Polyamide- and additive-based composition

Abstract

The present invention relates to a composition comprising: - an additive (A) comprising: o at least one compound selected from a diamide (A1) obtained by the reaction between at least one diamine and at least one carboxylic acid; a monoamide (A2); or a triamide (A3); o optionally, a vegetable oil (A4); o optionally, an optionally functionalized polymer (A5); - a polyamide (B) comprising the polycondensation product of an acid component and an amine component, the acid component comprising: o at least one fatty acid dimer; o at least one aliphatic diacid; o optionally, at least one chain limiter; the amine component comprising: o at least one aliphatic diamine; o optionally, at least one cycloaliphatic diamine; o optionally, at least one polyetherdiamine; the composition being characterized in that, when the diamide (A1) comprises ethylene bis-stearamide, its mass content is greater than 10% by weight relative to the total weight of the composition; and the composition comprising at least 60% by weight of polyamide (B) relative to the total weight of the composition.

Description

[0001] COMPOSITION BASED ON POLYAMIDE AND ADDITIVE

[0002] Scope of the invention

[0003] The present invention relates to a composition based on polyamide and amide or diamide additive.

[0004] TECHNOLOGICAL BACKGROUND

[0005] It is known that acid-modified polyolefin or maleic anhydride waxes are used as rheology agents in polyamide-based hot melt adhesive compositions. However, these compositions are generally labeled as skin irritants or allergens. New regulations are therefore aimed at restricting the use of these waxes in polyamide compositions.

[0006] Polyamide-based hot melt adhesives are typically used in furniture applications, for example, for filling wood knots. However, polyethylene-wax-free adhesives have application disadvantages, such as the formation of filaments on applicators at the end of the application, which is unacceptable to the user and can lead to contamination during subsequent applications.

[0007] Therefore, there is a need for new polyamide-based compositions to address at least one of the aforementioned disadvantages.

[0008] In particular, there is a need for new polyamide-based compositions that allow for application without filament residue, and that have a high content of bio-based ingredients.

[0009] There is a need for new polyamide-based compositions that allow for application without filament residue and are transparent.

[0010] DESCRIPTION OF THE INVENTION

[0011] The present invention relates to a composition comprising: an additive (A) comprising: o at least one compound selected from a diamide (A1) obtained by the reaction between at least one diamine and at least one carboxylic acid; a monoamide (A2); and a triamide (A3); o optionally a vegetable oil (A4); o optionally a polymer optionally functionalized (A5); a polyamide (B) comprising the polycondensation product of an acid component and an amine component, the acid component comprising: o at least one fatty acid dimer; o at least one aliphatic diacid; o optionally at least one chain limiter; the amine component comprising: o at least one aliphatic diamine; o optionally at least one cycloaliphatic diamine; o optionally at least one polyetherdiamine;said composition being characterized in that when the diamide (A1) comprises ethylene bis-stearamide, its mass content is greater than 10% by weight relative to the total weight of the composition; and said composition comprising at least 60% by weight of polyamide (B) relative to the total weight of the composition.

[0012] Addendum (A)

[0013] Diamide (A1)

[0014] The additive (A) may comprise a diamide (A1) or a mixture of diamides (A1).

[0015] For the purposes of the present invention, a diamide is a compound having two amide functions (-NH-C(=O)-).

[0016] A diamide is obtained by reacting at least one diamine with at least one carboxylic acid. An asymmetric diamide can be obtained by reacting a diamine with separate carboxylic acids. A mixture of diamides can be obtained by using separate diamines and / or separate carboxylic acids.

[0017] Preferably, the diamide (A1) is obtained with at least one diamine selected from a C2-C24 aliphatic diamine, a C6-C18 cycloaliphatic diamine, a C6-C24 aromatic diamine, a polyetherdiamine, and mixtures thereof. The diamide may be obtained with a mixture of said diamines. For the purposes of the present invention, a diamine is a compound having two primary amine groups (-NH2).

[0018] For the purposes of this invention, an aliphatic diamine is an acyclic diamine. A C2 to C24 aliphatic diamine is an aliphatic diamine comprising 2 to 24 carbon atoms. An aliphatic diamine may be linear or branched, preferably linear.

[0019] Linear aliphatic amines may be selected from the group consisting of 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,10-decanediamine, 1,12-dodecamethylenediamine and mixtures thereof; preferably selected from the group consisting of 1,2-ethylenediamine, 1,5-pentamethylenediamine and 1,6-hexamethylenediamine.

[0020] Branched aliphatic amines can be selected from 1,2-propylenediamine, 2,2-dimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine and mixtures thereof.

[0021] For the purposes of this invention, a cycloaliphatic diamine is a non-aromatic diamine comprising a ring, in particular a ring having 6 carbon atoms. A C6 to C18 cycloaliphatic diamine is a cycloaliphatic diamine comprising 6 to 18 carbon atoms.

