Rheological additives based on hydroxylated di- or tri-amides and mixtures thereof

Description

[0001] The present invention relates to a specific multifunctional amide (di- and triamide) suitable for use as an organogelator, in particular as a rheology additive and more particularly in coating compositions.

[0002] EP 1 514 912 describes branched triamides of non-hydroxylated fatty acids, based on polyether amines and used as a phase change vector agent in phase change inks (so-called "hot melt inks") with the function of changing the ink from the solid state at room temperature to the liquid state at high temperature in inkjet printers and allowing the liquid ink droplets to solidify quickly after their jet at this temperature. EP 1 514 912 does not suggest the use of these polyamides as organogelling agents or thixotropic agents and does not suggest hydroxylated polyamides based on a mixture of hydroxylated fatty acids and shorter chain hydroxylated monocarboxylic acids.

[0003] Fatty diamides based on aliphatic diamines (without polyether segments) based on hydroxylated fatty acids are known as organogelling agents and in particular as thixotropic agents.

[0004] WO 2014 / 053774 describes hydroxylated fatty acid diamides as organogelling agent or also called rheology additive, in particular in coating, molding, mastics or sealing agent or cosmetic compositions.

[0005] WO 2015 / 011375 describes fatty acid diamines comprising in its structure both cycloaliphatic and aliphatic diamines with a specific molar ratio and the use of these products as organogelling agent or as rheology additive, in particular in coating, molding, mastics or sealing agent or cosmetic compositions.

[0006] FR 2 993 885 describes a fatty acid diamide comprising in its structure specific hydroxylated carboxylic acids and the use of this product as an organogelator in coating, molding, mastic or sealing agent compositions.

[0007] These known diamides need to be micronized to powder form and then require prior "activation" to achieve the required rheological performance. The activation process requires high-speed shear and heating, sometimes up to 100°C depending on the product. In addition, a minimum duration is required, depending on the temperature conditions and the polarity of the system. Furthermore, these additives may be poorly compatible with some binders in reactive formulations or with some diluents or plasticizers used for activation. Therefore, this activation phase is a particular disadvantage for polyamide powders and hydrogenated castor oil derivatives, used as additives in this field.

[0008] There is therefore a need for new fatty polyamides allowing simpler and easier shaping (shaping in the form of flakes easily soluble in plasticizers or binders of reactive formulations of final application, without the need for prior preactivation) with a broader spectrum of compatibility with reactive binders and plasticizers / diluents used in reactive formulations such as: silane-terminated polyether, silane-terminated polyurethane, isocyanate-terminated polyurethane, silicone, polysulfide, epoxy, etc. The polyamides (meaning multi-functional and non-polymeric amides) required as rheology additives must lead to final products in particular coatings, sealant joints or sealant joints which have an improved surface appearance and aesthetics which are transparent without surface defects, this being linked to the specific structure and composition of these targeted polyamides.

[0009] The present invention with the new fatty polyamides (multifunctional fatty amides, in particular di- and triamides) based on primary polyamines (di- and triamines) comprising at least one polyether segment in its structure and in particular based on polyoxypropylene and based on fatty acids comprising at least one hydroxylated fatty acid in the presence of a shorter chain hydroxylated acid, makes it possible to meet the new needs defined above.

[0010] The first subject of the present invention therefore relates to a multi-functional fatty amide which is a fatty diamide or triamide or their mixture, based on a polyamine polyether (diamine or triamine) and at least one linear saturated fatty acid carrying a non-terminal hydroxy group in the presence of another shorter C 2 -C 10 monocarboxylic acid carrying a hydroxy group.

[0011] The second subject of the invention relates to a composition for formulating an organic binder, which composition comprises at least one organic binder and at least one fatty amide as defined according to the present invention, in particular as a rheological additive.

[0012] The present invention also covers the use of at least one fatty amide as defined according to the present invention, as a rheology additive.

[0013] Finally, the invention also covers the final product obtained which results from the use of at least one fatty amide as defined according to the present invention, as a rheology additive, in particular as a thixotropic agent.

