Rheological additives based on di- or triamides and their mixtures

Abstract

To provide a novel fatty polyamide that improves the surface and aesthetic appearance of a final product through coatings, mastic seals, or sealing agent seals which are transparent without surface defect.SOLUTION: The invention relates to a fatty amide which is a di- or tri-amide based on a polyether diamine or a triamine which can be used as an organogelling agent, and in particular as a rheology additive. The invention also relates to a formulation composition using the fatty amide as a rheology additive and the use the fatty amide for the purpose in coating, adhesive, or PVC plastisol compositions, in particular transparent or non-transparent mastic compositions. The rheology additive has the advantage of not requiring a specific activation process before use, unlike other known fatty amide additives based on hydrogenated castor oil derivatives.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to certain multifunctional amides (di- and triamides) suitable for use as organogelators, particularly as rheological additives, and more particularly in coating compositions. [Background technology]

[0002] EP 1 514 912 describes branched triamides of non-hydroxylated fatty acids based on polyetheramines, which are used as phase change vector agents in phase change inks (known as "hot melt inks"), with the function of passing the ink from a solid state at ambient temperature to a liquid state at elevated temperatures in an inkjet printer, allowing the liquid ink droplets to solidify rapidly after being ejected at this temperature. EP 1 514 912 does not suggest the use of these polyamides as organogelators or thixotropic agents, at least not polyamides with non-terminal hydroxyl groups due to the fatty acids used.

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

[0004] WO 2014 / 053774 describes hydroxylated fatty acid diamides, which are also known as organogelling agents or rheological additives, especially in coating, moulding, mastics, leakproofing or cosmetic compositions.

[0005] WO2015 / 011375 describes fatty acid diamines containing in their structure both cycloaliphatic and aliphatic diamines in specific molar ratios and the use of these products as organogelling agents or rheological additives, especially in coating, molding, mastic, leakproofing or cosmetic compositions.

[0006] FR2993885 describes fatty acid diamides containing specific hydroxylated carboxylic acids in their structure and the use of these products as organogelling agents in coating, molding, mastic and leakproofing compositions.

[0007] This type of diamide must be pulverized into a powder form and then "activated" beforehand to achieve the required rheological performance qualities. The activation process requires high shear and, depending on the product, heating, sometimes up to 100°C. Furthermore, a minimum time is required, depending on the temperature conditions and the polarity of the system. Furthermore, these additives may be poorly compatible with some binders for reactive formulations or with some diluents or plasticizers used for activation. As a result, this activation step is particularly disadvantageous for polyamide powders and hydrogenated castor oil derivatives used as additives in this field. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] European Patent No. 1514912 [Patent Document 2] International Publication No. 2014 / 053774 [Patent Document 3] International Publication No. 2015 / 011375 [Patent Document 4] French Patent Application Publication No. 2993885 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, there is a need for new fatty polyamides that have a wider range of compatibility with reactive binders and plasticizers / diluents used in reactive formulations such as silane-terminated polyethers, silane-terminated polyurethanes, isocyanate-terminated polyurethanes, silicones, polysulfides, epoxies, etc., that allow for simpler and easier molding and use (molded into flake form that is easily dissolved in the plasticizer or binder of the end-use reactive formulation without the need for prior preactivation), and that ultimately improve the surface and aesthetic appearance of the final product, especially by providing a clear coating, mastic seal, or sealant seal that is free of surface defects, which is related to the specific structure and specific composition of these targeted polyamides. [Means for solving the problem]

[0010] The present invention makes it possible to meet these new requirements by means of novel fatty polyamides (polyfunctional fatty acid amides, in particular di- and triamides) based on primary polyamines (di- and triamines) containing at least one polyether segment in their structure, in particular based on polyoxypropylene, and based on fatty acids, including at least one hydroxylated fatty acid.