[0022] Cycloaliphatic diamines can be chosen from 1,2-, 1,3- or 1,4-diaminocyclohexane, 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-

[0023] 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 selected from 1,3- or 1,4-bis(aminomethyl)cyclohexane, 1,2-, 1,3- or

[0024] 1,4-bis(aminomethyl)cyclohexane, isophorone diamine and 4,4'-diaminodicyclohexylmethane.

[0025] For the purposes of the present invention, an aromatic diamine is a diamine comprising an aromatic ring. A C6 to C24 aromatic diamine is an aromatic diamine comprising 6 to 24 carbon atoms.

[0026] Aromatic diamines may be selected from meta- and para-phenylenediamine, meta- and para-xylylenediamine, meta- and para-toluynediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and mixtures thereof; preferably from meta- and para-xylylenediamine.

[0027] The polyetherdiamine can be chosen from polyoxyalkylene diamines with a number molecular weight (Mn) ranging from 200 to 4000 g / mol. Preferably, it is a polyoxyalkylene chain with an amine group at the end of the chain.

[0028] Polyetherdiamine is preferably chosen from polyoxypropylenediamines, polyoxybutylenediamines, bis-(diaminopropyl)-polytetrahydrofuran and mixtures thereof.

[0029] Preferably, polyetherdiamine is a polyoxypropylenediamine.

[0030] Polyetherdiamines are commercially available under the names Baxxodur® from BASF and Jeffamine® from Huntsman (such as Jeffamine® D-2000, which is a primary polyoxypropylene diamine with 2 primary amine groups and 33 oxypropylene units, or Jeffamine® D-400, which is a primary polyoxypropylene diamine with 2 primary amine groups and a maximum of 6 oxypropylene units).

[0031] Preferably, the diamide (A1) is a diamide obtained with at least one diamine selected from a C2-C24 aliphatic diamine, in particular a C2-C18 linear aliphatic diamine, more particularly a C4-C10 linear aliphatic diamine, more particularly 1,5-pentamethylenediamine or 1,6-hexamethylenediamine.

[0032] Preferably, the diamide (A1) is a diamide obtained with at least one carboxylic acid in C2 to C36. The diamide can be obtained with a mixture of carboxylic acids in C2 to C36.

[0033] For the purposes of this invention, a C2 to C36 carboxylic acid is a compound having a carboxylic acid functional group (-COOH) and 2 to 36 carbon atoms. The carboxylic acid may be linear or branched, preferably linear. The carboxylic acid may be saturated or unsaturated, preferably saturated. The carboxylic acid may be unsubstituted or hydroxylated. A hydroxylated carboxylic acid is a carboxylic acid substituted with one or more hydroxyl groups, preferably with a hydroxyl group.

[0034] The carboxylic acid can be a hydroxylated carboxylic acid possibly mixed with an unsubstituted carboxylic acid.

[0035] Hydroxylated carboxylic acids are preferably chosen from the following: 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, hydroxy decanoic acid and mixtures thereof; preferably 12-hydroxy stearic acid or a binary or ternary mixture of 12-hydroxy stearic acid with the other hydroxylated acids mentioned above.

[0036] Unsubstituted carboxylic acids are preferably selected from the following: acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic 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.

[0037] Preferably, the diamide (A1) is obtained with at least one carboxylic acid selected from a C2 to C22 carboxylic acid, in particular a C2 to C22 hydroxylated carboxylic acid and possibly an unsubstituted C2 to C22 carboxylic acid, more particularly a C12 to C20 hydroxylated carboxylic acid and possibly an unsubstituted C2 to C14 carboxylic acid.

[0038] Preferably, the diamide (A1) is obtained:

[0039] - with at least one diamine chosen from a linear aliphatic diamine in C4 to C10;

[0040] - with at least one carboxylic acid chosen from a carboxylic acid hydroxylated at C2 to C22, an unsubstituted carboxylic acid at C2 to C14, and mixtures thereof.

[0041] According to a particularly preferred embodiment, the diamide (A1) is obtained by reaction between 1,5-pentamethylenediamine or 1,6-hexamethylenediamine, 12-hydroxystearic acid, and optionally an unsubstituted acid at C2 to C14.

[0042] Preferably, when the diamide (A1) comprises ethylene bis-stearamide, its mass content is greater than or equal to 12% by weight relative to the total weight of the composition.

[0043] If present, the mass content of diamide (A1) preferably ranges from 5% to 40% by weight, more preferably from 10% to 35% by weight relative to the total weight of the composition. Monoamide (A2)

[0044] The additive (A) may comprise a monoamide (A2) or a mixture of monoamide (A2).

[0045] For the purposes of the present invention, monoamide means an amide comprising a single amide function, preferably a primary amide function.

[0046] The amide (A2) is preferably chosen from the group consisting of stearamide, behenamide, capramide, caproamide, caprylamide, elaidamide, erucamide, palmitamide, oleamide, and mixtures thereof.

[0047] The amide can be prepared by any method known to a person skilled in the art, such as, for example, by reaction between fatty acids and ammonia.

[0048] If present, the mass content of monoamide (A2) preferably ranges from 5% by weight to 40% by weight, more preferably from 10% to 35% by weight relative to the total weight of the composition.