[0014] Thus, the first object of the present invention is a multi-functional fatty amide, which is a diamide or a triamide or their mixture and said fatty amide is represented by: A) according to the following formula (I): R[(-X-R1-NHCO-R2) n(1-y ] [(-X-R1-NHCO-R2') ny ] (I) with n being 2 or 3, preferably 3 R(-X-R1-) n being the residue of valence n of a primary polyamine R(-X-R1-NH 2 ) n which is a primary diamine or triamine, with each primary amine group -NH 2 being a terminal group carried by a bivalent segment of oligomeric chain R1 chosen from polyether and polyester which is alkoxylated (alkoxylated polyester), preferably polyether and more preferably polyoxypropylene or oxypropylene / oxyethylene copolymers with a majority of oxypropylene units R: C 3 -C 10 alkylene residue of valence n derived from a polyol R(OH) n or from a polyamine R(NH 2 ) n or R(NH-R3) n , preferably of a polyol R(OH) n X: O, NH or NR3, preferably O R2 being the fatty residue, without carboxy group, in C 12 -C 52 , preferably in C 16 -C 36 , more preferably in C 16 -C 24 of hydroxylated fatty acid R2CO 2 H,in particular saturated and linear R2' being the monocarboxylic acid residue R2'CO 2 H, in C 2 to C 10 , preferably from C 2 to C 8 , more preferably in C 2 to C 6 , and carrying at least one hydroxy group and preferably at least two hydroxy groups with y representing the molar fraction of R2'CO 2 H relative to the sum R2CO 2 H + R2'CO 2 H (R2' / (R2+R2')) in said diamide, with y varying from 0.05 to 0.50, preferably from 0.10 to 0.40, with R2CO 2 H and / or R2'CO 2 H possibly being mixtures of respective acids,R3 being a C 1 -C 2 alkyl substituent or (said fatty amide is represented) by: B) according to the following formula (II) in the case where said amide is a diamide: (R2CONH) (1-y) -R'-O-[CH 2 -CH(R4)-O] x -CH 2 -CH(R4)-(NHCOR'2) y (II) with R' being the residue of monopropylene glycol without OH: -CH(CH 3 )-CH 2 - and x being the number of oxyalkylene units -CH 2 -CH(R4)-O- and being able to vary from 5 to 45 preferably from 5 to 40 and more preferably from 5 to 35. R2 and R'2 and "y" being defined as in formula (I) above and R4 being H or methyl with the repeating oxyalkylene unit -CH 2 -CH(R4)-O- being ethoxy for R4 being H and propoxy for R4 being methyl or R4 corresponds to an ethoxy / propoxy mixture and preferably R4 is methyl with said oxyalkylene unit being propoxy and said amide having a melting point meaning melting temperature, measured by DSC after two passes, 10°C / min ranging from 10 to 110°C, preferably from 20 to 100°C. ,

[0015] The term "melting point" refers to the melting temperature measured by differential scanning calorimetry (DSC) at a heating rate of 10°C / min. This temperature is the temperature that corresponds to the melting peak recorded by DSC at the specified heating rate.

[0016] Regarding the residue R, said C 3 -C 10 alkylene in addition to the carbon-carbon bonds may comprise an ether bridge -O- in the case of a polyol residue or an -NH- bridge in the case of a polyamine residue.

[0017] In the case where X:N, as appears evident from the formulas specified above of polyamines with R residue, this means that N represents -NH- and -N(R3)-.

[0018] Regarding the meaning of R2CO2H, these are linear hydroxylated fatty acids with non-terminal hydroxy. These linear fatty acids have a linear fatty chain of C12-C52, preferably C16-C36, more preferably C16-C24, in particular consisting exclusively of CC bonds and therefore without ester groups in this linear chain. This definition therefore excludes from the definition of R2CO2H any polyester or oligoester resulting from the self-polycondensation of a hydroxylated fatty acid.

[0019] In the case of monocarboxylic acids R2'CO 2 H, the term "C 2 -C 10 , preferably C 2 -C 8 , more preferably C 2 -C 6 " means that it is the length of the R2' chain expressed in number of chained carbon atoms (-CC-), without taking into account the side substituents.

[0020] According to a specific option the acid R2CO 2 H is a mixture of hydroxylated fatty acids and / or the acid R2'CO 2 H is a mixture of shorter chain hydroxylated monocarboxylic acids (than the hydroxylated fatty acids) as defined according to the invention. Suitable examples of primary polyamines having the formula R(-X-R1-NH 2 ) n which are primary diamines or triamines as defined above include the following: as diamine (n = 2) or triamine (n = 3): a primary diamine with the two primary amine functions carried by a polyether segment or an alkoxylated polyester segment (polyester-polyether) or a triamine with 3 primary amine functions carried by 3 alkoxylated polyether or polyester segments (polyester-polyether), said alkoxylated polyether or polyester segment for a diamine or all 3 alkoxylated polyether or polyester segments in the case of a triamine, having a number-average molecular mass Mn ranging from 500 to 3000.In particular, these are primary polyether diamines and triamines and more particularly primary polyoxypropylene diamines and triamines such as Jeffamine ®< diamines and triamines marketed by Hunstmann with, as more particular suitable examples, Jeffamine ®< D-2000 (primary diamine with a polyoxypropylene segment carrying 2 primary amine groups with a number of oxypropylene units of 33) or Jeffamine ®< T-3000 (primary triamine with 3 polyoxypropylene segments and a total number of oxypropylene units of 50). Other amines can also be used: Jeffamine ®< D-400, Jeffamine ®< D-2010, Jeffamine ®< T-403, Jeffamine ®< T-5000, etc.