[0011] A first subject of the present invention relates to polyfunctional fatty acid amides, which are fatty diamides or triamides or mixtures thereof, based on polyether polyamines (diamines or triamines) and at least one saturated linear fatty acid, at least one of which may optionally be a shorter C2-C 10 In the presence of acid, it has non-terminal hydroxyl groups.

[0012] A second subject of the present invention relates to a formulation composition of organic binders, in particular as rheological additives, comprising at least one organic binder and at least one fatty acid amide as defined according to the invention.

[0013] The present invention also encompasses the use of at least one fatty acid amide as defined in accordance with the invention as a rheological additive.

[0014] Finally, the present invention also encompasses the end products resulting from the use of at least one fatty acid amide as defined according to the invention as a rheological additive, in particular as a thixotropic agent.

[0015] A first subject of the present invention is therefore a polyfunctional fatty acid amide which is a diamide or triamide or a mixture thereof, said fatty acid amide comprising: A) The following formula (I): R[(-X-R1-NHCO-R2)n-n1][(-X-R1-NHCO-R2′)n1](I) (In the formula, - n is 2 or 3, preferably 3; -n1 is equal to 0 or 1, R-(X-R1-)n is the residue of a primary polyamine R(-X-R1-NH2)n of valence n, which is a primary diamine or triamine, and each primary amine group -NH2 is an end group of a divalent oligomeric chain segment R1 selected from polyethers and alkoxylated polyesters, preferably polyethers, more preferably polyoxypropylene or oxypropylene / oxyethylene copolymers with a predominance of oxypropylene units, -R is a C3-C alkyl group of valence 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. 10 is an alkylene residue, -X is O or N, preferably O; -R2 is a saturated linear alkyl group, especially C 12 -C 52 , preferably C 16 -C 36 , more preferably C 16 -C 24 is the fatty residue of a fatty acid R2CO2H, -R2' is C2-C 10, preferably a C3-C8 monocarboxylic acid residue, and at least one R2 residue, preferably at least two, more preferably all R2 residues, are residues of hydroxylated fatty acids R2CO2H having a non-terminal hydroxyl group, said R2 residues being the same or different; -R3 is a C1-C2 alkyl substituent; or B) When the amide is a diamide, it has the following formula (II): R2CONH-R′-O-[CH2-CH(R4)-O] x -CH2-CH(R4)-NHCOR'2(II) (In the formula, R' is a monopropylene glycol residue containing no OH: -CH(CH3)-CH2-; R2 and R'2 are defined above in formula (I), R4 is H or methyl, the repeating oxyalkylene unit -CH2-CH(R4)-O- is ethoxy when R4 is H and propoxy when R4 is methyl, or R4 corresponds to an ethoxy / propoxy mixture, preferably R4 is methyl where the oxyalkylene unit is propoxy, and the melting point, meaning the melting temperature of the amide, is in the range of 10-110°C, preferably 25-100°C, measured by DSC after two passes at 10°C / min, The polyfunctional fatty acid amide is represented by the formula:

[0016] The term "melting point" corresponds to the melting temperature measured by DSC at a heating rate of 10°C / min. This temperature corresponds to the melting peak recorded by DSC at the specified heating rate.

[0017] Regarding residue R, the above C3-C 10 In addition to carbon-carbon bonds, the alkylene may contain ether bridges -O- in the case of polyol residues or -NH- bridges in the case of polyamine residues.

[0018] When X=N, this means that N represents -NH- and -N(R3)-, as is evident from the above formula of the polyamine containing the R residues.

[0019] Regarding the meaning of R2CO2H, this refers to straight-chain hydroxylated fatty acids with non-terminal hydroxyl groups. These straight-chain fatty acids are straight-chain C 12 -C 52 , preferably C 16 -C 36 , more preferentially C 16 -C 24 It contains a fatty chain, in particular consisting of only C-C bonds, and therefore does not contain ester groups within this linear chain. This definition therefore excludes from the definition of R2CO2H polyesters or oligoesters derived from the self-polycondensation of hydroxylated fatty acids.