[0049] Triamide (A3)

[0050] The additive (A) may comprise a triamide (A3) or a mixture of triamide (A3).

[0051] For the purposes of the present invention, triamide means an amide comprising three amide functions, preferably three primary amide functions.

[0052] Triamide (A3) can be obtained by reaction between at least one triamine and at least one carboxylic acid.

[0053] Preferably, triamide (A3) is obtained with at least one triamine selected from a C2-C24 aliphatic triamine, a C6-C18 cycloaliphatic triamine, a C6-C24 aromatic triamine, a polyethertriamine, and mixtures thereof. Even more preferably, triamide (A3) is obtained with at least one polyethertriamine.

[0054] For the purposes of the present invention, a triamine is a compound having three primary amine functions (-NH2).

[0055] Polyethertriamine can be chosen from polyoxyalkylene triamines with a number molecular weight (Mn) ranging from 200 to 4000 g / mol.

[0056] Polyethertriamine is preferably chosen from polyoxypropylenetriamines, polyoxybutylenetriamines, and mixtures thereof.

[0057] Preferably, polyethertriamine is a polyoxypropylenetriamine.

[0058] Examples of commercially available triamines include Jeffamine® T-3000, which is a primary polyoxypropylene triamine carrying 3 primary amine groups with a number of 50 oxypropylene units, or Jeffamine® T-403 from HUNSTMAN.

[0059] Preferably, the triamide (A3) is a triamide obtained with at least one carboxylic acid in C2 to C36. The triamide can be obtained with a mixture of carboxylic acids in C2 to C36.

[0060] For the purposes of this invention, a C2 to C36 carboxylic acid is a compound having a carboxylic acid functional group (-COOH) and 2 to 36 carbon atoms. The carboxylic acid may be linear or branched, preferably linear. The carboxylic acid may be saturated or unsaturated, preferably saturated. The carboxylic acid may be unsubstituted or hydroxylated. A hydroxylated carboxylic acid is a carboxylic acid substituted with one or more hydroxyl groups, preferably with a hydroxyl group.

[0061] The carboxylic acid can be a hydroxylated carboxylic acid possibly mixed with an unsubstituted carboxylic acid.

[0062] Hydroxylated carboxylic acids are preferably chosen from the following: 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, hydroxy decanoic acid and mixtures thereof; preferably 12-hydroxy stearic acid or a binary or ternary mixture of 12-hydroxy stearic acid with the other hydroxylated acids mentioned above.

[0063] Unsubstituted carboxylic acids are preferably selected from the following: acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic 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. Vegetable oil (A4)

[0064] The vegetable oil can be chosen from castor oil, linseed oil, rapeseed oil, sunflower oil, soybean oil, corn oil, palm oil, copra (coconut) oil, ethoxylated hydrogenated castor oil, and mixtures thereof.

[0065] Vegetable oil can be partially or totally hydrogenated.

[0066] Preferably, castor oil is hydrogenated castor oil.

[0067] Hydrogenated castor oil is a commercially available compound, for example, under CAS No. 8001-78-3. It typically consists of 85 to 90% by mass of ricinoleic acid triglycerides, a large proportion of whose double bonds have been hydrogenated. It also contains, in smaller quantities, hydrogenated linoleic acid triglycerides, hydrogenated oleic acid triglycerides, and hydrogenated stearic acid triglycerides, among others.

[0068] Examples include Kao 85P wax from Kao Corporation or C waxes from Kokura Synthetic Industries.

[0069] Optionally functionalized polymer (A5)

[0070] The additive (A) may comprise an optionally functionalized polymer (A5) or a mixture of optionally functionalized polymers (A5).

[0071] For the purposes of this invention, a functionalized polymer is a polymer comprising a backbone bearing functional groups. Functional groups are groups capable of reacting with other compounds during a reaction or of facilitating the compatibility of the polymer with the additive. The polymer backbone is the main chain comprising motifs resulting from the polymerization of monomers, in particular ethylenically unsaturated monomers. A functionalized polymer can be obtained by functionalizing an existing polymer, notably by oxidation or grafting reactions. Alternatively, a functionalized polymer can be obtained by introducing monomers bearing functional groups during the polymerization reaction.

[0072] The optionally functionalized polymer (A5) can notably have a weight average molecular mass of 600 to 80,000 g / mol, in particular of 1000 to 5000 g / mol.

[0073] The optionally functionalized polymer (A5) may be selected from a polyolefin, polyester, polyether, (meth)acrylic polymer, polyurethane, polyamide, styrene-maleic copolymer, and mixtures thereof. The functionalized polymer may include a backbone formed by the polymerization of one or more monomers selected from polyol, poly(carboxylic acid), polyester, anhydride, polyisocyanate, polyamine, diepoxide, an ethylenically unsaturated monomer, and mixtures thereof. Ethylenically unsaturated monomers are those having a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is generally included in a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl, and corresponding combinations thereof.The carbon-carbon double bonds of a phenyl ring are not considered polymerizable carbon-carbon double bonds. Preferably, the polymer (A5) is a functionalized polyolefin, in particular an oxidized polyolefin, more specifically an oxidized polyethylene.