[0021] In principle, said polyether diamines or polyether triamines suitable for the preparation of the diamides and triamides according to the present invention can be obtained from corresponding polyether polyol precursors (respective diols or triols) by reductive amination of the terminal OH functions in the presence of a catalyst as described in US 4766245 or GB 2175910.

[0022] Concerning the polyether polyols (diols or triols) respective precursors of polyether diamines or triamines, they can be obtained by anionic polymerization in basic medium of the corresponding alkylene oxide (ethylene oxide for polyoxyethylene diol / triol, propylene oxide for polyoxypropylene diol / triol) or of a mixture of said alkylene oxides in the presence of a polyol alcoholate initiator with primary OH which is respectively diol or triol (with primary OH) or a polyamine initiator respectively diamine and triamine (depending on the functionality of said polyether: diol or triol). As an example of a diol initiator, mention may be made of ethylene glycol, diethylene glycol, propylene 1,3-glycol, butylene 1,4-glycol. As an example of a triol initiator, mention may be made of trimethylol propane.

[0023] In the case of bivalent initiators (two primary alcoholate functions or two amine functions), they lead to a symmetrical structure with the initiator incorporated in the middle of the chain (via ether bond -O- or -NH-) and with the departure of a polyether chain for each alcoholate or amine function of the initiator used.

[0024] In the case of a trivalent initiator (primary alcoholate triol or triamine), each alcoholate or amine is the starting point of a polyether chain resulting in 3 polyether chains carried by a molecule of said initiator whose residue corresponds to R in the formula defined above for the amide according to the invention.

[0025] In the particular case of polyether diamines, the polyether diol precursors can also be obtained by anionic polymerization of alkylene oxide or a corresponding mixture of alkylene oxides (e.g. ethylene oxide or propylene oxide or a mixture of ethylene oxide and propylene oxide for polyoxyethylene diols, polyoxypropylene diols and (oxyethylene-oxypropylene) diol copolymers respectively) from a monovalent primary alcoholate initiator carrying on a secondary carbon of said initiator an OH (secondary OH not reacting to open the alkylene oxide). In such a case, a single polyether chain is formed from the primary alcoholate with the other (secondary) OH end of the initiator remaining free and unchanged and thus with the polyether formed being a diol (precursor of the polyether diamine by conversion of the terminal OHs into NH2 as mentioned above).An example of a monovalent initiator diol (only 1 primary OH) is monopropylene glycol in the primary alcoholate form as below: HO-CH(CH 3 )-CH 2 O -< .

[0026] In the more specific case of polyoxypropylene-based polyether diamines, monopropylene glycol acts as a monovalent initiator with unaffected secondary hydroxyl during the polymerization of propylene oxide (initiation by ring opening by attack of the anionic alcoholate initiator on the least electron-rich carbon atom (-CH 2 -) of propylene oxide and then chain propagation, leading to the polyoxypropylene diol of the following formula which carries two secondary OH: HO-CH(CH 3 )-CH 2 -O-(CH 2 -CH(CH 3 )-O) x -CH 2 -CH(CH 3 )-OH

[0027] After conversion of the terminal secondary hydroxyls (by pressure-catalyzed reductive amination NH 3 as described in US 4766245 or GB2175910), the polyoxypropylene diamine of the following formula can be obtained: H 2 N-CH(CH 3 )-CH 2 O-(CH 2 -CH(CH 3 )-O) x -CH 2 -CH(CH 3 )-NH 2

[0028] An example of such a polyoxypropylene diamine is Jeffamine ®< D2000 marketed by Huntsman.

[0029] As linear saturated hydroxylated fatty acids R2CO2H (with R2 carrying a non-terminal OH) as defined according to the invention, a hydroxy fatty acid may be used from 12-hydroxy stearic acid (12-HSA), 9-hydroxy stearic acid (9-HSA), 10-hydroxystearic acid (10-HSA), 14-hydroxy eicosanoic acid (14-HEA) or mixtures thereof.

[0030] As shorter acids R2'CO2H in C 2 -C 10 , one can use 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, hydroxyacetic acid (or glycolic acid), 2-hydroxy propionic acid (lactic acid), 2-hydroxy-3-(3-pyridyl) propionic acid, 3-hydroxy butyric acid, 2-hydroxy butyric acid, 2-methyl-2-hydroxy butyric acid, 2-ethyl-2-hydroxy butyric acid, hydroxy pentanoic acid, hydroxy hexanoic acid, hydroxy heptanoic acid, hydroxy octanoic acid, hydroxy nonanoic acid, hydroxy decanoic acid and mixtures thereof;preferably 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl)butyric acid, hydroxyacetic acid (or glycolic acid), 2-hydroxypropionic acid (lactic acid), 2-hydroxy-3-(3-pyridyl)propionic acid, 3-hydroxybutyric acid, 2-hydroxybutyric acid, 2-methyl-2-hydroxybutyric acid, 2-ethyl-2-hydroxybutyric acid, hydroxypentanoic acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid and mixtures thereof; more preferably 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, hydroxyacetic acid (or glycolic acid), 2-hydroxy propionic acid (lactic acid), 2-hydroxy-3-(3-pyridyl) propionic acid, 3-hydroxy butyric acid, 2-hydroxy butyric acid, 2-methyl-2-hydroxy butyric acid, 2-ethyl-2-hydroxy butyric acid, hydroxy pentanoic acid, hydroxy hexanoic acid and mixtures thereof.;