[0020] Suitable examples of primary polyamines corresponding to the formula R(—X—R 1 —NH 2 ) n , which are primary diamines or triamines as defined above, include:

[0021] For example, the amine (n=2) or triamine (n=3) may be a primary diamine having two primary amine functional groups carried by a polyether segment or an alkoxylated polyester (polyester-polyether) segment, or a triamine having three primary amine functional groups carried by three polyether or alkoxylated polyester (polyester-polyether) segments, wherein the polyether or alkoxylated polyether segments of the diamine, or in the case of a triamine, combination of three polyether or alkoxylated polyester segments have a number average molecular weight Mn in the range of 500 to 3,000. In particular, these are primary diamine and triamine polyethers, more particularly primary diamine and triamine polyoxypropylenes such as the Jeffamine® diamines and triamines sold by Huntsman, more particularly suitable examples being Jeffamine® D-2000 (a primary diamine having a polyoxypropylene segment with two primary amine groups and a total of 33 oxypropylene units) or Jeffamine® T-3000 (a primary triamine having three polyoxypropylene segments with a total of 50 oxypropylene units).Other amines can also be used, such as Jeffamine® D-400, Jeffamine® D-2010, Jeffamine® T-403, Jeffamine® T-5000, etc.

[0022] In principle, the above-mentioned polyetherdiamines or polyethertriamines suitable for preparing the diamides and triamides according to the invention can be obtained from the corresponding polyetherpolyol (diol or triol, respectively) precursors by reductive amination of the terminal OH functions in the presence of a catalyst, as described in US Pat. No. 4,766,245 or GB 2,175,910.

[0023] The polyether polyol (diol or triol) precursors of polyether diamines or triamines are obtained by anionic polymerization of the corresponding alkylene oxide (ethylene oxide in the case of polyoxyethylene diols / triols, propylene oxide in the case of polyoxypropylene diols / triols) or a mixture of the alkylene oxides in a basic medium in the presence of a polyol alkoxide initiator (diol or triol, respectively, having a primary OH group) or a polyamine initiator (diamine or triamine, respectively, depending on the functionality of the polyether:diol or triol). Examples of diol initiators include ethylene glycol, diethylene glycol, 1,3-propylene glycol, and 1,4-butylene glycol. Examples of triol initiators include trimethylolpropane.

[0024] In the case of a divalent initiator (two primary alkoxide functionalities or two amine functionalities), a symmetrical structure is obtained with the initiator incorporated in the middle of the chain (via an ether linkage -O- or -NH-), with a starting point for the polyether chain for each alkoxide or amine functional group of the initiator used.

[0025] In the case of trivalent initiators (primary alkoxide triols or triamines), each alkoxide or amine is the starting point of a polyether chain, so that the initiator molecule has three polyether chains, the residues of which correspond to R in the formula defined above for the amides according to the invention.

[0026] In the specific case of polyetherdiamines, polyetherdiol precursors can also be obtained by anionic polymerization of alkylene oxides or mixtures of corresponding alkylene oxides (e.g., ethylene oxide or propylene oxide or mixtures of ethylene oxide and propylene oxide in the case of polyoxyethylene diols, polyoxypropylene diols, and (oxyethylene-oxypropylene) diol copolymers, respectively) derived from monovalent primary alkoxide initiators bearing an OH on the secondary carbon of the initiator (the secondary OH does not react to open the alkylene oxide). In such cases, a single polyether chain is formed from the primary alkoxide, and the other (secondary) OH moiety of the initiator is free and unchanged, so the polyether formed is a diol (a polyetherdiamine precursor by conversion of the terminal OH to NH2 as described above). Examples of monovalent diol initiators (one single primary OH) are: HO-CH(CH3)-CHO - and monopropylene glycol in the form of a primary alkoxide such as:

[0027] In the more specific case of polyoxypropylene-based polyether diamines, monopropylene glycol acts as a monovalent initiator, and during the polymerization of propylene oxide (ring-opening initiation of propylene oxide by attack of the anionic alkoxide initiator on the electron-poorest carbon atom (-CH-) followed by chain growth), the secondary hydroxyl is left unaffected, resulting in the formation of a propylene oxide having two secondary OH groups, as follows: HO-CH(CH3)-CH2-O-(CH2-CH(CH3)-O) x -CH2-CH(CH3)-OH of polyoxypropylene diol is produced.