[0074] For the purposes of this invention, a polyolefin is a polymer comprising repeating units resulting from the polymerization of olefins. An olefin is an alkene, in particular an alkene having 2 to 8, especially 2 to 6, more particularly 2 to 4, carbon atoms. Preferably, the olefins used to obtain polyolefins are α-olefins, that is, olefins having a terminal carbon-carbon double bond. Examples of suitable olefins are ethylene, propylene, 1-butene, isobutene, and mixtures thereof, preferably ethylene and propylene. A polyolefin may be a homopolymer of a single type of olefin (e.g., ethylene homopolymer), or a copolymer of at least two olefins (e.g., polymers of mixtures of ethylene, propylene, 1-butene, and / or isobutene).Furthermore, a polyolefin may also comprise one or more units resulting from the polymerization of ethylenically unsaturated monomers other than olefins, particularly ethylenically unsaturated monomers possessing a carboxylic acid or anhydride group. These ethylenically unsaturated monomers may be copolymerized with the olefins or added subsequently, for example, by grafting. When ethylenically unsaturated monomers with carboxyl or anhydride groups are used, the resulting polyolefin is functionalized with carboxylic acid or anhydride groups.

[0075] For the purposes of this invention, an oxidized polyolefin is a polyolefin containing at least carboxylic acid groups. An oxidized polyolefin may further comprise one or more groups selected from aldehydes, ketones, ethers, alcohols, and mixtures thereof. An oxidized polyolefin may, in particular, be obtained by one of the following methods:

[0076] 1) by oxidation, in particular oxidation in the molten state, of a nonpolar polyolefin, in particular of a nonpolar polyethylene; 2) by oxidative degradation of polyolefin plastics, in particular of polyethylene plastics;

[0077] 3) by polymerization of olefins, in particular ethylene and / or propylene, with ethylenically unsaturated monomers having a carboxylic acid or anhydride group, in particular (meth)acrylic acid;

[0078] 4) by radical grafting of ethylenically unsaturated monomers having a carboxylic acid or anhydride group, in particular maleic anhydride, onto a nonpolar polyolefin, in particular a nonpolar polyethylene and / or polypropylene.

[0079] According to one embodiment, the oxidized polyolefin is a homopolymer or a copolymer of at least one olefin, in particular an α-olefin, more particularly ethylene and / or propylene.

[0080] Oxidized polyolefin can notably be selected from oxidized polyethylene, oxidized polypropylene, oxidized poly(ethylene-co-propylene), oxidized ethylene-α-olefin copolymer, ethylene and (meth)acrylic acid copolymer, ethylene and / or propylene polymer grafted with an ethylenically unsaturated monomer bearing a carboxylic acid or anhydride group, for example with (meth)acrylic acid or maleic anhydride.

[0081] Preferably, the additive (A) does not include polymer (A5).

[0082] Addendum (A)

[0083] The additive (A) is preferably a solid compound at 23°C.

[0084] Preferably, the additive (A) is malleable at 23°C.

[0085] The additive (A) preferably has a weight average molecular mass (Mw) less than or equal to 3000 g / mol, preferably less than or equal to 2000 g / mol, even more preferably ranging from 400 to 1800 g / mol.

[0086] The weight-average molecular mass (Mw) can be measured by gel permeation chromatography (GC).

[0087] The composition according to the invention preferably comprises 5% to 40% by weight of additive(s) (A), more preferably 10% to 30% by weight, and even more preferably 15% to 30% by weight, relative to the total weight of the composition.

[0088] The additive (A) according to the invention may in particular be in solid form, especially in the form of solid particles, more particularly in the form of solid particles having a volume average size of less than 50 pm. The size may be determined by laser diffraction.

[0089] The additive (A) can be obtained by a process comprising the following steps: a) mixing of the components (A1) or (A2) or (A3), and optionally (A4) and optionally (A5) at high temperature (140 to 220°C) to form a homogeneous mixture; b) cooling of the mixture obtained in step a) to ambient temperature (20-25°C) to obtain a solid; c) micronization of the solid obtained in step b) to obtain solid particles having a volume average size of less than 50 pm.

[0090] The additive (A) preferably has a melting point from 60°C to 180°C, preferably from 100°C to 160°C. The melting point can be determined by DSC.

[0091] Commercially available additives (A) are also available, such as, for example, Deurex A28P, Deurex A24K marketed by the Deurex company, and Ekfa RM1900 marketed by BASF.

[0092] For the purposes of the present invention, a polyamide is a compound comprising more than 2 amide functions within its main chain, preferably more than 5 amide functions.

[0093] According to the invention, the composition therefore comprises two different ingredients: the additive (A) and the polyamide (B).

[0094] Polyamide (B) preferably has a weight average molecular mass (Mw) greater than 8,000 g / mol, even more preferably from 10,000 to 150,000 g / mol, and even more preferably from 12,000 to 100,000 g / mol.

[0095] The weight average molecular mass (Mw) of polyamide can be measured by gel permeation chromatography (GC).

