Diamide, functionalized polymer, and wax-based rheological additives

Abstract

Since diamides offer advantages in terms of thixotropic effects under activation conditions imposed at relatively low temperatures, i.e., between 40°C and 80°C, we provide a novel additive that can contain a large amount of diamide. [Solution] - Component A) is 30% to 90% of which is at least one type of diamide, - Component B) consisting of 5% to 40% of at least one functionalized polymer, - Component C) consists of 5% to 60% of at least one type of wax, An additive is provided in which the % value is a weight percentage of the weight of the additive.

Description

[Technical Field]

[0001] The present invention relates to additives based on diamides, functionalized polymers, and waxes, as well as their use as rheological agents, particularly thixotropic agents, in binder compositions, especially coating compositions, adhesives, glues or mastic compositions, molding compositions, composite material compositions, chemical sealing compositions, leak-proofing compositions, and photocrosslinkable compositions for stereolithography or 3D printing of objects. [Background technology]

[0002] Diamides based on hydroxylated and / or non-hydroxylated fatty acids are already known as organic gelling agents, i.e., as small organic molecules capable of gelling all kinds of organic solvents even at relatively low weight concentrations (less than 1% by weight), or as rheological additives, i.e., as additives that enable modification of the rheology of the applied formulation. They enable, for example, obtaining thixotropic or pseudoplastic effects.

[0003] Other examples of thixotropic agents include waxes, oils, and functionalized polymers.

[0004] Combining several different thixotropic agents within an additive can improve its rheological properties. However, this can lead to miscibility issues between different thixotropic agents and / or impair the aesthetic and mechanical properties of the final formulation. Therefore, it is desirable to combine several thixotropic agents together to obtain a stable additive that is easy to use and has improved performance quality without impairing the properties of the binder composition into which they are introduced.

[0005] International Publication No. 2018 / 146114 describes additives based on diamides and carboxylated polyolefins, as well as their use as rheological additives and anti-sagging agents for liquid systems. The content of the diamide used is 20% to 40% by weight relative to the total weight of the diamide and polyolefin. The document also states that when additives with a diamide content exceeding 40% by weight are introduced into a composition, certain properties of the resulting coating are reduced, particularly adhesion, as well as yellowing and increased sliding resistance. Furthermore, the applicant's company has found that additives with a higher proportion of diamide relative to carboxylated polyolefin exhibit a non-uniform appearance due to miscibility issues between the diamide and polyolefin, as well as insufficient rheological properties.

[0006] Description of the invention Since diamides offer advantages in terms of thixotropic effects under activation conditions imposed at relatively low temperatures, i.e., between 40°C and 80°C, there is a need for novel additives that can contain large amounts of diamides. The resulting additives should be stable, easy to use, and possess improved performance qualities without impairing the properties of the binder composition into which they are introduced.

[0007] After numerous studies, the applicant's company found that the introduction of wax into additives based on diamides and functionalized polymers makes it possible to satisfy this need. [Overview of the project]

[0008] The first subject of this invention is, - Component A) is 30% to 90% of which is at least one type of diamide, - Component B) consisting of 5% to 40% of at least one functionalized polymer, - Component C) consists of 5% to 60% of at least one type of wax, This is an additive containing [the specified substance], and the percentage value is the weight percentage of the additive's weight.

[0009] A second object of the present invention is a pre-activated additive composition comprising the additive according to the present invention and a plasticizer.

[0010] A third object of the present invention is a binder composition comprising a binder and the additive according to the present invention or the pre-activated additive composition according to the present invention.

[0011] Another object of the present invention is the use of the additive according to the present invention or the pre-activated additive composition according to the present invention as a rheological agent, in particular as a thixotropic agent. Mode for Carrying Out the Invention

[0012] Definitions In the present patent application, the terms "comprises a" and "comprises an" mean "comprises one or more".

[0013] Unless otherwise specified, weight percentages of a compound or composition are expressed relative to the weight of the compound or composition.

[0014] Component A) The additive according to the present invention comprises component A).

[0015] Component A) is a diamide or a mixture of diamides.

[0016] Within the meaning of the present invention, a diamide is a compound having two amide (-NH-C(=O)-) functional groups.

[0017] The diamide is obtained by reaction of at least one diamine with at least one carboxylic acid. Asymmetric diamides can be obtained by reaction of a diamine with different carboxylic acids. Mixtures of diamides can be obtained by using different diamines and / or different carboxylic acids.

[0018] According to a particular embodiment, component A) is C2~C24 Aliphatic diamines, C6~C 18 Alicyclic diamines, C6~C 24 The invention comprises a diamide obtained from at least one diamine selected from aromatic diamines and mixtures thereof. The diamide can be obtained by using a mixture of said diamines.

[0019] Within the meaning of the present invention, a diamine is a compound having two primary amine (-NH2) functional groups.

[0020] Within the meaning of the present invention, an aliphatic diamine is an acyclic diamine. C2~C 24 The aliphatic diamine is an aliphatic diamine containing 2 to 24 carbon atoms. The aliphatic diamine can be linear or branched, preferably linear. Examples of suitable linear aliphatic diamines include 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, and mixtures thereof, preferably 1,2-ethylenediamine, 1,5-pentamethylenediamine and 1,6-hexamethylenediamine. Examples of suitable branched aliphatic diamines are 1,2-propylenediamine, 2,2-dimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, and mixtures thereof.