[0028] After conversion of the terminal secondary hydroxyl (by catalytic reductive amination under NH3 pressure as described in US4766245 or GB2175910), the compound of the formula: H2N-CH(CH3)-CH2O-(CH2-CH(CH3)-O) x -CH2-CH(CH3)-NH2 The resulting polyoxypropylenediamine is

[0029] An example of such a polyoxypropylene diamine is Jeffamine® D2000 sold by Huntsman.

[0030] As the hydroxylated saturated straight-chain fatty acid R2CO2H (wherein R2 has a non-terminal OH) defined according to the present invention, a hydroxy fatty acid selected from 12-hydroxystearic acid (12-HSA), 9-hydroxystearic acid (9-HSA), 10-hydroxystearic acid (10-HSA) or 14-hydroxyeicosanoic acid (14-HEA) can be used.

[0031] Shorter C2-C 10 As the acid R2'CO2H, acetic acid, propanoic acid, butyric acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid, octanoic acid, nonanoic acid or decanoic acid can be used. Preferably, any of these acids is a C2-C8 acid.

[0032] The fatty acid amide according to the present invention has a number average molecular weight Mn of the fatty acid amide represented by A) according to formula (I), measured by GPC in THF as a polystyrene equivalent (calibrated by polystyrene standards): - When n=2 (diamide), 800 to 4000, preferably 1000 to 3800, - When n=3 (triamide), 1000 to 6000, preferably 2000 to 5500 It is preferable that the temperature varies with the temperature.

[0033] The diamide represented by B) according to formula (II) preferably has a number average molecular weight Mn in the range of 800 to 4000, preferably 1000 to 3800, as measured by GPC in THF as a polystyrene equivalent (calibrated with a polystyrene standard), which is the same as the number average molecular weight Mn range of the diamide represented by A).

[0034] According to a particular choice of said fatty acid amide, it is a diamide represented by B) according to formula (II).

[0035] According to a preferred option, said oligomeric chain segment R1 (according to formula (I) of option A)) is a polyether chain segment.

[0036] According to a more particularly preferred option, the oligomeric chain segment R1 is a polyoxypropylene chain segment.

[0037] The oligomer chain segment R1 may have a number average molecular weight Mn in the range of 400-2000, preferably 500-1500.

[0038] According to a preferred option, the 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 acid, 14-hydroxyeicosanoic acid (14-HEA) or a mixture of pairs thereof. The most preferred hydroxylated acid R2CO2H is 12-hydroxystearic acid.

[0039] Preferably, the monocarboxylic acid R2'CO2H is selected from acetic acid, propionic acid, butyric acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid or octanoic acid.

[0040] According to a particularly preferred option, the amide is a diamide or triamide in which all R2 residues originate from hydroxylated fatty acids R2CO2H. More particularly, the amide is a diamide in which the R2 residues originate from hydroxylated fatty acids R2CO2H.

[0041] According to another particular option of the invention, the amide is a triamide in which two R2 residues result from hydroxylated fatty acids R2CO2H and one R2 residue results from a non-hydroxylated fatty acid R2CO2H.

[0042] A second subject of the invention relates to a formulation of an organic binder, said composition comprising: a) at least one organic binder; b) at least one fatty acid amide as defined above according to the invention, in particular as a rheological additive; The present invention is characterized by comprising:

[0043] More specifically, in the binder blend composition, the binder a) is selected from a polysiloxane resin terminated with a blocked silane group, a polyether resin terminated with a blocked silane group, a polysulfide resin terminated with a blocked silane group, a polyurethane prepolymer resin terminated with an isocyanate group, a PVC resin for plastisol, and an epoxy resin having an epoxy group.