[0096] The molar ratio -COOH / (-NH and / or -NH2) in polyamide can range from 0.2 to 4.0, preferably from 0.3 to 3.5.

[0097] The molar ratio of -COOH to (-NH₂ and / or -NH₂) between carboxylic acid groups and primary and / or secondary amine groups, the contents of which are expressed in mg KOH / g, is determined potentiometrically. Polyamide (B) may have an acid value index (AI) ranging from 0.20 to 17 mg KOH / g, preferably from 0.5 to 15 mg KOH / g, and most preferably from 1 to 12 mg KOH / g.

[0098] The Acid Value (AV), determined by potentiometry according to ASTM D 4662 and ISO 2114, represents the amount of carboxylic functional groups expressed in milligrams of potassium required to neutralize the acidity of 1 gram of polyamide (mg KOH / g).

[0099] Polyamide (B) may have a viscosity less than or equal to 4 Pa.s at 205°C, preferably still from 0.2 to 3.0 Pa.s, and even more preferably from 0.3 to 2.0 Pa.s.

[0100] Viscosity is measured according to ASTM D3236-15 (2021), using Brookfield equipment and an SC4-A27 needle.

[0101] The softening point can be measured according to ASTM D3461-18 (2018), using a "Cup & Bail" device and a temperature ramp of 2°C / min.

[0102] Polyamide (B) can have a softening temperature ranging from 150°C to 180°C.

[0103] Polyamide (B) comprises the polycondensation product of an acid component and an amine component, the acid component comprising: o at least one fatty acid dimer; o at least one aliphatic diacid; o optionally at least one chain limiter; the amine component comprising: o at least one aliphatic diamine; o optionally at least one cycloaliphatic diamine; o optionally at least one polyetherdiamine.

[0104] Fatty acid dimer(s)

[0105] The acid component preferably comprises, per mole of acid component, 30 to 90 moles, more preferably 40 to 80 moles, and even more preferably 50 to 70 moles of fatty acid dimer(s).

[0106] Fatty acid dimers are polymerized fatty acids, referring to compounds produced from coupling reactions of unsaturated fatty acids that lead to mixtures of products bearing two acidic functional groups. Fatty acid dimers can be obtained by the dimerization of unsaturated monocarboxylic acids. These unsaturated monocarboxylic acids can be selected from those containing 10 to 22 carbon atoms (C10 to C22); preferably from those containing 12 to 18 carbon atoms (C12 to Cis); and most preferably from those containing 16 to 18 carbon atoms (C16 to Cis).

[0107] Fatty acid dimers can be obtained from unsaturated monocarboxylic acids by well-known processes such as those described, for example, in US patent applications 2,793,219 and 2,955,121. The unsaturated monocarboxylic acids can be selected from oleic acid, linoleic acid, linolenic acid, and mixtures thereof.

[0108] Depending on whether they are crude or distilled, fatty acid dimers can have a dimer content ranging from 75% to over 98%, mixed with varying amounts of higher monomers, trimers and homologues depending on the commercial grades.

[0109] Fatty acid dimers are commercially available under the names RadiacidO from Oleon, Pripol® from Cargill, or Unydime® from Kraton.

[0110] Aliphatic diacids

[0111] Throughout the description, the terms "diacid" or "dicarboxylic acid" or "dicarboxylic acid" refer to the same product.

[0112] The acid component preferably comprises, per mole of acid component, 5 to 65 moles, more preferably 8 to 40 moles, and even more preferably 10 to 30 moles of aliphatic diacid(s).

[0113] The aliphatic diacid can be chosen from among the saturated aliphatic dicarboxylic acids, preferably from linear or branched saturated aliphatic dicarboxylic acids.

[0114] Dicarboxylic acids can be selected from the group consisting of succinic acid (butanedioic acid) (C4), glutaric acid (pentanedioic acid) (C5), adipic acid (hexanedioic acid) (Ce), pimelic acid (heptanedioic acid) (C7), suberic acid (octanedioic acid) (Cs), azelaic acid (nonanedioic acid) (C9), sebacic acid (decanedioic acid) (C10), undecanedioic acid (Cn), dodecanedioic acid (C12), brassylic acid (tridecanedoic acid) (C13), tetradecanedioic acid (C14), pentadecanedioic acid (C15), thapsic acid (hexadecanedioic acid) (Cie), and mixtures thereof; even more preferentially among azelaic acid (C9), sebacic acid (C10), dodecanedioic acid (C12), and mixtures thereof.

[0115] Preferably, saturated aliphatic dicarboxylic acids comprise from 4 to 22 carbon atoms (C4-22), even more preferably from 4 to 20 (C4-20), and even more preferably from 6 to 18 (Ce-is).

[0116] According to one embodiment, adipic acid (C6) represents at least 75 mol% of the aliphatic dicarboxylic acids, preferably at least 80 mol%.

[0117] The acid component comprises in total at least 50 moles, preferably at least 60 moles, and even more preferably at least 70 moles of fatty acid dimer(s) and aliphatic diacid(s).

[0118] Chain limiters

[0119] Polyamide (B) can be synthesized in the presence of one or more chain limiter(s).

