilfatty acid") or from a derivative of a tall oil fatty acid, for example, from a tall oil fatty acid dimer. The tall oil fatty acid is obtained from crude tall oil (or CTO for "Crude Tall OU") by distillation. Crude tall oil is a by-product of the wood pulping process, also known as the Kraft process. Distillation of crude tall oil yields, in addition to the 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 acids are the next cut, containing mainly C18 and C2O 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 (or DTO for "Distilled Tall OU"), is a mixture consisting primarily of tall oil fatty acids and a smaller proportion of tall oil rosin. Tall oil rosin (or TOR for "Tall OU Rosin"), isolated next, consists largely of a tricyclic C19-C2O monocarboxylic acid. The lowest cut from the distillation is known as tall oil pitch (or simply "pitch"). In general, any cut that contains at least one tall oil fatty acid is preferred for the preparation of an ester compound suitable for the invention.

[0068] As previously stated, polymerized fatty acids can be used to manufacture 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, unsaturated fatty acids undergo intermolecular addition reactions, for example, the "Alder-ene reaction," to form polymerized fatty acids. The mechanism is complex and not well understood. However, the product mainly comprises dimerized fatty acids and a unique mixture of monomeric fatty acids. Distillation yields a fraction highly enriched in dimerized fatty acids, commonly referred to as the "dimeric acid." These dimeric acids can be used for the manufacture of rejuvenating agents. ester function.

[0069] Distillation of polymerized tall oil fatty acid yields a fraction enriched in monomeric fatty acids, known as the "Monomer" (with a capital "M") or "Monomeric 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[8] carboxylic acids, primarily oleic and linoleic acids, the Monomer contains relatively small amounts of oleic and linoleic acids, and, conversely, significant amounts of branched and cyclic, saturated and unsaturated C[8] 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 accepted that the reaction of the Monomer with alcohols to produce "Monomer" esters will yield unique derivatives that differ from the corresponding tall oil-based fatty acid esters. CAS number 68955-98-6 has been assigned to the "Monomer." Examples of Monomer include 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.

[0070] The ester compounds of the invention include, for example, ethylene glycol tallate (i.e., ethylene glycol fatty acid ester of tall oil), 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 their derivatives. Particularly preferred ester compounds are tallates and monomerates, notably trimethylolpropane tallate, ethylene glycol monomerate, glycerol monomerate, and any mixture thereof.

[0071] Ester compounds are typically non-crystalline, that is to say they have a solidification temperature, determined according to the ASTM D1982 method, below 30°C, preferably below 20°C, more preferably below 10°C, and most preferably below 0°C.

[0072] 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 cooling gradually a pure and molten sample and observing the temperature at which the clear sample becomes just cloudy.

[0073] Preferably, the plasticizing agent has a Gardner color index, determined according to ASTM D6166, of less than or equal to 10, more preferably less than or equal to 8.

[0074] Preferably, the plasticizing agent has a flash point, determined according to 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.

[0075] Preferably, the plasticizing agent has an acidity index, determined according to the ASTM D465 method, of 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.

[0076] Advantageously, the plasticizing agent has an acidity index, determined according to ASTM D465 method, of 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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, and even more preferably between 20 cSt and 30 cSt, typically 23 cSt.

[0083] 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.

[0084] 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.

[0085] For example, an oil usable in clear binder compositions according to the invention may be a product marketed by the company KRATON under the name: SYLVAROAD® RP1000.

[0086] 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.

[0087] Advantageously, in the clear binder compositions of the invention, vegetable oils, as defined above, represent at least 90% by mass relative to the total mass of the plasticizing agent, preferably at least 95%, even more advantageously at least 98%, and advantageously still at least 99%. The structuring agent

[0088] By “structuring agent”, we mean any chemical constituent that confers mechanical properties and satisfactory cohesiveness to said binder.

[0089] The structuring agent used in the composition of the invention is a resin chosen from resins of vegetable origin.

[0090] Resins of plant origin can be said to be harvested, that is to say, harvested from the living plant. They can be used as is, in which case they are called natural resins, or they can be chemically transformed, in which case they are called modified natural resins.