[0044] The composition may comprise, in addition to a) and b), depending on the binder, a plasticizer or reactive diluent as defined below: c) Plasticizers for polysiloxane resins, polyurethane prepolymer resins and PVC resins for plastisols, or d) reactive diluents from epoxidized monomers for epoxy resins; and optionally, e) In the case of two-component systems, hardeners for epoxy or polyurethane resins may include:

[0045] More specifically, in the composition according to the invention, the fatty acid amide is used as a rheological additive, which is a thixotropic agent.

[0046] In the composition, the organic binder a) may be selected from polysiloxane resins, polyurethane prepolymer resins or PVC resins for plastisols, and the plasticizer may be selected from phthalates, adipates, trimellitates, sebacates, benzoates, citrates, phosphates, epoxides, polyesters, alkylsulfonic acid esters and non-phthalate substitutes for phthalates.

[0047] According to a particular option, the composition is a transparent or opaque mastic formulation. According to a more particular option, the composition is a transparent mastic formulation.

[0048] Another subject of the present invention includes the use according to the invention of at least one fatty acid amide as defined above, in which said amide is used as a rheological additive.

[0049] In the above uses, the rheological additive can be used as a thixotropic agent.

[0050] More specifically, the use may be in coatings, adhesives, PVC plastisol or mastic compositions, preferably PVC plastisol and mastic compositions.

[0051] Another particular use is in PVC plastisol compositions.

[0052] Another particular use is in moisture-crosslinkable mastic compositions based on blocked silane-terminated polysiloxane resins, blocked silane-terminated polyether resins, blocked silane-terminated polysulfide resins, in particular alkoxy-blocked silane or isocyanate-terminated polyurethane prepolymer resins.

[0053] Another particular use is in mastic compositions that are crosslinkable by moisture, the mastic being either transparent or not.

[0054] Finally, the present invention encompasses an end product, which may be a coating, in particular a PVC plastisol coating, or an adhesive or mastic seal, which end product is obtained according to the invention by using at least one fatty acid amide as defined above as a rheological additive, in particular a thixotropic agent.

[0055] The following examples in the experimental section below are presented to illustrate the present invention and its performance qualities and are not intended to limit its scope in any way.

[0056] Experimental part 1) Starting materials and codes used See Table 1 below.

[0057] [Table 1]

[0058] For clarity, the following abbreviations are used:

[0059] 12HSA: 12-hydroxystearic acid SA: Stearic acid HMDA: Hexamethylenediamine D2000: Jeffamine® D-2000 polyetheramine T3000: Jeffamine® T-3000 polyetheramine

[0060] 2) Example Example A-T3000-12HSA3 according to the present invention 305.9 g of Jeffamine® T-3000 (0.099 mol, 1 eq) and 94.1 g of 12-hydroxystearic acid (0.297 mol, 3 eq) are added to a 1-liter round-bottom flask equipped with a thermometer, Dean-Stark apparatus, condenser, and stirrer. The mixture is heated to 180 °C under an inert atmosphere. The removed water accumulates in the Dean-Stark apparatus from 150 °C. The reaction is monitored by the acid number and amine number. The reaction is stopped when the acid number and amine number are each less than 6. The reaction mixture is cooled to 140 °C and poured into a silicone mold. Once cooled to ambient temperature, the product is flaked.

[0061] Examples B-12HSA-D2000-12HSA according to the present invention 304.4 g of Jeffamine® D-2000 (0.15 mol, 1 eq) and 95.6 g of 12-hydroxystearic acid (0.3 mol, 2 eq) are added to a 1-liter round-bottom flask equipped with a thermometer, Dean-Stark apparatus, condenser, and stirrer. The mixture is heated to 180 °C under an inert atmosphere. The removed water accumulates in the Dean-Stark apparatus from 150 °C. The reaction is monitored by the acid number and amine number. The reaction is stopped when the acid number and amine number are each less than 6. The reaction mixture is cooled to 140 °C and poured into a silicone mold. Once cooled to ambient temperature, the product is flaked.