[0120] The chain limiter can be chosen from monocarboxylic acids that can contain at least one heteroatom (O, S, Cl, F) or the corresponding esters, or mono-isocyanates.

[0121] Preferably, the chain limiter is a monocarboxylic acid.

[0122] The monocarboxylic acid can be chosen from aliphatic monocarboxylic acids, alicyclic acids, aromatic monocarboxylic acids and mixtures thereof.

[0123] The monocarboxylic acid may be an aliphatic monocarboxylic acid selected from acetic acid, propionic acid, lactic acid, valeric acid, caproic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid or mixtures thereof.

[0124] Alicyclic acid can be a cyclohexanecarboxylic acid.

[0125] The monocarboxylic aromatic acid may be chosen from benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and mixtures thereof.

[0126] Preferably, the chain limiter is an aliphatic monocarboxylic acid.

[0127] For example, we can mention Radiacid®, which is commercially available from

[0128] Oleon. The acid component may comprise, per mole of acid component, from 0% to 40 moles % of chain limiter(s), preferably from 5 to 30 moles %, and even more preferably from 15 to 30 moles %.

[0129] Aliphatic diamines

[0130] The amine component may comprise, per mole of amine component, from 30 to 100 moles, preferably from 60% to 100 moles, and even more preferably from 70 to 100 moles % of aliphatic diamine(s).

[0131] The aliphatic diamine can be chosen from linear or branched saturated aliphatic diamines comprising 2 to 12 carbon atoms, and mixtures thereof.

[0132] Among the branched aliphatic diamines of interest are 2-methylpentamethylenediamine, 1,3-pentanediamine, methylpentanediamine and trimethylhexamethylenediamine.

[0133] Preferably, the aliphatic diamine is chosen from among the saturated linear aliphatic diamines of formula H2N-(CH2) n -NH2 with n ranging from 2 to 12, and their mixtures.

[0134] Preferably, the aliphatic diamine is chosen from the group consisting of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexamethylene diamine, decamethylene diamine and mixtures thereof.

[0135] Preferably, the aliphatic diamine is chosen from ethylene diamine, hexamethylene diamine, and mixtures thereof.

[0136] Polyetherdiamines

[0137] The amine component may comprise, per mole of amine component, from 0 to 20 moles%, preferably from 5 to 20 moles%, and even more preferably from 8 to 18 moles% of polyetherdiamine(s).

[0138] Polyetherdiamine can be chosen from polyoxyalkylene diamines with a number molecular weight (Mn) ranging from 200 to 4000 g / mol.

[0139] Preferably, it is a polyoxyalkylene chain with an amine group at the end of the chain.

[0140] Polyetherdiamine can be selected from polyoxypropylenediamines, polyoxybutylenediamines, bis-(diaminopropyl)-polytetrahydrofuran and mixtures thereof.

[0141] Preferably, the polyetherdiamine is a polyoxypropylenediamine. Polyetherdiamines are commercially available under the names Jeffamine® from Huntsman and Baxxodur® from BASF.

[0142] cvcloaliphatic diamines

[0143] The amine component may include one or more cycloaliphatic diamines.

[0144] The cycloaliphatic diamine can be chosen from bis-(3,5-dialkyl-4-aminocyclohexyl)-methane, bis-(3,5-dialkyl-4-aminocyclohexyl)-ethane, bis-(3,5-dialkyl-4-aminocyclohexyl)-propane, bis-(3,5-dialkyl-4-aminocyclohexyl)-butane, bis-(3-methyl-4-aminocyclohexyl)-methane (BMACM or MACM), p-bis(aminocyclohexyl)-methane (PACM), isopropylidenedi(cyclohexylamine) (PACP), isophoronediamine, piperazine, aminoethylpiperazine, dimethylpiperazine, 4,4'-trimethylenedipiperidine, 1,4-cyclohexanediamine, or a cycloaliphatic diamine having a carbon skeleton (e.g., norbomyl). methane, cyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl), di(methylcyclohexyl)propane), and their mixtures.

[0145] A non-exhaustive list of these cycloaliphatic diamines is given in the publication "Cycloaliphatic amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp.386-405).

[0146] The amine component may comprise, per mole of amine component, from 0 to 70 moles %, of cycloaliphatic diamine(s).

[0147] Polyamide (B)

[0148] Preferably, the polyamide (B) comprises the polycondensation product of an acid component and an amine component, the acid component comprising: o 30 to 90 moles % of fatty acid dimer(s); o 5 to 64 moles % of aliphatic diacid(s); o 0 to 30 moles % of chain limiter(s); the amine component comprising: o 30 to 100 moles % of aliphatic diamine(s) preferably selected from the group consisting of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexamethylene diamine, decamethylene diamine and mixtures thereof; o 0 to 70 moles % of cycloaliphatic diamine(s); o 0 to 20 moles % of polyetheramine(s). Polyamide can be obtained by polycondensation of the acid component and the amine component according to a conventional process.Polyamide can notably be prepared by mixing the reagents, then heating to a temperature greater than or equal to 100°C, preferably greater than or equal to 150°C, and even more preferably greater than or equal to 200°C.