[0031] The fatty amide according to the invention represented by A according to formula (I) preferably has a number-average molecular mass Mn measured by GPC in THF in polystyrene equivalents (calibration by polystyrene standards) which varies for: n = 2 (a diamide) from 800 to 4000, preferably from 1000 to 3800 n = 3 (a triamide) from 1000 to 6000, preferably from 2000 to 5500.

[0032] The fatty amide according to the invention represented by B according to formula (II) which is a fatty diamide preferably has the same number-average molecular mass range Mn measured by GPC in THF in polystyrene equivalents (calibration by polystyrene standards) as the diamide (n = 2) represented by option A) according to formula (I), i.e.: from 800 to 4000, preferably from 1000 to 3800.

[0033] According to a preferred option for the fatty amide represented by option A) according to formula (I), said oligomeric chain segment R1 is a polyether chain segment.

[0034] According to a more particularly preferred option, said oligomeric chain segment R1 is a polyoxypropylene chain segment.

[0035] Said oligomeric chain segment R1 may have a number average molecular weight Mn ranging from 400 to 2000, preferably from 500 to 1500.

[0036] According to a specific option of the invention, said fatty amide is a fatty diamide represented by option B) according to formula (II) as defined above.

[0037] According to a preferred option, said hydroxylated fatty acid R2CO 2 H is selected from 12-hydroxy stearic acid (12-HSA); 9- or 10-hydroxy stearic acid (9-HSA or 10-HSA), preferably a mixture of 9- and 10-hydroxy stearic acid; 14-hydroxy eicosanoic acid (14-HEA) and mixtures thereof in pairs. The most preferred hydroxylated acid R2CO 2 H is 12-hydroxystearic acid.

[0038] More preferably, said monocarboxylic acid R2'CO 2 H is selected from: 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, hydroxyacetic acid (or glycolic acid), 2-hydroxy propionic acid (lactic acid), 2-hydroxy-3-(3-pyridyl) propionic acid, 3-hydroxy butyric acid, 2-hydroxy butyric acid, 2-methyl-2-hydroxy butyric acid, 2-ethyl-2-hydroxy butyric acid.

[0039] According to another particular option of the invention, said amide is a diamide according to A) or B) or a triamide according to A), with the ratio “y / (1-y)” varying from 1 / 20 to 1 / 2 and preferably from 1 / 10 to 4 / 10.

[0040] According to another alternative option, said amide is a diamide according to A) or B) with the ratio y / (1-y) varying from 1 / 10 to 1 / 2 and preferably from 1 / 10 to 4 / 10.

[0041] According to a particular option, said amide is a triamide according to A) with two residues (R2) derived from hydroxylated fatty acid R2CO 2 H and one (R2') derived from acid R2'CO 2 H.

[0042] More particularly and alternatively, said amide is a diamide represented according to option A) and represented by formula (I) or according to option B) and represented by formula (II) as defined above.

[0043] The second subject of the invention relates to a composition for formulating an organic binder characterized in that it comprises: a) at least one organic binder and b) at least one fatty amide as defined above according to the invention, in particular as a rheological additive.

[0044] More particularly, in said binder formulation composition, said binder a) is selected from: polysiloxane resins terminated by blocked silane groups, polyether resins terminated by blocked silane groups, polysulfide resins terminated by blocked silane groups, polyurethane prepolymer resins terminated by isocyanate groups, PVC resins for plastisols, epoxy resins carrying epoxy groups.

[0045] Said composition may comprise, in addition to a) and b) and depending on said binder, a plasticizer or a reactive diluent as defined below: c) a plasticizer for polysiloxane resins, polyurethane prepolymers and PVC resins for plastisols or d) a reactive diluent among epoxidized monomers for epoxy resins and optionally e) for two-component systems a hardener for epoxy or polyurethane resins.

[0046] More particularly in said composition according to the invention, said fatty amide is used as a rheological additive which is a thixotropic agent.

[0047] In said composition, said organic binder a) may be selected from a polysiloxane resin, a polyurethane prepolymer resin or a PVC resin for plastisol and said plasticizer may be selected from: phthalates, adipates, trimellitates, sebacates, benzoates, citrates, phosphates, epoxides, polyesters, alkyl-sulfonate esters and non-phthalate phthalate substitutes.

[0048] Said composition may be a transparent or non-transparent sealant formulation composition. In particular, it may be a transparent sealant formulation composition.