[0021] Within the meaning of the present invention, an alicyclic diamine is a non-aromatic diamine comprising a ring, particularly a ring having 6 carbon atoms. C6~C 18The alicyclic diamine is an alicyclic diamine containing 6 to 18 carbon atoms. Examples of suitable alicyclic diamines include 1,2-, 1,3- or 1,4-diaminocyclohexane, 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, isophoronediamine, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, diaminodecahydronaphthalene, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, bis(aminomethyl)norbornane and mixtures thereof, preferably 1,3- or 1,4-bis(aminomethyl)cyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, isophoronediamine and 4,4'-diaminodicyclohexylmethane.

[0022] Within the meaning of the present invention, an aromatic diamine is a diamine containing an aromatic ring. C6~C 24 The aromatic diamine is an aromatic diamine containing 6 to 24 carbon atoms. Examples of suitable aromatic diamines include meta- and para-phenylenediamine, meta- and para-xylylenediamine, meta- and para-toluylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and mixtures thereof, preferably meta- and para-xylylenediamine.

[0023] Preferably, component A) is C2~C 24 Aliphatic diamines, particularly linear C2~C 18 Aliphatic diamines, more specifically linear C2~C 12 It includes a diamide obtained from an aliphatic diamine, more specifically at least one diamine selected from 1,2-ethylenediamine, 1,5-pentamethylenediamine or 1,6-hexamethylenediamine.

[0024] According to a specific embodiment, component A) is at least one C2~C 36 It includes a diamide obtained from a carboxylic acid. The diamide is C2~C36 It can be obtained using a mixture of carboxylic acids.

[0025] Within the meaning of the present invention, C2~C 36 A carboxylic acid is a compound having a carboxylic acid (-COOH) functional group and 2 to 36 carbon atoms. Carboxylic acids can be linear or branched, preferably linear. Carboxylic acids can be saturated or unsaturated, preferably saturated. Carboxylic acids can be unsubstituted or hydroxylated. A hydroxylated carboxylic acid is a carboxylic acid substituted with one or two hydroxyl groups, preferably one hydroxyl group.

[0026] According to certain embodiments, the carboxylic acid may optionally be a hydroxylated carboxylic acid as a mixture with an unsubstituted carboxylic acid.

[0027] Suitable examples of hydroxylated carboxylic acids include 12-hydroxystearic acid (12-HSA), 9-hydroxystearic acid (9-HSA), 10-hydroxystearic acid (10-HSA), 14-hydroxyeicosanoic acid (14-HEA), 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, hydroxynonanoic acid, hydroxydecanoic acid, and mixtures thereof, preferably 12-hydroxystearic acid, or a two- or three-component mixture of 12-hydroxystearic acid and other hydroxylated acids.

[0028] Suitable examples of unsubstituted carboxylic acids include acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, palmitoleic acid, oleic acid, 11-eicosenoic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and mixtures thereof, preferably decanoic acid.

[0029] Preferably, component A) is C2~C 22 Carboxylic acids, especially hydroxylated C2-C2 22 Carboxylic acids and optionally unsubstituted C2-C2 22 Carboxylic acids, more specifically hydroxylated C 12 ~C 20 Carboxylic acids and optionally unsubstituted C2-C2 14 The present invention includes a diamide obtained from at least one carboxylic acid selected from carboxylic acids.

[0030] According to a preferred embodiment, component A) comprises a diamide having a melting point of less than 250°C, less than 225°C, less than 210°C, or less than 200°C. According to a particularly preferred embodiment, component A) comprises a diamide obtained by the reaction of 1,2-ethylenediamine, 1,5-pentamethylenediamine, or 1,6-hexamethylenediamine with 12-hydroxystearic acid and any decanoic acid.

[0031] The additive according to the present invention contains component A) in an amount of 30% to 90% by weight relative to the weight of the additive. The additive may contain component A) in an amount of 35% to 90% by weight, particularly 40% to 90% by weight, and more specifically 40% to 85% by weight relative to the weight of the additive.

[0032] According to a particular embodiment, the additive may contain component A) in an amount of 30% to 60% by weight, particularly 35% to 55% by weight, and more specifically 40% to 50% by weight, relative to the weight of the additive.

[0033] According to another embodiment, the additive may contain component A) in an amount of 70% to 90% by weight, particularly 75% to 90% by weight, and more specifically 80% to 90% by weight, relative to the weight of the additive.

[0034] Component B) The additive according to the present invention contains component B). Component B is different from components A) and C).

[0035] Component B) is a functionalized polymer or a mixture of functionalized polymers.

[0036] Within the scope of the present invention, a functionalized polymer is a polymer comprising a backbone having a functional group. A functional group is a group that can react with other compounds during a reaction, or a group that can promote the compatibility of the polymer with additives. The polymer backbone is a main chain comprising units resulting from the polymerization of monomers, particularly ethylenically unsaturated monomers. Functionalized polymers can be obtained by functionalizing existing polymers, particularly by oxidation or grafting reactions. Alternatively, functionalized polymers can be obtained by introducing monomers having a functional group into a polymerization reaction.

[0037] Functionalized polymers may have a weight-average molecular weight of 600 to 20,000 g / mol, and especially 1,000 to 5,000 g / mol.