[0091] Among the harvested resins are natural rosins, modified rosins, and rosin esters. These can be taken alone or in mixtures. Natural rosins include resin and wood rosins, particularly pine rosin, and / or tall oil. These natural rosins can be taken alone or in mixtures.

[0092] Among the modified rosins, examples include hydrogenated rosins, dismutated rosins, polymerized rosins, and / or maleated rosins. These modified natural rosins can be taken alone or in mixtures and may undergo one or more dismutation, polymerization, and / or maleization treatments.

[0093] Preferably, the resin is chosen from rosin esters, possibly modified.

[0094] More preferably, the resin is chosen from among the modified rosin esters.

[0095] Even more preferably, the resin is chosen from tall oil rosin esters, possibly modified.

[0096] Advantageously, the resin is chosen from among the esters of modified tall oil rosin.

[0097] Examples of rosin esters include methyl esters of natural rosins, methyl esters of hydrogenated rosins, esters of glycerol and natural rosins, esters of glycerol and hydrogenated rosins, esters of glycerol and dismutated rosins, esters of glycerol and polymerized rosins, esters of glycerol and maleated rosins, pentaerythritol esters of natural rosins, and pentaerythritol esters of hydrogenated rosins. These rosin esters may be taken alone or in mixtures and may be derived from rosins that have undergone one or more dismutation, polymerization, and / or maleization treatments.

[0098] Advantageously, the resin is selected from pentaerythritol esters of natural rosins, pentaerythritol esters of hydrogenated rosins and any of their mixtures, more advantageously from pentaerythritol esters of natural rosins.

[0099] According to a preferred embodiment, the resin is selected from pentaerythritol esters of tall oil rosins.

[0100] For more information on plant-based resins that can be used according to the invention, reference can be made to article K340 by Bernard Delmond published in "Techniques de l'ingénieur".

[0101] Preferably, the resin of vegetable origin has a softening temperature, determined according to the AQCM 003 method, between 60°C and 200°C, preferably between 80°C and 150°C, more preferably between 90°C and 110°C.

[0102] The resin of vegetable origin typically has an acidity index, determined according to the ASTM D465 method, of less than 8 mg KOH / g.

[0103] Preferably, the resin of vegetable 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.

[0104] Advantageously, the resin of vegetable origin has an acidity index, determined according to the ASTM D465 method, less than or equal to 5 mg KOH / g.

[0105] Preferably, the resin has a Gardner color index, determined according to ASTM D6166, of 10 or less, more preferably less than or equal to 5, or even more preferably less than or equal to 1, typically 0.9.

[0106] Preferably, the resin of plant origin has a glass transition temperature, measured according to the AQCM 218 method, between 10°C and 80°C, preferably between 20°C and 60°C, more preferably between 40°C and 50°C.

[0107] Preferably, the resin of vegetable 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.

[0108] Preferably, the resin of vegetable 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.

[0109] Preferably, the resin of vegetable 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.

[0110] For example, a resin usable in clear binder compositions according to the invention may be a product marketed by the company KRATON under the name: SYLVALITE® 2100 Rosin Ester.

[0111] 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.

[0112] 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. The polymer

[0113] The polymer used in the process for preparing the clear binder according to the invention is a copolymer based on conjugated diene units and aromatic monovinyl hydrocarbon units. The conjugated diene is preferably chosen from those having 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.

[0114] The aromatic monovinyl 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 analogues or mixtures thereof, in particular styrene.

[0115] Advantageously, the polymer is selected from conjugated styrene-diene copolymers. More particularly, the polymer consists of one or more copolymers selected from the following sequence copolymers: styrene-butadiene, styrene-isoprene, styrene-chloroprene, styrene-carboxylated butadiene, or styrene-carboxylated isoprene. Preferably, the polymer consists of one or more copolymers selected from styrene-butadiene copolymers.

[0116] For example, the polymer can be chosen from one or more of the following copolymers: SB copolymers (styrene-butadiene block copolymers), SBS (styrene-butadiene-styrene block copolymers), SIS (styrene-isoprene-styrene), SBS* (styrene-butadiene-styrene star block copolymer), SBR (styrene-butadiene-rubber).