[0149] The reaction can be carried out under an inert atmosphere such as, for example, under nitrogen.

[0150] A second heating stage at a pressure between 500 and 50,000 Pa (5 and 500 mbar) can be implemented to allow the elimination of traces of water, and of all volatile compounds.

[0151] Preferably, the composition includes at least 65% by weight of polyamide (B).

[0152] The composition according to the invention is preferably a hot melt adhesive composition.

[0153] The composition may comprise more than 90% by weight of the aforementioned additive (A) and polyamide (B), preferably more than 92% by weight, and even more preferably more than 95% by weight, relative to the total weight of said composition.

[0154] The composition may include at least one additive (different from the aforementioned additive (A).

[0155] The additive can be chosen from fillers, plasticizers, tackifying resins, antioxidants or stabilizers, release agents, surfactants, pigments and mixtures thereof.

[0156] One example of pigments is carbon black.

[0157] Examples of antioxidants include amino, phenolic, and phosphorus compounds.

[0158] The polyamide composition may include from 0 to 8% by weight of additives, preferably from 1 to 6% relative to the total weight of said composition.

[0159] The composition can be obtained by simply mixing the ingredients, for example, by mixing the additive (A) and the polyamide (B), optionally with one or more additional additives. The composition preferably has a viscosity at 205°C ranging from 0.1 Pa·s to 1.5 Pa·s. The viscosity is measured according to ASTM D3236-15 (2021), using Brookfield equipment and an SC4-A27 needle.

[0160] Use

[0161] The present invention also relates to the use of the composition as defined above, as a hot melt adhesive in particular in the filter market or when using nozzles.

[0162] The present invention relates to the use of the composition as defined above as a hot melt adhesive to fill defects in various substrates such as, for example, wood, or to hold a filter in a folded position (for example, folded like an accordion).

[0163] The composition according to the invention advantageously allows to be deposited by robot or gun with limited or even no formation of adhesive threads after stopping the deposit.

[0164] Experimental section

[0165] The following examples illustrate the invention without limiting it.

[0166] The products used are as follows:

[0167] Ekfa RM1900: amide wax and hydrogenated castor oil (Mw = 1404 g / mol) with a melting point of 136-140°C, marketed by BASF

[0168] Deurex A28P: stearamide wax with a Mw = 416 g / mol, marketed by Deurex

[0169] Deurex A24K: behenamide wax with a Mw = 511 g / mol, marketed by Deurex

[0170] Example 1: Polyamide preparation process

[0171] In a suitable reactor equipped with a mixer, all the reactive raw materials are introduced and then heated under nitrogen for 4.5 hours to a temperature of 225°C (see ingredient composition in the table below). The reaction mixture is maintained at 225°C for 2.5 hours and then placed under vacuum (pressure between 10 and 30 mbar) for 1 hour. Finally, the additives are added as a mass percentage relative to the weight of the polyamide.

[0172] Polyamide

[0173] Example 2: Preparation of an additive (A)

[0174] In a 1 L round-bottom flask equipped with a thermometer, a Dean-Stark flask, a condenser, and a stirrer, 49.96 grams of hexamethylenediamine (0.43 moles, 0.86 amine equivalents) and 271.04 grams of a mixture of 12-hydroxystearic acid (0.86 moles, 0.86 acid equivalents) are introduced into a nitrogen atmosphere. The mixture is heated to 200°C under a continuous flow of nitrogen. The water removed accumulates in the Dean-Stark flask at 150°C. The reaction is monitored by the acid and amine values. When the acid and amine values ​​are below 10 mg KOH / g, the reaction mixture is cooled to 150°C and then discharged into a silicone mold. Once cooled to room temperature, the product is mechanically micronized by grinding and sieving to obtain a fine and controlled particle size with an average size of 7 microns.

[0175] 5 Example 3: Process for preparing hot-melt compositions

[0176] At atmospheric pressure, the polyamide P1 from Example 1 and the additive (A) are mixed for 15 minutes under nitrogen, followed by 30 minutes under vacuum. The product is then returned to atmospheric pressure for unloading. The following compositions were prepared:

[0177] Viscosity was measured using a Brookfield apparatus according to ASTM D3236-15. The measurement was taken using an SC4-A27 needle at 190°C and 50 rpm. Transparency or opacity was assessed visually.