[0038] Functionalized polymers can be waxes in particular. Within the scope of the present invention, waxes are compounds that are solid at 20°C. Waxes can begin to melt at temperatures above 45°C without decomposing. Waxes can exhibit low viscosity (less than 50 mPa·s) above their melting point. Waxes can be insoluble in water. Waxes can be malleable, especially at 20°C. Waxes can exhibit a softening point, especially above 70°C, and especially between 70°C and 120°C.

[0039] According to certain embodiments, component B) comprises a polymer functionalized with polar groups, particularly polar groups selected from carboxylic acids, anhydrides, ethers, aldehydes, alcohols, amines, and mixtures thereof. More specifically, the functionalized polymer contains at least a carboxylic acid group.

[0040] Component B) may, in particular, contain a functionalized polymer having an acid value of 3-50, or 5-40, or 8-35, or 10-25 mgKOH / g.

[0041] Functionalized polymers can be selected from polyolefins, polyesters, polyethers, (meth)acrylic polymers, polyurethanes, polyamides, styrene / maleic acid copolymers, and mixtures thereof. Functionalized polymers may contain a backbone resulting from the polymerization of one or more monomers selected from polyols, poly(carboxylic acids), polyesters, anhydrides, polyisocyanates, polyamines, diepoxides, ethylenically unsaturated monomers, and mixtures thereof. Ethylenelycol-unsaturated monomers are monomers having polymerizable carbon-carbon double bonds. Polymerizable carbon-carbon double bonds are generally found in groups selected from acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls, and corresponding combinations. Carbon-carbon double bonds of phenyl rings are not considered polymerizable carbon-carbon double bonds.

[0042] According to certain embodiments, component B) comprises a functionalized polyolefin, in particular an oxidized polyolefin, and more specifically an oxidized polyethylene.

[0043] Within the scope of the present invention, polyolefins are polymers containing units resulting from the polymerization of olefins. Olefins are alkenes, particularly those having 2 to 8 carbon atoms, especially 2 to 6, and more specifically 2 to 4 carbon atoms. Preferably, the olefins used to obtain polyolefins are α-olefins, i.e., olefins having terminal carbon-carbon double bonds. Examples of preferred olefins are ethylene, propylene, 1-butene, isobutene, and mixtures thereof, preferably ethylene and propylene.

[0044] Polyolefins can be homopolymers of a single type of olefin (e.g., ethylene homopolymers) or copolymers of at least two olefins (e.g., polymers of a mixture of ethylene, propylene, 1-butene, and / or isobutene). Furthermore, polyolefins may also comprise one or more units resulting from the polymerization of ethylenically unsaturated monomers other than olefins, more specifically, ethylenically unsaturated monomers having carboxylic acid or anhydride groups. These ethylenically unsaturated monomers can be copolymerized with olefins or subsequently added, for example, by grafting. When ethylenically unsaturated monomers having carboxyl or anhydride groups are used, the resulting polyolefins are functionalized with carboxylic acid or anhydride groups.

[0045] Within the scope of the present invention, oxidized polyolefins are polyolefins containing at least a carboxylic acid group. Oxidized polyolefins may further contain one or more groups selected from aldehydes, ketones, ethers, alcohols, and mixtures thereof. Oxidized polyolefins can be obtained, in particular, by one of the following methods. 1) Oxidation of nonpolar polyolefins, especially nonpolar polyethylene, particularly by oxidation in a molten state. 2) Methods for the oxidative decomposition of polyolefin plastics, particularly polyethylene plastics. 3) A method by polymerization of olefins, particularly ethylene and / or propylene, with ethylenically unsaturated monomers having a carboxylic acid group or an anhydride group, particularly a (meth)acrylic acid group. 4) A method by radical grafting of an ethylenically unsaturated monomer having a carboxylic acid group or an anhydride group, particularly maleic anhydride, onto a nonpolar polyolefin, especially nonpolar polyethylene and / or polypropylene.

[0046] According to one embodiment, the oxidized polyolefin is at least one olefin, particularly an α-olefin, and more specifically, a homopolymer or copolymer of ethylene and / or propylene.

[0047] Oxidized polyolefins can be selected from, in particular, oxidized polyethylene, oxidized polypropylene, oxidized poly(ethylene-co-propylene), ethylene oxide / α-olefin copolymers, copolymers of ethylene and (meth)acrylic acid, ethylenically unsaturated monomers having carboxylic acid or anhydride groups, such as polymers of ethylene and / or propylene grafted with (meth)acrylic acid or maleic anhydride.

[0048] Products of this type are available under the reference symbols, for example, AC 680, AC 629, or AC 673P sold by Honeywell; Viscowax® 252 and Viscowax® 253 sold by Innospec Leuna; Deurex E040 sold by Deurex; Licowax® PED 521, Licowax® PED 522, or Licolub® H 12 sold by Clariant; or Epolene® E 14 sold by Westlake.

[0049] The additive according to the present invention contains component B) in an amount of 5% to 40% by weight relative to the weight of the additive. The additive may contain component B) in an amount of 5% to 35% by weight, particularly 10% to 35% by weight, and more specifically 10% to 30% by weight relative to the weight of the additive.

[0050] According to a particular embodiment, the additive may contain component B) in an amount of 15% to 40% by weight, particularly 20% to 40% by weight, and more specifically 25% to 35% by weight, relative to the weight of the additive.

