Filaments Comprising Polyamide (PA) Polymers and Their Use for Additive Manufacturing - Patent application

Abstract

The present invention relates to a method for producing three-dimensional (3D) articles, parts or composites from filaments comprising polyamide (PA) exhibiting 4,4'-diaminodicyclohexylmethane moieties, and to such filaments. The present invention also relates to the 3D articles, parts or composites obtained from such methods, and to the use of the articles, parts or composites in oil and gas applications, automotive applications, electrical and electronic applications, aerospace, medical and consumer goods.

Description

[Technical field]

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 323514, filed March 25, 2022, and European Patent Application No. 22169722.0, filed April 25, 2022.

[0002] The present invention relates to filaments based on polyamide (PA) containing 4,4'-diaminodicyclohexylmethane moieties, as well as a method for producing three-dimensional (3D) articles, parts, or composites from such filaments. [Background technology]

[0003] Many objects, from household items to motor parts, are manufactured from a single lump of material, or they are milled or milled out of a larger block of material. Another approach to manufacturing an object is to deposit a layer of material, then add another layer on top of it, followed by another layer, and so on. This additive process gave rise to the name Additive Manufacturing (AM), more commonly known as 3D printing. The range of specially designed 3D printed products on the market, from motor parts to dental implants, is now considerable. They can be manufactured using plastics in particular. Additive manufacturing promises to disrupt established practices and overturn traditional assumptions about mass production in distant factories. Local manufacturing of small quantities, or even single items, close to the end user, will become viable.

[0004] In extrusion-based AM systems, 3D parts are printed from a digital representation of the 3D part in a layer-by-layer fashion by extruding and abutting strips of part material. The part material is extruded through an extrusion tip carried by the system's print head and deposited as a series of tracks in the xy plane on the platen. The extruded part material fuses to the previously deposited part material and solidifies upon a drop in temperature. The position of the print head relative to the substrate is then incremented along the z-axis (perpendicular to the xy plane), and the process is then repeated to form a 3D part that resembles the digital representation. One example of an extrusion-based AM system that starts from a filament is called Fused Filament Fabrication (FFF), also known as Fused Deposition Modeling (FDM).

[0005] One of the fundamental limitations associated with known extrusion-based AM methods that use polymer part materials in the form of filaments is based on the failure to identify polymer materials that exhibit a suitable set of properties for printing articles, parts, or composites with acceptable properties, particularly thermal and mechanical properties.

[0006] Certain polyamides have been used for the manufacture of articles by extrusion-based 3D printing. For example, polyamide 12 (PA12) and polyamide 6 (PA6) can be mentioned. These polyamides advantageously have a melting point (Tm) lower than 280 ° C and therefore a much wider temperature window for their synthesis and processing in the melt, which firstly provides more flexibility in synthesis and processing, but also leads to printed parts with reduced coloration due to degradation. However, these polyamides usually exhibit a low glass transition temperature (Tg), for example below 50 ° C, above which their mechanical properties, such as modulus and strength, decrease significantly, making them unsuitable for the manufacture of articles used in applications requiring high temperature resistance. For example, the Tg of PA12 is 40 ° C and that of PA6 is 50 ° C. Moreover, PA6 absorbs so much moisture when exposed to the ambient environment or immersed in water (about 9% by weight) that the Tg drops dramatically and parts manufactured with PA6 lose their modulus when exposed to temperatures higher than room temperature. In addition, these polyamides and their filaments require a drying step before use. Summary of the Invention [Problem to be solved by the invention]

[0007] Some applications may require the production of 3D objects by FFF that exhibit a combination of excellent mechanical properties (e.g. modulus and strength) and other physicochemical properties even at high temperatures. For example, articles used in applications such as automotive interiors and exteriors must withstand temperatures as high as 80°C. These properties should also not be affected by humidity present in the environment.

[0008] The filament used in the 3D printing process also needs to be easily processable by available 3D printers.

[0009] The 3D object must also exhibit UV and chemical resistance, which is necessary, for example, if the 3D object is to be left outdoors or in the sun.

[0010] Finally, customers are becoming increasingly receptive to using materials prepared from bio-based components, and some are even interested in producing translucent or transparent 3D objects.

[0011] The filaments of the present invention address this technical problem.