[0178] The presence of filaments was determined using the following method: A thin layer of polyamide was spread at 200°C using a spatula onto a metal substrate, and the presence or absence of filaments was visually observed when the spatula separated from the deposited polyamide. The results are presented according to the following criteria:

Claims

DEMANDS 1. Composition comprising: an additive (A) comprising: o at least one compound selected from a diamide (A1) obtained by the reaction between at least one diamine and at least one carboxylic acid; a monoamide (A2); and a triamide (A3); o optionally a vegetable oil (A4); o optionally a polymer optionally functionalized (A5); a polyamide (B) comprising the polycondensation product of an acid component and an amine component, the acid component comprising: o at least one fatty acid dimer; o at least one aliphatic diacid; o optionally at least one chain limiter; the amine component comprising: o at least one aliphatic diamine; o optionally at least one cycloaliphatic diamine; o optionally at least one polyetherdiamine; said composition being characterized in that when the diamide (A1) comprises ethylene bis-stearamide, its mass content is greater than 10% by weight relative to the total weight of the composition;and said composition comprising at least 60% by weight of polyamide (B) relative to the total weight of the composition.; 2. Composition according to claim 1, characterized in that the additive (A) comprises a diamide (A1) obtained with at least one diamine selected from a C2-C24 aliphatic diamine, a C6-C18 cycloaliphatic diamine, a C6-C24 aromatic diamine, a polyetherdiamine, and mixtures thereof.

3. Composition according to any one of claims 1 or 2, characterized in that the additive (A) comprises a diamide (A1) obtained with at least one diamine selected from a C2 to C18 aliphatic diamine, preferably a linear aliphatic diamine in C4 to C10, even more preferentially 1,5-pentamethylenediamine or 1,6-hexamethylenediamine.

4. Composition according to any one of claims 1 to 3, characterized in that the additive (A) comprises a diamide (A1) obtained with at least one carboxylic acid in C2 to C36.

5. Composition according to any one of claims 1 to 4, characterized in that the additive (A) comprises a diamide (A1) obtained with at least one carboxylic acid selected from a C2 to C22 carboxylic acid, preferably a C2 to C22 hydroxylated carboxylic acid and optionally a C2 to C22 unsubstituted carboxylic acid, more preferably a C12 to C20 hydroxylated carboxylic acid and optionally a C2 to C14 unsubstituted carboxylic acid.

6. Composition according to any one of claims 1 to 5, characterized in that the additive (A) comprises a diamide (A1) obtained: - with at least one diamine chosen from a linear aliphatic diamine in C4 to C10; - with at least one carboxylic acid chosen from a carboxylic acid hydroxylated at C2 to C22, an unsubstituted carboxylic acid at C2 to C14, and mixtures thereof.

7. Composition according to any one of claims 1 to 6, characterized in that the additive (A) comprises a diamide (A1) obtained by reaction between 1,5-pentamethylenediamine or 1,6-hexamethylenediamine, 12-hydroxystearic acid, and optionally an acid not substituted at C2 to C14.

8. Composition according to any one of claims 1 to 7, characterized in that it comprises from 5% to 40% by weight, preferably from 10% to 35% by weight of diamide (A1), relative to the total weight of said composition.

9. Composition according to any one of claims 1 to 8, characterized in that when the diamide (A1) comprises ethylene bis-stearamide, its mass content is greater than or equal to 12% by weight relative to the total weight of the composition.

10. Composition according to any one of claims 1 to 9, characterized in that the additive (A) comprises the amide (A2) selected from the group consisting of stearamide, behenamide, capramide, caproamide, caprylamide, elaidamide, erucamide, palmitamide, oleamide, and mixtures thereof.

11. Composition according to any one of claims 1 to 10, characterized in that the additive (A) comprises a vegetable oil (A4) selected from castor oil, linseed oil, rapeseed oil, sunflower oil, soybean oil, maize oil, palm oil, copra (coconut) oil, ethoxylated hydrogenated castor oil, and mixtures thereof.

12. Composition according to any one of claims 1 to 11, characterized in that the additive (A) does not comprise polymer (A5).

13. Composition according to any one of claims 1 to 12, characterized in that the additive (A) has an average molecular mass by weight less than or equal to 3000 g / mol, preferably less than or equal to 2000 g / mol, even more preferably ranging from 400 to 1800 g / mol.

14. Composition according to any one of claims 1 to 13, characterized in that the polyamide (B) has a weight average molecular mass greater than 8,000 g / mol, preferably from 10,000 to 150,000 g / mol, even more preferably from 12,000 to 100,000 g / mol.

15. A composition according to any one of claims 1 to 14, characterized in that the polyamide (B) comprises the polycondensation product of an acid component and an amine component, the acid component comprising: 30 to 90 moles % of fatty acid dimer(s); 5 to 64 moles % of aliphatic diacid(s); and 5 to 30 moles % of chain limiter(s); the amine component comprising: 30 to 100 moles % of aliphatic diamine(s), preferably selected from the group consisting of ethylenediamine and propylene. diamine, butylene diamine, pentylene diamine, hexamethylene diamine, decamethylene diamine and mixtures thereof; o 0 to 70 moles % of cycloaliphatic diamine(s); o 0 to 20 moles % of polyetherdiamine(s).

16. Composition according to any one of claims 1 to 15, characterized in that it is a hot melt adhesive composition.

17. Composition according to any one of claims 1 to 16, characterized in that it comprises more than 90% by weight of the additive (A) and the polyamide (B), preferably more than 92% by weight, and even more preferably more than 95% by weight, relative to the total weight of said composition.

18. Use of the composition according to any one of claims 1 to 17, to fill defects in various substrates such as wood, for holding in a folded position of filter (for example folded accordion-style).

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