[0051] According to another embodiment, the additive may contain component B) in an amount of 5% to 25% by weight, particularly 5% to 20% by weight, and more specifically 5% to 15% by weight, relative to the weight of the additive.

[0052] Component C) The additive according to the present invention contains component C). Component C is different from components A) and B).

[0053] Component C) is a wax or a mixture of waxes.

[0054] Component C) advantageously allows components A) and B) to be miscible so that the additive can be atomized into a homogeneous mixture.

[0055] Component C) may contain waxes having a softening point above 70°C, particularly between 70°C and 120°C.

[0056] Component C) may contain a wax having an acid value of less than 10 mg KOH / g, particularly less than 5 mg KOH / g, more specifically less than 3 mg KOH / g, and even more specifically less than 2.5 mg KOH / g.

[0057] According to a particular embodiment, component C) comprises a wax selected from mineral waxes, natural waxes, synthetic waxes, and mixtures thereof.

[0058] Mineral waxes are obtained from crude oils, coal, or lignite. Mineral waxes can be selected from paraffin wax, microcrystalline wax, ceresin, montan wax, and mixtures thereof. The fraction obtained by distillation of crude oils at 400°C–500°C also contains paraffin wax and microcrystalline wax. These are saturated hydrocarbons having 18–60 carbon atoms. Microcrystalline waxes have long branched chains that confer a microcrystalline structure. They are soft, white, opaque, and have a melting point above 70°C. Paraffin waxes have slightly shorter straight chains that confer a macrocrystalline structure. They are easily broken, white, opaque, and hard solids with a melting point between 50°C and 70°C. Ceresin is a mixture of hydrocarbons obtained by the purification of ozokerite. Montan wax (an ester of montanic acid with an alcohol selected from ethylene glycol, butane-1,3-diol, or glycerol) is obtained by extraction of lignite (fossil plant-rich coal).

[0059] Natural waxes can be selected from, in particular, cerides, diols or triols completely or partially esterified with fatty acids, vegetable waxes or animal waxes, and mixtures thereof. Cerides are esters of fatty acids and fatty alcohols. Fatty acids may be saturated or unsaturated, unsubstituted or hydroxylated linear carboxylic acids having 12 to 36 carbon atoms, preferably an even number. Fatty alcohols may be monoalcohols having 12 to 36 carbon atoms. Diols and triols completely or partially esterified with fatty acids (preferably hydroxylated fatty acids) can be selected from, in particular, ethylene glycol, propane-1,2-diol, glycerol, diols having 12 to 36 carbon atoms, and mixtures thereof. Vegetable or animal waxes include a group of compounds extracted from plants or animals during the manufacture of waxes, oils or butters, and conversion products obtained from these compounds, particularly those converted by hydrogenation or metathesis reactions. Therefore, oils and butters that are solid at 20°C, especially partially or completely hydrogenated vegetable oils, are considered vegetable or animal waxes within the scope of the present invention. Oils and butters primarily contain fatty acids (preferably hydroxylated fatty acids) and glycerol diesters and triesters. Examples of cerides include cetyl palmitate, dodecyl laurate, octadecyl stearate, tetradecyl myristate, myricyl palmitate, and myricyl cerotate. Examples of vegetable or animal waxes include beeswax, candelilla wax, carnauba wax, rice bran wax, wood wax, soybean wax, rapeseed wax, palm wax, whale wax, shea butter, cocoa butter, tristearin, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated cottonseed oil, hydrogenated rapeseed oil, hydrogenated soybean oil, hydrogenated palm oil, and mixtures thereof.

[0060] Synthetic waxes are mainly hydrocarbons (alkanes and alkenes) and polyoxyalkylenes synthesized by humans. Synthetic waxes may include, in particular, Fischer-Tropsch wax, polyethylene and / or polypropylene wax, poly(ethylene oxide) and / or poly(propylene oxide) wax, and mixtures thereof. Fischer-Tropsch wax mainly contains alkanes and is obtained from a mixture of CO and H2. This wax is hard and has a macrocrystalline structure comparable to natural paraffin wax. Polyethylene and / or polypropylene wax can be obtained by cracking polyethylene and / or polypropylene. Formula H-(CH2-CHR) n A polymer with shorter H chains is obtained, where each R is independently H or methyl, and n varies from 50 to 100. Poly(ethylene oxide) and / or poly(propylene oxide) waxes have the unit H-(O-CHR-CH 2)n This corresponds to a polymer of -OH, where each R is independently either H or methyl, and n varies from 20 to 100.

[0061] According to a preferred embodiment, component C) comprises a hydroxylated wax, particularly a hydroxylated wax having an OH value of greater than 25 mg KOH / g, greater than 50 mg KOH / g, greater than 75 mg KOH / g, greater than 100 mg KOH / g, greater than 125 mg KOH / g, greater than 150 mg KOH / g, or greater than 155 mg KOH / g.

[0062] In particular, component C) may include natural waxes selected from fatty acids, diols or triols that are fully or partially esterified with esters of fatty acids and fatty alcohols, wherein the fatty acids are saturated or unsaturated linear hydroxylated carboxylic acids having 12 to 36, preferably even, carbon atoms.

[0063] In a particularly preferred embodiment, component C) comprises hydrogenated castor oil.