[0117] Advantageously, the polymer is chosen from among block copolymers.

[0118] A preferred polymer is a copolymer based on butadiene motifs and styrene motifs, in particular such as a styrene / butadiene SB block copolymer or a styrene / butadiene / styrene SBS block copolymer, or a mixture of such copolymers.

[0119] More preferably, the polymer is a mixture of a styrene / butadiene / styrene SBS block copolymer and a styrene / butadiene SB block copolymer.

[0120] Advantageously, the polymer is a mixture of a styrene / butadiene / styrene block copolymer SBS and a styrene / butadiene block copolymer SB in a mass ratio SB / SBS 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.

[0121] The conjugated styrene-diene block copolymer, in particular the styrene-butadiene copolymer, advantageously has a styrene weight content of 5 to 50%, preferably 20 to 40%, even better 25 to 35%.

[0122] The conjugated styrene-diene copolymer, in particular the styrene-butadiene copolymer, advantageously has a styrene weight content of 20 to 40%, preferably 25 to 35% by mass relative to the total mass of the copolymer.

[0123] According to one embodiment, the average molecular mass of the conjugated styrene-diene copolymer, and in particular that of the styrene-butadiene copolymer, can 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.

[0124] According to one variant, the average molecular mass of the conjugated styrene-diene copolymer, and in particular that of the styrene-butadiene copolymer, can 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.

[0125] The polymer can have a linear, branched or radial structure. Preferably, the conjugated styrene-diene copolymer, in particular the styrene-butadiene copolymer, used in the clear binder composition according to the invention, has a radial structure.

[0126] In a preferred embodiment, the total quantity of polymer used in the clear binder preparation process 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. Coloring agents

[0127] The clear binder may also include one or more coloring agents, such as mineral pigments or organic colorants. 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, and titanium oxides may be used to obtain red, yellow, gray, green, blue, or white. The pigments may be added either to the clear binder, to the asphalt mix (mixed with the aggregates, for example), or to an emulsion of the clear binder. Process for preparing clear binder

[0128] The present invention also relates to a method for preparing the clear binder composition described above. This method comprises the following steps:

[0129] (i) bringing the plasticizing agent and the structuring agent into contact, and heating to a temperature between 140-200°C, for example from 10 minutes to 1 hour,

[0130] (ii) mixing the plasticizing agent and the structuring agent with stirring at a temperature between 140°C and 200°C, for example from 30 minutes to 2 hours,

[0131] (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,

[0132] (iv) possible addition of an adhesiveness doping, mixing and heating at a temperature between 140-200°C, for example, from 5 minutes to 30 minutes.

[0133] The order of steps (i) to (iv) can be changed.

[0134] Advantageously, a clear binder composition according to the invention comprises, by weight relative to the total weight of clear binder, or better, essentially consists of:

[0135] - from 1% to 40% by weight of plasticizing agent, in particular of the ester compound derived from tall oil, preferably at 5 to 30% by weight, more preferably between 10% and 20% by weight,

[0136] - 50 to 90% by weight of structuring agent, in particular of the original resin vegetable-based, preferably 60 to 85% by weight, more preferably 70 to 85% by weight,

[0137] - from 0.5 to 20% by weight of polymer, in particular styrene copolymer and butadiene, preferably from 1 to 10%, even better from 1 to 7.5%, advantageously from 1.5 to 5% by weight,

[0138] - possibly from 0.05% to 0.5% by weight of doping, preferably between 0.1% and 0.3% by weight of doping, for example a doping chosen from among the amines.

[0139] 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, and more preferably between 30 and 100 1 / 10 mm. Those skilled in the art can adjust the penetrability of the clear binder, in particular by judiciously choosing the weight ratio of [structuring agent / plasticizing agent] in the composition of the clear binder. Indeed, it is known that increasing this ratio reduces the penetrability at 25°C.

[0140] Advantageously, the clear binder according to the invention has a ball and ring softening temperature (BRT), measured according to the NF EN 1427 method, ranging from 40 to 80°C, advantageously from 45 to 70°C. Applications of the clear binder

[0141] The clear binder composition according to the invention can be used and applied interchangeably via the so-called "hot", "warm" or "cold" techniques well known to those skilled in the art.