[0062] Comparative Example C-T3000-SA3 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 to a 1-liter round-bottom flask equipped with a thermometer, Dean-Stark apparatus, condenser, and stirrer. The mixture is heated to 180 °C under an inert atmosphere. The removed water accumulates in the Dean-Stark apparatus from 150 °C. The reaction is monitored by the acid number and amine number. The reaction is stopped when the acid number and amine number are each less than 6. The reaction mixture is cooled to 140 °C and poured into a silicone mold.

[0063] Comparative Example D-SA-D2000-SA 312.2 g of Jeffamine® D-2000 (0.15 mol, 1 eq) and 87.8 g of stearic acid (0.3 mol, 2 eq) are added to a 1-liter round-bottom flask equipped with a thermometer, Dean-Stark apparatus, condenser, and stirrer. The mixture is heated to 180 °C under an inert atmosphere. The removed water accumulates in the Dean-Stark apparatus from 150 °C. The reaction is monitored by the acid number and amine number. The reaction is stopped when the acid number and amine number are each less than 6. The reaction mixture is cooled to 140 °C and poured into a silicone mold.

[0064] 3) Study of the gelling power of organogelators This comparative example investigates the ability of the rheological additive to form a gel in a simplified formulation containing only a conventional plasticizer (Jayflex® DIUP) used in PVC plastisol formulations.

[0065] The formulations were prepared using a laboratory "planetary" mixer (type Molteni® EMD 1) equipped with a dispersing disc and scraper, which allows for the mixing of powders in non-fluid systems as well as highly viscous products. It is equipped with a vacuum pump to prevent the ingress of moisture during dispersion. The temperature inside the Molteni® EMD 1 is recorded by a probe attached to the scraper and can be regulated by a bath.

[0066] [Table 2]

[0067] The rheological additives are introduced into the plasticizer and the mixture is brought to the consolidation temperature (see Table 3) and dispersed for 5 minutes. At the end of the dispersion, the mixture is cooled to ambient temperature and the gel behavior is visually investigated.

[0068] [Table 3]

[0069] The results of the gel test show that the products according to the invention (T3000-12HSA3, 12HSA-D2000-12HSA) form gels, while the comparative products are in liquid form.Therefore, in particular, the compound T3000-SA3 described in patent EP1514912A2 does not give gels (see formulation F3), which strongly indicates that the presence of hydroxyl groups is essential for the formation of supramolecular assemblies and 3D network structures of fibers.

[0070] The behavior of organogelators can also be influenced by the initial structure of the diamine used. Thus, when comparing the organogelator described in WO 2014 / 053774 A1 (12HSA-HMDA-12HSA) with the compound 12HSA-D2000-12HSA according to the present invention, significant differences in gel strength can be observed. In particular, replacing the aliphatic amine with a polyetheramine increases the gelling power and even allows the production of transparent gels. It should be noted that for complete dissolution, the compound 12HSA-HMDA-12HSA (see formulation F5) requires a higher temperature than the product according to the present invention.

[0071] Furthermore, the performance quality of the gel may be related to the physical properties of the rheological additive. As a result, differences in gel strength are observed for formulations F6 and F7, where the integration of the rheological additive begins at a certain temperature (60°C). That is, when the additive is in flake form (see formulation F6), the gel strength decreases, which can be explained by incomplete integration of the product in the formulation due to lack of solubility. Furthermore, granules could be observed, which could support this hypothesis.