[0064] The additive according to the present invention contains component C) in an amount of 5% to 60% by weight relative to the weight of the additive. The additive may contain component C) in an amount of 5% to 55% by weight, particularly 10% to 55% by weight, and more specifically 10% to 50% by weight relative to the weight of the additive.

[0065] According to a particular embodiment, the additive may contain component C) in an amount of 10% to 40% by weight, particularly 15% to 35% by weight, and more specifically 20% to 30% by weight, relative to the weight of the additive.

[0066] According to another embodiment, the additive may contain component C) in an amount of 5% to 25% by weight, particularly 5% to 20% by weight, and more specifically 10% to 20% by weight, relative to the weight of the additive.

[0067] additives The additive according to the present invention is -Component A) consisting of 30% to 90%, particularly 35% to 90%, more specifically 40% to 90%, and even more specifically 40% to 85%, -Component B) consisting of 5% to 40%, particularly 5% to 35%, more specifically 10% to 35%, and even more specifically 10% to 30%, -5% to 60%, especially 5% to 55%, more specifically 10% to 55%, and even more specifically 10% to 50% of component C) The percentage value is the weight percentage relative to the weight of the additive.

[0068] According to a particular embodiment, the additive is -Component A) is 30% to 60%, especially 35% to 55%, and more specifically 40% to 50%, -Component B) is 15% to 40%, especially 20% to 40%, and more specifically 25% to 35%, -10% to 40%, especially 15% to 35%, and more specifically 20% to 30% of component C) The percentage value is the weight percentage relative to the weight of the additive.

[0069] According to another specific embodiment, the additive is -Component A) is 70% to 90%, especially 75% to 90%, and more specifically 80% to 90%. -Component B) is 5% to 25%, especially 5% to 20%, and more specifically 5% to 15%, - Component C) at 5% to 25%, especially 5% to 20%, and more specifically 10% to 20% The percentage value is the weight percentage relative to the weight of the additive.

[0070] The additive may further contain component D) in an amount of 0% to 10%, particularly 0% to 5%, and more specifically 0% to 2%, relative to the weight of the additive, wherein component D) is at least one compound other than components A), B), and C).

[0071] Component D) may include by-products related to the preparation of components A), B), and C). Examples of such by-products are catalysts, particularly inorganic salts, metal oxides or metalloid oxides, diamines, and C2-C2 compounds. 36 Carboxylic acid, diamine and 1 equivalent of C2-C 36 It is a monoamide produced by the reaction with a carboxylic acid.

[0072] The additive may essentially consist of or be composed of components A), B), C), and D). Therefore, the total weight of components A), B), C), and D) may equal 100% of the weight of the additive.

[0073] According to a particular embodiment, the weight ratio of component A) to component B) is in the range of 0.8 to 10, particularly 1 to 9, and more specifically 1.5 to 8.5.

[0074] The additive according to the present invention may be in the form of a solid, more specifically in the form of solid particles, and more specifically in the form of solid particles having a volume average size of less than 50 μm or less than 25 μm.

[0075] The additive can be obtained by following a method that includes the following steps: a) Mixing components A), B), C), and optionally D) at a high temperature (140-220°C) to form a homogeneous mixture. b) In order to obtain a solid, the mixture obtained in step a) is cooled to room temperature (20-25°C). c) A step of micronizing the solid obtained in step b) in order to obtain solid particles having a volume average size of less than 50 μm.

[0076] Alternatively, the additive according to the present invention may be in the form of a pre-activated paste. Therefore, the additive according to the present invention can be mixed with a plasticizer to form the pre-activated additive composition described below.

[0077] Pre-activation additive composition The pre-activation additive composition according to the present invention comprises the above-mentioned additives and plasticizers.

[0078] Within the scope of the present invention, a plasticizer is a compound that facilitates the use of additives.

[0079] Preferably, the plasticizer is a polar organic plasticizer comprising at least one polar group, preferably an ether group and / or an ester group and / or an epoxy group.

[0080] Among plasticizers having an ester group, at least one C6-C 10 Examples include plasticizers containing aromatic acid ester groups, particularly monoalkyl phthalates and / or dialkyl phthalates, more preferably dialkyl phthalates, wherein the alkyl groups may be the same or different, C7-C 18 Preferably C 10 ~C 12 Selected from alkyl groups. Examples include alkyl sulfonates, preferably esters of alkyl sulfonic acid with phenol, and dibenzoates.

[0081] Among plasticizers having an ether group, examples include homopolymer polyethers of propylene oxide (polypropylene glycol) having a weight-average molecular weight Mw in the range of 1000 to 3000, more specifically polypropylene glycol (PPG) having an Mw equal to 2000, and / or monoesters, preferably C2-C4 monoesters, or C1-C4 monoethers, such as monomethoxylated derivatives or monoethoxylated derivatives, and derivatives thereof selected from these.

[0082] According to certain embodiments, the plasticizer comprises mono- and / or dialkyl phthalates.

[0083] Pre-activated additive compositions are conveniently prepared for use by end-users (formulators of mastics, glues, adhesives, or coatings, e.g., paints, varnishes, gel coats, inks, or molding compositions) by simple mixing in the end-use formulation, without requiring any specific in situ activation in that formulation (specific conditions of temperature, shear, and observed duration).