[0142] Hot mixing techniques are understood to be techniques in which the clear binder composition is heated to relatively high temperatures during its application. Hot mixing techniques result in coatings, asphalts, and so-called "hot mix" asphalts such as asphalt-aggregate mixes, high-modulus asphalt mixes, asphalt sands, semi-coarse bituminous concrete (BBSG), high-modulus bituminous concrete (BBME), flexible bituminous concrete (BBS), thin bituminous concrete (BBM), draining bituminous concrete (BBDr), very thin bituminous concrete (BBTM), and ultra-thin bituminous concrete (BBUM). The clear binder composition according to the invention is suitable for the preparation of all types of asphalts, coatings, and asphalts, and in particular those mentioned above.

[0143] The invention therefore also relates to coatings comprising a clear binder composition according to the invention, aggregates, possibly fillers and possibly pigments.

[0144] The fillers (or fines) are particles with dimensions less than 0.063 mm. The aggregates comprise particles with dimensions 0 / 2 (sand), 2 / 4 (gravel), 4 / 6 and 6 / 10.

[0145] The asphalt mix generally comprises 1 to 10% by weight of clear binder, relative to the total weight of the asphalt mix, preferably 4 to 8% by mass, the remainder consisting of aggregates, possibly fillers, and possibly pigments. Typically, pigments represent 0 to 1% by mass of the asphalt mix, and fillers represent 0 to 2% by weight of the asphalt mix.

[0146] The invention also relates to cast 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 the fillers and optionally the pigments (the pigments representing a quantity by mass of 0 to 1% of the asphalt).

[0147] Cold techniques are defined as techniques based on the use of clear binder emulsions in aqueous phase at lower temperatures. Cold techniques result in surface coatings, grouts, cold-applied asphalt mixes, cold-mix asphalt, cold-mix asphalt, emulsion-treated aggregates, and cold-mix asphalt that can be stored. The clear binder composition according to the invention is suitable for preparing the products mentioned above.

[0148] 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.

[0149] The invention therefore also relates to a method for preparing a clear binder emulsion comprising:

[0150] (i) the preparation of a clear binder composition by mixing at least one agent plasticizer, at least one structuring agent and at least one polymer, as defined above,

[0151] (ii) the preparation of an emulsifying solution by mixing water and the emulsifying agent,

[0152] (iii) the dispersion of the clear binder from step (i) in the emulsifying solution from step (ii).

[0153] The clear binder emulsion according to the invention preferably comprises 50% to 80% by weight of the clear binder composition, preferably 60% to 70%, relative to the total weight of the clear binder emulsion.

[0154] The various embodiments, variants, preferences and advantages described above for the plasticizing agent, the structuring agent and the other components of the clear binder composition apply to use according to the invention.

[0155] Surprisingly, it has been observed that the combination of a vegetable oil comprising an ester compound derived from tall oil and a resin of A specific type of rosin in a clear binder composition allows, compared to other vegetable oils and resins, for improved resistance to aging and cold weather conditions. This improvement was observed using a standardized test known as BBR (flexural modulus test, NF EN14771:2012), which is performed before and after an aging protocol applied to the sample. This enhanced resistance to aging and cold weather conditions makes it possible to formulate surface coatings, particularly for road construction, that degrade less over time and / or under climatic conditions.

[0156] The invention is illustrated by the following examples, which are given by way of non-limiting example. Examples

[0157] In the examples below, parts and percentages are expressed by weight unless otherwise indicated. Materials and methods:

[0158] Plasticizer: the oil available under the trade name SYLVAROAD® RP1000 from the company KRATON was used. This is a vegetable oil obtained from tall oil.

[0159] Resin: The resin available under the trade name SYLVALITE® 2100 Rosin ester from the company KRATON was used. It is a resin of vegetable origin comprising a mixture of pentaerythritol esters of rosin and tall oil.

[0160] Styrene and butadiene copolymer: a mixture of thermoplastic block copolymers SB and SBS was used, having a constituent unit content of 70 / 30 Butadiene / Styrene monomers, of radial structure, obtained by solution polymerization, of molecular mass of about 330,000 daltons equivalent polystyrene (PS), commercially available under the name Calprene 411 from the company Dynasol.