[0072] It can also be observed that when powdered additives are consolidated at temperatures higher than their optimum (60 °C for F7) (80 °C for F7), a decrease in gel strength can be observed, further indicating a sensitivity to temperature, possibly due to complete dissolution of the product. Therefore, for standard products, it is important to actually observe the temperature range in which the organogelator is effective.

[0073] For formulations F1 and F2 based on the product according to the invention, a strong gel formation can be observed, regardless of the consolidation temperature. It should be noted that at the temperatures investigated, the rheological additives are completely dissolved. Furthermore, the formulations show a completely transparent appearance.

[0074] 4) Evaluation of rheological performance qualities in simplified hybrid mastic formulations This comparative example demonstrates the rheological performance qualities of the additive in a simplified hybrid mastic formulation.

[0075] [Table 4]

[0076] To do this, the same Molteni® EMD 1 mixer is used to prepare the formulation. The resin and plasticizer are added in the indicated proportions in the first stage and homogenized. The additives are weighed and then added in the second stage. The reaction mixture is then kept under vacuum during the mixing stage and brought to 80°C for 5 minutes. At the end of this stage, the mixture is cooled to 25°C and discharged.

[0077] [Table 5]

[0078] The triamide rheological additive T3000-12HSA3 according to the invention is found to be much more effective in terms of rheological performance qualities (see formulation F8) compared to the standard powder additive Crayvallac® Antisettles CVP (see formulation F9). The diamide product 12HSA-D2000-12HSA likewise shows better rheological performance qualities (see formulation F10) than when the powdered compound 12HSA-HMDA-12HSA is used (see formulation F11).

[0079] Furthermore, the products according to the invention do not require specific processing steps to develop the rheology, as is necessary with conventional powdered additives based on hydrogenated castor oil derivatives.

[0080] Furthermore, the products according to the invention are in flake form, thus eliminating the problems that arise when using powders (handling, toxicity, etc.) It should also be noted that these products make it possible to obtain completely transparent MS mastic formulations.

Claims

1. 1. A PVC plastisol, adhesive seal or mastic seal resulting from the use of at least one fatty acid amide as rheological additive, said fatty acid amide being a diamide or triamide or a mixture thereof, said fatty acid amide comprising: A) The following formula (I): R[(-X-R1-NHCO-R2) ｎ－ｎ１ ][(-X-R1-NHCO-R2′) ｎ１ ](I) (In the formula, n is 2 or 3; n １ is equal to 0 or 1, R-(X-R1-) ｎ is a primary polyamine R(-X-R1-NH ２ ) ｎ is a residue of valence n of Each primary amine group -NH ２ is an end group of a divalent oligomeric chain segment R1 selected from polyethers, R is a polyol R(OH) ｎ or Polyamine R(NH ２ ) ｎ or R(NH-R3) ｎ C of valence n resulting from ３ -C １０ is a hydrocarbon group, X is O, NH or NR3; R2 is C １２ -C ５２ Fatty acid R2CO ２ is the fatty residue of H, R2' is C ２ -C １０ Acid R2'CO ２ H is a monocarboxylic acid residue, At least one R2 residue is a hydroxylated fatty acid R2CO having a non-terminal hydroxyl group. ２ H, and the R2 residues can be the same or different; R3 is C １ -C ２ alkyl substituents), or B) When the amide is a diamide, it is represented by the following formula (II): R2CONH-R′-O-[CH ２ -CH(R4)-O] ｘ -CH ２ -CH(R4)-NHCOR2′(II) (In the formula, R' is a monopropylene glycol residue containing no OH: -CH(CH ３ )-CH ２ - and R and R are defined above in formula (I), R4 is H or methyl and has a repeating oxyalkylene unit -CH ２ -CH(R4)-O- is ethoxy when R4 is H or propoxy when R4 is methyl, or R4 corresponds to an ethoxy / propoxy mixture; x is a value such that the number average molecular weight Mn of the fatty acid amide measured by GPC in THF as a polystyrene equivalent is 800 to 4000. is represented by The melting point, meaning the melting temperature of the amide, is in the range of 10 to 110°C, as measured by DSC after two passes at 10°C / min. A PVC plastisol, adhesive seal or mastic seal, characterized in that:

2. The number average molecular weight Mn of the fatty acid amide according to A), measured by GPC in THF as a polystyrene equivalent, is: When n = 2, it is 800 to 4000. When n = 3, it is 1000 to 6000.