[0084] Binder composition The additives according to the present invention are advantageously introduced into binder compositions to modify their rheology, particularly to impart thixotropic or pseudoplastic effects.

[0085] The binder composition according to the present invention comprises a binder and the above-mentioned additive or the above-mentioned pre-activating additive composition.

[0086] According to certain embodiments, the binder composition is a coating composition, particularly a varnish, rendering, surface gel, paint or ink composition, adhesive, glue or mastic composition, molding composition, composite material composition, chemical sealing composition, leak-proofing composition, or a photocrosslinkable composition for stereolithography or 3D printing of objects, particularly by inkjet printing.

[0087] The binder composition may contain additives in an amount of 0.5% to 15% by weight, particularly 1% to 10% by weight, and more specifically 2% to 7% by weight, relative to the total weight of the composition.

[0088] According to certain embodiments, the binder compositions according to the present invention are crosslinkable or non-crosslinkable by thermal or irradiation under radiation such as UV (in the presence of at least one photoinitiator) and / or EB (electron beam without initiator), including self-crosslinking at room temperature. The binder compositions may be crosslinkable monocomponent (a single reactive component) or crosslinkable biancomponent (a binder based on two components that react together by mixing during use).

[0089] The binder can be selected from at least one epoxy-amine reaction system (crosslinkable two-component), unsaturated polyester, vinyl ester, epoxidized resin, reactive silicone resin, alkyd grafted by polyester or polyamide or diurea / diurethane modification, or ungrafted alkyd, polyurethane or silicone resin, crosslinkable two-component polyurethane, polysiloxane, polysulfide polymer, reactive acrylic polymer, (meth)acrylate polyfunctional oligomer or acrylic oligomer or allyl polyfunctional oligomer, SBR elastomer, polychloroprene or butyl rubber type, or silane prepolymer, preferably silane polyether or silane polyurethane, or silane polyether-urethane having -OH or -CO2H functional groups.

[0090] In more specific examples, the binder can be selected from the following crosslinkable two-component reaction systems: epoxy-amine or epoxy-polyamide systems comprising at least one epoxy resin containing at least two epoxy groups and at least one amino compound or polyamide compound containing at least two amine groups; polyurethane systems comprising at least one polyisocyanate and at least one polyol; polyol-melamine systems; and polyester systems based on polyols that react with at least one epoxy or at least one acid or one corresponding anhydride.

[0091] In other specific examples, the binder may be a crosslinkable two-component polyurethane system or crosslinkable two-component polyester system starting from an epoxy-carboxylic acid or anhydride reaction system, or a polyol-melamine reaction system in which the polyol is a hydroxylated acrylic resin, polyester, or polyether polyol.

[0092] The binder composition according to the present invention may also include other components, such as fillers, plasticizers, wetting agents, or pigments.

[0093] In an alternative embodiment, the binder composition according to the present invention is a self-crosslinking mastic, glue, adhesive, or leak-proofing composition based on a polyether-silane or polyurethane-silane binder.

[0094] More specifically, the binder composition according to the present invention may be a one-component mastic composition based on silylation (or silaneization, this term is considered synonymous with silylation in the present invention), preferably silylated polyether or silylated polyurethane (silylated polyether-urethane), for example, Kaneka MS Polymer® and Kaneka Silyl®.

[0095] Other components, such as other types of binders, coloring pigments, various plasticizers, precipitated or pulverized calcium carbonate type fillers, glyceride derivatives, silica, such as fumed silica, other additives, such as UVA (UV antioxidant), such as 2,4-di(tert-butyl)-6-(5-chlorobenzotriazole-2-yl)phenol (BASF's Tinuvin® 327), sterically hindered amine-based light stabilizers, such as HALS (hindered amine light stabilizers), such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (BASF's Tinuvin® 770), waxes, and other types of catalysts, such as tin salts, can be added to or substituted for the one-component mastic composition based on the silylated prepolymer.

[0096] use The additive or pre-activated additive composition according to the present invention is used as a rheological agent, particularly as a thixotropic agent.

[0097] Therefore, by incorporating additives or pre-activating additive compositions into a binder composition, it becomes possible to modify its rheology, particularly by imparting a thixotropic effect. Consequently, the binder composition may be in the form of a gel when at rest (without mechanical stress). This increase in viscosity compared to a binder composition without thixotropic additives is advantageous because it prevents the composition from spreading and run-off after it has been applied to a substrate. When the binder composition is subjected to shearing, its viscosity decreases, making it easier to apply to a substrate.

[0098] The following examples illustrate the performance and quality of the additives according to the present invention, but are not limited to these examples. [Examples]

[0099] Starting material In the examples, the following starting materials were used: TIFF2026143477000001.tif76170

[0100] Measurement method The following measurement method was used in this patent application.

[0101] Weight average molecular weight: The weight-average molecular weight was measured according to OECD (1996), Test No. 118: Determination of the Number-Average Molecular Weight and the Molecular Weight Distribution of Polymers using Gel Permeation Chromatography, OECD Guidelines for the Testing of Chemicals, Section 1, Editions OCDE [OECD Publications], Paris.