[0049] Another subject of the invention covers the use of at least one fatty amide as defined above according to the invention where said amide is used as a rheology additive.

[0050] In said use, said rheology additive can be used as a thixotropic agent.

[0051] More particularly, said use may be in coating, adhesive, PVC plastisol or sealant compositions, preferably PVC plastisol compositions and sealant compositions.

[0052] Another particular use is in PVC plastisol compositions.

[0053] Another particular use is in moisture-curable sealant compositions based on polysiloxane resins terminated with blocked silane groups, polyether resins terminated with blocked silane groups, polysulfide resins terminated with blocked silane groups, in particular silanes blocked by alkoxy groups or polyurethane prepolymer resins terminated with isocyanate groups.

[0054] Another particular use is in compositions of moisture-curable sealants, transparent or not.

[0055] Finally, the invention covers a final product which may be a coating, in particular a PVC plastisol coating, or an adhesive seal or a mastic seal, which results from the use of at least one fatty amide as defined above according to the invention, as a rheology additive and in particular as a thixotropic agent.

[0056] The following examples in the experimental part below are presented for the purpose of illustrating the invention and its performance and in no way limit its scope. EXPERIMENTAL PART 1) Raw materials used and codes See Table 1 below

[0057] Summary table of raw materials used in synthesis and formulations [Table 1] Product used Chemical name Function Supplier 12HSA 12-Hydroxy Stearic Acid Hydroxy fatty acid Jayant Agro Stearine Stearic acid Non-hydroxylated fatty acid, according to R2CO2H Sogis bMBA 2,2-bis(hydroxymethyl) butyric acid Short hydroxy acid according to R2'CO 2 H Sigma Aldrich JEFFAMINE ®< T-3000 Polyetheramine Jeffamine ® Polyetheramine < T-3000 Polyoxypropylene triamine (primary) with overall ∼50 oxypropylene units (OP) Huntsmann JEFFAMINE ®< D-2000 Polyetheramine Jeffamine ® Polyetheramine < D-2000 Polyoxypropylene diamine (primary) with -33 OP units Huntsmann HCO (in scales) Hydrogenated Castor Oil Reference rheology additive Gokul Agro Crayvallac ®< Antisettle CVP (micronized powder) Hydrogenated Castor Oil Reference rheology additive Arkema Standard fatty diamide 12HSA-HMDA-12HSA Reference diamide rheology additive for comparison / MS Polymer ®< S203H Silylated polyether Application formulation resin Kaneka Jayflex ®< IUD Diisoundecylphthalate Plasticizer for formulation BASF

[0058] For the sake of clarity, we will use the following abbreviations: 12HSA: 12-Hydroxystearic acid SA: Stearic acid HMDA: Hexamethylenediamine D2000: Polyetheramine Jeffamine ®< D-2000 T3000: Polyetheramine Jeffamine ®< T-3000 bMBA: 2,2-bis(hydroxymethyl)butyric acid 2) Examples Example A according to the invention - T3000-(12HSA-bMBA) 3

[0059] In a 1 liter flask equipped with a thermometer, a Dean Stark, a condenser and a stirrer, 231.40 g of Jeffamine ®< T-3000 (0.078 mol, 1 eq), 63.11 g of 12-hydroxystearic acid (0.199 mol, 2.55 eq) and 5.2 g of 2,2-bis(hydroxymethyl) butyric acid (0.035 mol, 0.45 eq) are added. The mixture is heated to 180°C under an inert atmosphere. The eliminated water accumulates in the Dean Stark from 150°C. The reaction is controlled by the acid and amine numbers. When the acid and amine numbers are respectively less than 6, the reaction is stopped. The reaction mixture is cooled to 140°C and discharged into a silicone mold. Once cooled to room temperature, the product is transformed into flakes. Example B according to the invention - D2000-(12HSA-bMBA) 2

[0060] In a 1 liter flask equipped with a thermometer, a Dean Stark, a condenser and a stirrer, 232.3 g of Jeffamine ®< D-2000 (0.115 mol, 1 eq), 62.12 g of 12-hydroxystearic acid (0.196 mol, 1.7 eq) and 5.11 g of 2,2-bis(hydroxymethyl) butyric acid (0.034 mol, 0.3 eq) are added. The mixture is heated to 180°C under an inert atmosphere. The removed water accumulates in the Dean Stark from 150°C. The reaction is controlled by the acid and amine numbers. When the acid and amine numbers are respectively less than 6, the reaction is stopped. The reaction mixture is cooled to 140°C and discharged into a silicone mold. Once cooled to room temperature, the product is transformed into flakes. Comparative Example C - T3000-(SA) 3