[0161] Preparation of a clear binder composition according to the invention (Cl)

[0162] The clear binder is prepared according to the following process:

[0163] - The oil and resin are brought into contact and the assembly is heated to a temperature of 175°C;

[0164] - The oil and resin, heated for 1 to 2 hours, are mixed with a stirring speed at 200 rpm, while maintaining the mixture at a temperature of 175°C;

[0165] - The styrene-butadiene copolymer, in powder form, is added, and mix for 2 hours at 175°C with a stirring speed of 250 rpm.

[0166] Methods for determining the properties of clear binder compositions

[0167] [Tables 1] Property Abbreviation Unit Measurement Standard Needle penetration at 25°C P25 1 / 10 mm NF EN 1426 Ball and ring softening temperature TBA °C NF EN 1427 Viscosity at 160°C V160 mPa.S NF EN 13302 BBR test (determination of flexural modulus) Ts and Tm °C NF EN 14771 Measurement of springback - % NF EN 13398 Aging Acceleration Protocol (PAV) - - NF EN 14769 Clear binder compositions

[0168] The clear binder composition according to the invention Cl is prepared according to the protocol described in the preceding paragraph with the constituents and proportions (as a percentage by weight relative to the total weight of clear binder) reported in Table 2.

[0169] [Tables2] Composition Cl Plasticizing agent 16.1 Structuring agent 78.9 SB / SBS copolymer 5 Characterization at t=0 Penetration at 25 °C (dmm) 69 TBA (°C) 55.7 Elastic recovery (%) 89 Viscosity at 160°C (mPa.s) 569 BBR T°@S=300MPa (°C) -14.6 T @m=0.3 (°C) -17.7 Properties after PAV 25h Penetration at 25 °C (dmm) 65 TBA (°C) 52.4 Elastic recovery (%) 82 BBR T°@S=300MPa (°C) -13.4 T @m=0.3 (°C) -16.6

[0170] The composition is formulated at a grade of 50 / 70. Results

[0171] It is observed that the composition according to the invention Cl exhibits good mechanical properties, suitable for use as a clear binder for both road and industrial applications.

[0172] It is also observed that the composition according to the invention Cl exhibits good cold resistance to aging. In particular, it is observed that the values ​​of the penetrability, the softening temperature (BWT), the elastic recovery and the flexural stiffness modulus of the composition, measured after accelerated aging of 25h (PAV), are very close to those of the initial composition Cl (before aging).

Claims

Demands

1. A clear binder composition 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, of less than 30°C and an acidity value, determined according to ASTM D465, of 150 mg KOH / g or less, (ii) a structuring agent comprising at least one vegetable resin selected from natural rosins, modified rosins, rosin esters, and any mixture thereof, said vegetable resin having an acidity value, determined according to ASTM D465, of less than 8 mg KOH / g and a softening temperature, determined according to AQCM 003, of between 90°C and 110°C, (iii) at least one diene-based polymer conjugated and aromatic monovinyl hydrocarbon motifs,and (iv) possibly an adhesiveness enhancer.

2. Composition according to claim 1, wherein the ester compound is selected from the 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: trimethyl-lolpropane tallates, ethylene glycol monomers, neopentyl glycol monomers, 2-ethylhexyl monomers, glycerol monomers, 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. A composition according to any one of the preceding claims, wherein the content of the structuring agent ranges from 50% to 95% by mass, relative to the total mass of the composition, preferably from 60% to 90% in niasse, more preferentially 75% to 85% in mass.

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

8. 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 the plasticizing agent and the structuring agent under agitation at a temperature between 140°C and 200°C, - adding the polymer, mixing and heating to a temperature from 140°C to 200°C, - adding the optional adhesion enhancer, mixing and heating to a temperature from 140°C to 200°C.

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

10. Coating comprising (i) a clear binder composition according to any one of claims 1 to 8 or an emulsion according to claim 9, (ii) aggregates and / or mineral fillers, and optionally (iii) one or more pigments.