[0102] Acid value: The acid value was determined according to standard DIN EN ISO 2114-November 2000, using a 50:50 (vol / vol) xylene / ethanol mixture as the titration solvent. The sample was weighed into a 250 ml Erlenmeyer flask and dissolved in 100 ml of high-temperature xylene / ethanol mixture (approximately 90°C) using a magnetic stirrer. Subsequently, the sample was placed in the magnetic stirrer of a titrator, the electrode was fully immersed, and the mixture was titrated with a 0.1 M ethanolic KOH solution.

[0103] Amine value: The amine value was determined according to standard DIN 53176-November 2002, using a 50:50 (vol / vol) xylene / ethanol mixture as the titration solvent. The sample was weighed into a 250 ml Erlenmeyer flask and dissolved in 100 ml of high-temperature xylene / ethanol mixture (approximately 90°C) using a magnetic stirrer. Subsequently, the sample was placed in the magnetic stirrer of a titrator, the electrode was fully immersed, and the mixture was titrated with 0.1 M isopropanol HCl solution.

[0104] Softening point: The softening point was measured according to the method of NF ISO 2176 - June 2006.

[0105] Particle size: Particle size was measured by laser particle size analysis using a Mastersizer 3000 (Malvern) instrument. The powder was dispersed in air and passed in front of a laser cell. Light intensity was measured and repeated to obtain an accurate particle size distribution. Particle size was expressed in terms of volume. Dv50 (also called D0.5 or x50) corresponds to the median diameter (50% of particles are smaller than the corresponding diameter).

[0106] Yield stress: The yield stress was measured using a Kinexus Pro (Malvern) rheometer. This corresponds to the stress located at the intersection of the storage modulus (G') and the loss modulus (G''), and is expressed in Pa. This explains the stress at which the liquid behavior of the sample replaces its solid properties and structural flow. The curves for the storage modulus (G') and loss modulus (G'') were determined according to the method described below.

[0107] Storage modulus (G'): The storage modulus was measured using a Kinexus Pro (Malvern) controlled stress rheometer. This modulus quantifies the properties of the solid, and therefore the level of the material's structure, and is expressed in Pa. To determine this, stress sweeps from 0.1 to 10000 Pa were performed at a frequency of 1 Hz. The plate / plate geometry used had a gap of 1 mm.

[0108] Example 1: Preparation of diamide (component A) 77.83 g of HMDA (0.67 mol, 1 equivalent) and 422.17 g of 12-HSA (1.34 mol, 2 equivalents) were added to a 1-liter round-bottom flask equipped with a thermometer, Dean and Stark apparatus, condenser, and stirrer. The mixture was heated to 180°C under an inert atmosphere. The removed water was collected in the Dean and Stark apparatus from 150°C. The reaction was monitored by acid and amine values. The reaction was stopped if the acid and amine values ​​were less than 5. The reaction mixture was cooled to 140°C and drained into a silicone mold. Upon cooling to room temperature (20-25°C), the product was converted into flakes.

[0109] Example 2: Preparation of the additive according to the present invention In a 1 L round-bottom flask equipped with a thermometer, Dean and Stark apparatus, condenser, and stirrer, 72 g of diamide, 18 g of polyethylene oxide wax, and 10 g of hydrogenated castor oil, prepared according to Example 1, were mixed at 140°C for 30 minutes under an inert atmosphere. The reaction mixture was then discharged into a silicone mold. Upon cooling to room temperature (20-25°C), the product was converted into flakes. Subsequently, the additives were atomized by air jet to obtain a fine particle size distribution (Dv50 less than 50 μm).

[0110] Example 3: Preparation of additive according to the present invention In a 1 L round-bottom flask equipped with a thermometer, Dean and Stark apparatus, condenser, and stirrer, 40 g of diamide, 10 g of polyethylene oxide wax, and 50 g of hydrogenated castor oil, prepared according to Example 1, were mixed at 140°C for 30 minutes under an inert atmosphere. The reaction mixture was then discharged into a silicone mold. Upon cooling to room temperature (20-25°C), the product was converted into flakes. Subsequently, the additives were atomized by air jet to obtain a fine particle size distribution (Dv50 less than 50 μm).

[0111] Example 4: Preparation of comparative additives In a 1 L round-bottom flask equipped with a thermometer, Dean and Stark apparatus, condenser, and stirrer, 80 g of diamide and 20 g of polyethylene oxide wax, prepared according to Example 1, were mixed at 140°C for 30 minutes under an inert atmosphere. The reaction mixture was then discharged into a silicone mold. Upon cooling to room temperature, the product was converted into flakes. Subsequently, the additive was atomized by air jet to obtain a fine (Dv50 less than 50 μm) and controlled particle size distribution.

[0112] Example 5: Evaluation of the performance quality of coatings in mastic 1) Preparation of mastic The prepared additives were evaluated using mastic formulations. Mastic formulations were prepared using the components shown in Table 2 below (weight percentage values ​​are expressed relative to the weight of the mastic formulation): TIFF2026143477000002.tif38170

[0113] The formulations were prepared using a high-speed disperser (HSD). The resin and plasticizer were added and homogenized in the proportions shown in the first stage (Table 2). The additives were weighed and then added in the second stage. Thus, the reaction mixture was heated to 50°C for 30 minutes under stirring at 3000 rpm. At the end of this phase, the mixture was discharged and the rheological performance quality of these formulations was evaluated.