[0061] In a 1 liter flask equipped with a thermometer, a Dean Stark, a condenser and a stirrer, 313.6 g of Jeffamine ®< T-3000 (0.10 mol, 1 eq) and 86.4 g of stearic acid (0.3 mol, 3 eq) are added. The mixture is heated to 180°C under an inert atmosphere. The eliminated water accumulates in the Dean Stark from 150°C. The reaction is controlled by the acid and amine numbers. When the acid and amine numbers are respectively less than 6, the reaction is stopped. The reaction mixture is cooled to 140°C and is discharged into a silicone mold. Comparative Example D - D2000-(SA) 2

[0062] In a 1 liter flask equipped with a thermometer, a Dean Stark, a condenser and a stirrer, 312.2 g of Jeffamine ®< D-2000 (0.15 moles, 1 eq) and 87.8 g of stearic acid (0.3 moles, 2 eq) are added. The mixture is heated to 180°C under an inert atmosphere. The eliminated water accumulates in the Dean Stark from 150°C. The reaction is controlled by the acid and amine numbers. When the acid and amine numbers are respectively less than 6, the reaction is stopped. The reaction mixture is cooled to 140°C and is discharged into a silicone mold. 3) Study of the gelling power of organogelators

[0063] In this study we compare the ability of the tested rheology additives to form a gel in a simplified formulation containing only a classic plasticizer (Jayflex ®< DIUP) used in PVC plastisol formulations.

[0064] The formulations are prepared using a so-called laboratory planetary mixer (Molteni ®< EMD 1 type) equipped with a dispersion disc and a scraper for mixing high-viscosity products, but also powders in non-fluid systems. It is equipped with a vacuum pump to prevent moisture from entering during dispersion. The temperature inside the Molteni ®< EMD 1 is measured by a probe attached to the scraper and can be regulated using a bath.

[0065] The simplified formulations tested / compared are presented in Table 2 below with the identical plasticizer being Jayflex ®< DIUP and the variable rheology additive tested and compared being the amides cited or other reference products cited. Composition of simplified formulations

[0066] [Table 2] Formulation Component % weight F1 Jayflex ® Plasticizer< DIUP 95 Amide Example A 5 F2 Jayflex ® Plasticizer< DIUP 95 Amide Example B 5 F3 Jayflex ® Plasticizer< DIUP 95 Amide Example C 5 F4 Jayflex ® Plasticizer< DIUP 95 Amide Example D 5 F5 Jayflex ® Plasticizer< DIUP 95 12HSA-HMDA-12HSA 5 F6 Jayflex ® Plasticizer< DIUP 95 HCO 5 F7 Jayflex ® Plasticizer< DIUP 95 Crayvallac ®< Antisettle CVP 5

[0067] The rheology additive is introduced into the plasticizer and the mixture is brought to the incorporation temperature (see Table 3) and dispersed for 5 minutes. At the end of the dispersion, the mixture is cooled to room temperature and the behavior of the gel is studied visually (see Table 3 below). Behavior and appearance of the gel as a function of the incorporation temperature

[0068] [Table 3] Formulation Temperature Gel behavior Appearance F1 60°C** Strong gel Transparent 80°C** Strong gel Transparent F2 60°C** Strong gel Transparent 80°C** Strong gel Transparent F3 60°C** Liquid Transparent 80°C** Liquid Transparent F4 60°C** Liquid Transparent 80°C** Liquid Transparent F5 60°C* Low frost Opaque 80°C* Low frost Opaque 100°C** Low frost Opaque F6 60°C* Light frost (presence of grains) Opaque 80°C** Low frost Opaque F7 60°C* Strong gel Opaque 80°C** Weak gel (slight syneresis) Opaque *partial solubilization; **total solubilization

[0069] The results of the gel tests show that the products according to the invention (amides according to examples A and B) form gels, while the comparative products are in liquid form. Thus, the compound of the example C described in particular in EP 1 514 912 A2 does not allow the gel to be obtained (see Formulation F3), which strongly shows that the presence of the hydroxy group, providing H bonds, is essential for the formation of the supramolecular assembly and the three-dimensional (3D) network of fibers formed.

[0070] The behavior of organogelating agents can also be influenced by the initial structure of the amine used. Thus, by comparing the organogelator described in WO 2014 / 053774A1 ( 12HSA-HMDA-12HSA ) with the compound of the Example B according to the invention, a significant difference in gel strength can be noted. In particular, if the aliphatic amine is replaced by a polyether amine, the gelling power increases, allowing, in addition, the production of a transparent gel. Note that to be fully solubilized, the compound 12HSA-HMDA-12HSA(see Formulation F5) requires higher temperatures than the products according to the invention.

[0071] Furthermore, the performance of the gels can be related to the physical nature of the rheology additive. Therefore, for formulations F6 and F7, a difference in gel strength is observed initially at a constant incorporation temperature (60°C) of the rheology additive. Namely, if the additive is in the form of flakes (see Formulation F5), the gel strength will decrease, which could probably be explained by an incomplete incorporation of the product in the formulation due to the lack of solubility. Furthermore, grains could be observed, which could corroborate this hypothesis.