2. A PVC plastisol, adhesive seal or mastic seal according to claim 1, characterized in that it varies with:

3. 3. A PVC plastisol, adhesive seal or mastic seal according to claim 1 or 2, characterized in that the oligomeric chain segment R1 is an oxypropylene / oxyethylene copolymer in which oxypropylene units predominate.

4. 3. A PVC plastisol, adhesive seal or mastic seal according to claim 1 or 2, characterized in that the oligomeric chain segment R1 is a polyoxypropylene chain segment.

5. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 to 4, characterized in that the oligomeric chain segment R1 has a number average molecular weight Mn in the range of 400 to 2000.

6. The hydroxylated fatty acid RCO ２ 6. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 to 5, characterized in that H is selected from 12-hydroxystearic acid (12-HSA), 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), and 14-hydroxyeicosanoic acid (14-HEA).

7. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 to 6, characterized in that the hydroxylated fatty acid is 12-hydroxystearic acid.

8. The acid R2'CO ２ 8. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 to 7, characterized in that H is selected from acetic acid, propionic acid, butyric acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid, octanoic acid.

9. The amide is a diamide according to A) or B) or a triamide according to A), in which all R2 residues are hydroxylated fatty acids R2CO ２ 9. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 to 8, characterized in that it is derived from H.

10. The amide is a diamide according to A) or B) and one R2 residue is a hydroxylated fatty acid R2CO ２ 9. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 to 8, characterized in that it is derived from H.

11. The amide is a triamide according to A) in which two R2 residues are hydroxylated fatty acids R2CO ２ 9. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 to 8, characterized in that the R residues arise from H and one R2 residue arises from a non-hydroxylated fatty acid.

12. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 to 8, characterized in that the amide is a diamide represented by A) according to formula (I).

13. A PVC plastisol, adhesive seal or mastic seal according to any one of claims 1 and 6 to 8, characterized in that the amide is a diamide represented by B) according to formula (II).

14. a) at least one organic binder; b) at least one fatty acid amide as defined in accordance with any one of claims 1 to 13; and PVC plastisols, adhesive seals or mastic seals, characterized in that they result from the use of

15. 15. The PVC plastisol, adhesive seal or mastic seal according to claim 14, characterized in that the binder a) is selected from polysiloxane resins terminated with blocked silane groups, polyether resins terminated with blocked silane groups, polysulfide resins terminated with blocked silane groups, polyurethane prepolymer resins terminated with isocyanate groups, PVC resins for plastisols, and epoxy resins having epoxy groups.

16. In addition to a) and b), depending on the binder, plasticizers or reactive diluents as defined below: c) plasticizers for polysiloxane resins, polyurethane prepolymer resins and PVC resins for plastisols, or d) reactive diluents from epoxidized monomers for epoxy resins; and optionally, e) In the case of two-component systems, a hardener for epoxy or polyurethane resins 16. A PVC plastisol, adhesive seal or mastic seal according to claim 14 or 15, characterized in that it comprises

17. 17. PVC plastisols, adhesive seals or mastic seals according to claim 16, characterized in that the organic binder a) is a polysiloxane resin, a polyurethane prepolymer resin or a PVC resin for plastisols and the plasticizer is selected from phthalates, adipates, trimellitates, sebacates, benzoates, citrates, phosphates, epoxides, polyesters, alkylsulfonic acid esters and non-phthalate substitutes for phthalates.

18. 18. A PVC plastisol, adhesive seal or mastic seal according to claim 17, characterized in that it is a transparent or opaque mastic seal.

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