[0114] 2) Characterization of mastic The yield stress and storage modulus (G') of the mastic prepared using the additives of Examples 2-4 are shown in Table 3 below. A control mastic (without additives) was also tested. TIFF2026143477000003.tif38170

[0115] The mastic containing the rheological additive according to the present invention exhibits superior rheological performance quality compared to mastic containing a mixture of diamide and polyethylene oxide that does not contain hydrogenated castor oil.

Claims

1. - Component A) is 30% to 90% of which is at least one type of diamide, - Component B) consisting of 5% to 40% of at least one functionalized polymer, - Component C) consisting of 5% to 60% of at least one type of wax, An additive that contains, and whose percentage value is a weight percentage relative to the weight of the additive.

2. Component A) includes a diamide obtained by the reaction of at least one diamine and at least one carboxylic acid, Diamine, C ２ ~C ２４ Aliphatic diamine, C ６ ~C １８ Alicyclic diamine, C ６ ~C ２４ Selected from aromatic diamines and mixtures thereof, Carboxylic acids are saturated or unsaturated, linear or branched, unsubstituted or hydroxylated. ２ ~C ３６ The additive according to claim 1, characterized in that it is a carboxylic acid.

3. Component A) is C ２ to C ２４ aliphatic diamines, particularly linear C ２ to C １８ aliphatic diamines, more specifically linear C ２ to C １２ The additive according to claim 2, characterized in that it comprises a diamide obtained from at least one diamine selected from aliphatic diamines.

4. Component A) is C ２ ~C ２２ Carboxylic acids, especially hydroxylated C ２ ~C ２２ Carboxylic acids and optionally unsubstituted C ２ ~C ２２ Carboxylic acids, more specifically hydroxylated C １２ ~C ２０ Carboxylic acids and optionally unsubstituted C ２ ~C １４ The additive according to claim 2 or 3, characterized by comprising a diamide obtained from at least one carboxylic acid selected from carboxylic acids.

5. The additive according to any one of claims 1 to 4, characterized in that component A) contains a diamide obtained by the reaction of 1,2-ethylenediamine, 1,5-pentamethylenediamine, or 1,6-hexamethylenediamine with 12-hydroxystearic acid and optionally decanoic acid.

6. The additive according to any one of claims 1 to 5, characterized in that it contains component A) in an amount of 35% to 90% by weight, particularly 40% to 90% by weight, and more specifically 40% to 85% by weight, relative to the weight of the additive.

7. The additive according to any one of claims 1 to 6, characterized in that component B) comprises a polymer functionalized with a polar group, particularly a polar group selected from carboxylic acids, anhydrides, ethers, aldehydes, alcohols, amines and mixtures thereof, more specifically, at least a carboxylic acid group.

8. The additive according to any one of claims 1 to 7, characterized in that component B) contains a functionalized polymer having an acid value of 3 to 50, or 5 to 40, or 8 to 35, or 10 to 25 mg KOH / g.

9. The additive according to any one of claims 1 to 8, characterized in that component B) comprises a functionalized polyolefin, particularly an oxidized polyolefin, and more specifically, an oxidized polyethylene.

10. The additive according to any one of claims 1 to 9, characterized in that it contains component B) in an amount of 5% to 35% by weight, particularly 10% to 35% by weight, more specifically 10% to 30% by weight, relative to the weight of the additive.

11. The additive according to any one of claims 1 to 10, characterized in that component C) contains a wax that exhibits a softening point above 70°C, particularly between 70°C and 120°C.

12. The additive according to any one of claims 1 to 11, characterized in that component C) comprises waxes selected from mineral waxes, natural waxes, synthetic waxes and mixtures thereof, in particular paraffin wax, microcrystalline wax, ceresin, montan wax, cerides, diols or triols completely or partially esterified with fatty acids, vegetable waxes or animal waxes, Fischer-Tropsch wax, polyethylene and / or polypropylene wax, poly(ethylene oxide) and / or poly(propylene oxide) wax and mixtures thereof, more specifically, hydrogenated castor oil.

13. The additive according to any one of claims 1 to 12, characterized in that component C) contains a hydroxylated wax, preferably hydrogenated castor oil.

14. The additive according to any one of claims 1 to 13, characterized in that it contains component C) in an amount of 5% to 55% by weight, particularly 10% to 55% by weight, or more specifically 10% to 50% by weight, relative to the weight of the additive.

15. The additive according to any one of claims 1 to 14, characterized in that the weight ratio of component A to component B) is in the range of 0.8 to 10, particularly 1 to 9, and more specifically 1.5 to 8.

5.

16. The additive according to any one of claims 1 to 15, characterized in that it is in solid form, particularly in the form of solid particles, more specifically in the form of solid particles having a volume average size of less than 50 μm or less than 25 μm.

17. A pre-activating additive composition comprising the additive and plasticizer according to any one of claims 1 to 16.

18. A binder composition comprising a binder and an additive according to any one of claims 1 to 16 or a pre-activating additive composition according to claim 17.

19. The binder composition according to claim 18, characterized in that it is a coating composition, particularly a varnish, rendering, surface gel, paint or ink composition, adhesive, glue or mastic composition, molding composition, composite material composition, chemical sealing composition, leak-proofing composition, and a photocrosslinkable composition for stereolithography or 3D printing of objects, particularly by inkjet printing.

20. Use of the additive according to any one of claims 1 to 16 or the pre-activated additive composition according to claim 17, as a rheological agent, particularly as a thixotropic agent.

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