[0072] Also, it can be observed that in the case where the additive is in powder form and incorporated at a higher temperature (80°C in F7) than its optimal incorporation temperature (60°C in F7), the gel strength will decrease. This also shows a sensitivity to temperature, probably due to over-solubilization of the product. It is therefore important for standard products to respect an incorporation temperature window so that the organogelator is effective.

[0073] As regards formulations F1 and F2 containing the products according to the invention, the formation of a strong gel can be observed, regardless of the incorporation temperature. It should be mentioned that at the temperatures studied, the rheology additive is completely solubilized. In addition, the formulations have a completely transparent appearance. 4) Evaluation of rheological performance in a simplified hybrid sealant formulation

[0074] In this study, the rheological performances of the additives of a simplified formulation of hybrid sealant comprising as plasticizer: Jayflex ®< DIUP and as rheology additive the cited compared product are compared. Composition of simplified hybrid sealant formulations

[0075] [Table 4] Formulation Component % by weight Function F8 Jayflex ® Plasticizer< DIUP 47,5 Plasticizer MS-Polymer ®< S 203 H 47,5 Resin Amide according to example A 5 Rheology additive F9 Jayflex ® Plasticizer< DIUP 47,5 Plasticizer MS-Polymer ®< S 203 H 47,5 Resin Crayvallac Antisettle CVP 5 Rheology additive F10 Jayflex ® Plasticizer< DIUP 47,5 Plasticizer MS-Polymer ®< S 203 H 47,5 Resin Amide according to example B 5 Rheology additive F11 Jayflex ® Plasticizer< DIUP 47,5 Plasticizer MS-Polymer ®< S 203 H 47,5 Resin 12HSA-HMDA-12HSA 5 Rheology additive

[0076] The formulations are prepared using the Molteni ®< EMD 1 mixer. In the first step and in the proportions indicated (Table 4), the resin and plasticizer are added and homogenized. The additive is weighed and then added in the second step. Thus, the reaction mixture, which is kept under vacuum during the mixing phases, is brought to 80°C for 5 minutes. At the end of this phase, the mixture is cooled to 25°C and discharged. The performance of these formulations is presented in Table 5 below. Rheological performance

[0077] [Table 5] Formulation Viscosity at 0.1 s-1 (Pa.s) Viscosity at 100 s-1 (Pa.s) Thixotropic index Flow threshold (Pa) Appearance F8 717 3,50 205 73 Transparent F9 296 6,06 49 4,4 Opaque F10 313 2,78 113 30 Transparent F11 47 2,21 21 3,1 Opaque

[0078] The triamide rheology additive of the example Aaccording to the invention is much more effective in terms of rheological performance (see Formulation F8), compared to the standard powder additive Crayvallac ®< Antisettle CVP (see Formulation F9). As for the diamide product of the example C, it also presents superior rheological performances (see Formulation F10) to that using the compound in powder form 12HSA-HMDA-12HSA (see Formulation F11).

[0079] Furthermore, the products according to the invention do not require a specific implementation process to develop the rheology (gel), as is necessary in the case of conventional additives in the form of powders based on hydrogenated castor oil derivatives.

[0080] Furthermore, since the products according to the invention are in the form of flakes, the problems encountered with the use of powders (micronization, handling, toxicity, etc.) are avoided. It should also be noted that these products make it possible to obtain completely transparent MS putty formulations.

Claims

1. Polyfunctional fatty amide, characterized in that it is a diamide or a triamide or a mixture thereof and that said fatty amide is represented by: A) according to the following formula (I):         R[(-X-R1-NHCO-R2)n(1-y)] [(-X-R1-NHCO-R2')ny]     (I) with - n being 2 or 3, preferably 3, - R(-X-R1-)n being the residue of valency n of a primary polyamine R(-X-R1-NH2)n which is a primary diamine or triamine, - with each primary amine group -NH2 being a terminal group borne by a bivalent oligomer chain segment R1 chosen from alkoxylated polyester and polyether, preferably polyether and more preferentially polyoxypropylene or oxypropylene / oxyethylene copolymers having a predominance of oxypropylene units, - R: C3-C10 alkylene residue of valency n resulting from a polyol R(OH)n or from a polyamine R(NH2)n or R(NH-R3)n, preferably from a polyol R(OH)n, - X: O, NH or NR3, preferably O, - R2 being the C12-C52, preferably C16-C36, more preferentially C16-C24, fatty residue of hydroxylated fatty acid R2CO2H, in particular saturated and linear, - R2' being the C2 to C10, preferably C2 to C8, monocarboxylic acid R2'CO2H residue bearing at least one hydroxyl group, preferably at least two hydroxyl groups, - y representing the mean molar fraction of R2'CO2H relative to the sum of R2'CO2H + R2CO2H, in said diamide, with y varying from 0.05 to 0.50, preferably from 0.10 to 0.40, with it being possible for R2CO2H and / or R2'CO2H to be mixtures of respective acids, - R3 being a C1-C2 alkyl substituent, or by B) according to the following formula (II) in the case in which said amide is a diamide:         (R2CONH)(1-y)-R'-O-[CH2-CH(R4)-O]x-CH2-CH(R4)-(NHCOR2')y     (II) with R' being the residue of monopropylene glycol without OH: -CH(CH3)-CH2- and R2 and R2' and y being defined as in formula (I) above, and x being the number of oxyalkylene units -CH2-CH(R4)-O- and it being possible for x to vary from 5 to 45, preferably from 5 to 40 and more preferentially from 5 to 35, R4 being H or methyl with the repeating oxyalkylene unit -CH2-CH(R4)-O- being ethoxy when R4 is H and propoxy when R4 is methyl or R4 corresponds to an ethoxy / propoxy mixture and preferably R4 is methyl with said oxyalkylene unit being propoxy, and said amide having a melting point, meaning melting temperature, measured by DSC after two passes at 10°C / min, ranging from 10 to 110°C, preferably from 20 to 100°C.

2. Fatty amide according to Claim 1, characterized in that the number-average molecular weight Mn of said fatty amide defined according to A) formula (I), measured by GPC in THF as polystyrene equivalents varies for: - n = 2 from 800 to 4000, preferably from 1000 to 3800, - n = 3 from 1000 to 6000, preferably from 2000 to 5500.

3. Fatty amide according to Claim 1 or 2, characterized in that said oligomer chain segment R1 for the fatty amide according to A) formula (I) is a polyether chain segment, in particular a polyoxypropylene chain segment.

4. Fatty amide according to one of Claims 1 to 3, characterized in that said oligomer chain segment R1 has a number-average molecular weight Mn ranging from 400 to 2000, preferably from 500 to 1500.

5. Fatty amide according to one of Claims 1 to 4, characterized in that said hydroxylated fatty acid R2CO2H is selected from 12-hydroxystearic acid (12-HSA); 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), preferably a mixture of 9- and 10-hydroxystearic acids; 14-hydroxyeicosanoic acid (14-HEA); and mixtures thereof; in particular 12-hydroxystearic acid.

6. Fatty amide according to one of Claims 1 to 5, characterized in that said amide is a diamide according to A) or B) or a triamide according to A) with y / (1-y) varying from 1 / 20 to 1 / 2 and preferably from 1 / 10 to 4 / 10.

7. Fatty amide according to one of Claims 1 to 6, characterized in that said amide is a triamide according to A) with two R2 residues resulting from hydroxylated fatty acid R2CO2H and 1 resulting from acid R2'CO2H.

8. Formulation composition of an organic binder, characterized in that it comprises: a) at least one organic binder, b) at least one fatty amide as defined in one of Claims 1 to 7, in particular as rheological additive.

9. Composition according to Claim 8, characterized in that said binder a) is selected from: polysiloxane resins terminated by blocked silane groups, polyether resins terminated by blocked silane groups, polysulfide resins terminated by blocked silane groups, polyurethane prepolymer resins terminated by isocyanate groups, PVC resins for plastisols, epoxy resins bearing epoxy groups.

10. Composition according to Claim 8 or 9, characterized in that it comprises, in addition to a) and b) and depending on said binder, a plasticizer or a reactive diluent as defined below: c) a plasticizer for polysiloxane resins, polyurethane prepolymer resins and PVC resins for plastisols or d) a reactive diluent from epoxidized monomers for epoxy resins and optionally e) for two-component systems, a hardener for the epoxy or polyurethane resins.

11. Composition according to Claim 10, characterized in that said organic binder a) is a polysiloxane resin, a polyurethane prepolymer resin or a PVC resin for plastisols and in that said plasticizer is selected from: phthalates, adipates, trimellitates, sebacates, benzoates, citrates, phosphates, epoxides, polyesters, alkylsulfonate esters and non-phthalate substitutes for phthalates.

12. Use of at least one fatty amide as defined in one of Claims 1 to 7, characterized in that said amide is used as rheology additive, in particular as thixotropic agent.

13. Use according to Claim 12, characterized in that it concerns use in coating, adhesive, PVC plastisol or mastic compositions, preferably PVC plastisol compositions and mastic compositions.

14. Use according to Claim 13, characterized in that it concerns use in mastic compositions which can be crosslinked by moisture based on polysiloxane resins terminated by blocked silane groups, polyether resins terminated by blocked silane groups, polysulfide resins terminated by blocked silane groups, in particular silanes blocked by alkoxy groups, or polyurethane prepolymer resins terminated by isocyanate groups.

15. Coating, in particular PVC plastisol coating, adhesive seal or mastic seal, characterized in that it results from the use of at least one fatty amide as defined in one of Claims 1 to 7, as rheology additive, in particular as thixotropic agent.