[0012] US Patent No. 5,360,891 (Huels) relates to colorless, transparent, amorphous, processable polyamides comprising as starting components I. the reaction products of linear aliphatic dicarboxylic acids; II.a) 35-60 mol % of trans,trans-bis(4-aminocyclohexyl)-methane; and II.b) 65-40 mol % of other aliphatic, cycloaliphatic, araliphatic or aromatic diamines.

[0013] US 2015 / 0099847 (Evonik) relates to a composition comprising a blend of two polyamides, one of which is a polyamide having as copolymerized units bis(4-aminocyclohexyl)methane (PACM) and linear dicarboxylic acids having 8 to 18 C atoms. There is no mention of filaments.

[0014] US Patent No. 8,399,557 (Arkema) relates to transparent blends or alloys comprising 1-99% by weight of a copolymer comprising two types of units: (A1) amide units containing at least one cycloaliphatic unit and (A2) flexible ether units, where the cycloaliphatic diamine can be selected from bis(3-methyl-4-aminocyclohexyl)methane (BMACM), para-aminodicyclohexylmethane (PACM), isophoronediamine (IPD), bis(4-aminocyclohexyl)methane (BACM), 2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP) or 2,6-bis(aminomethyl)norbornane (BAMN).

[0015] WO 2021 / 160959 discloses polyamide in powder form for 3D printing.

[0016] US Patent Application Publication No. 2021 / 0040318 discloses blends including amorphous and crystalline polyamides for 3D printing. The crystalline polyamide may be PACM12.

[0017] U.S. Pat. No. 3,393,210 (Dupont, 1968) describes fiber-forming polycarbonamides (including copolycarbonamides) exhibiting the following repeating units: [ka]

[0018] GB 1150860 (D1) discloses crystalline polyamide filaments in the field of fibers. D1 contains a compound of the formula: [ka] where n is 9 to 14, and at least 70% by weight of the diamino component has a trans-trans configuration. The bis(4-aminocyclohexyl)methane used for the preparation of the polyamide D1 contains a proportion of trans-trans stereoisomers of 70-100% by weight. The trans / trans proportion of the polyamide (PA) is less than 70% by weight.

[0019] WO 2019 / 170463 (D2) belongs to the field of 3D printing and discloses and encompasses a filament comprising a core material coated with a layer of a shell material, the core material and the shell material each comprising at least one fibrous filler, at least one thermoplastic polymer and optionally at least one additive component. The core thermoplastic polymer may be PACM12. Thus, D2 discloses a filament made from a non-uniform polymer composition. Furthermore, there is no information about the trans-trans proportion in PACM12.

[0020] US Pat. No. 11,148,374 (D3) is in the field of 3D printing and discloses a polymer-based material configured for use as a feedstock in an extrusion-based additive manufacturing system, the material comprising a substantially homogeneous blend of one or more semi-crystalline polyamides and one or more amorphous polyamides, the one or more amorphous polyamides and the one or more fillers comprising about 1% by weight to about 45% by weight of the total weight of the polymer-based material.

[0021] None of these patents describe the use of the filaments described in the claims. [Means for solving the problem]

[0022] The present invention is as set out in the accompanying set of claims.

[0023] The present invention relates to a filament according to any one of claims 1 to 39.

[0024] The invention also relates to a spool of filament according to claim 40.

[0025] The present invention relates to a method according to claims 41 to 43 and to the use of the filaments according to the invention according to claim 44.

[0026] More details and precision on all these topics are given hereinafter. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The filament of the present invention The filament is as disclosed in claim 1. The filament has the formula (I): [ka] Repeating units (R PA), Repeating unit (R PA ) is at least 50.0 mol %, this percentage being relative to the total number of repeat units in the polyamide (PA); n is an integer from 7 to 11; At least 30.0 mole percent of the 4,4'-diaminodicyclohexylmethane derived moieties are in the trans / trans configuration, this percentage being based on the total number of moles of 4,4'-diaminodicyclohexylmethane derived moieties in the polyamide (PA).

[0028] The filaments have a cylindrical or substantially cylindrical shape.

[0029] The filaments may have a cylindrical or substantially cylindrical shape with a diameter d between 0.5 mm and 5.0 mm, which may vary between 0.8 mm and 4.0 mm, or between 1.0 mm and 3.5 mm.

[0030] d can be selected to feed a particular FFF 3D printer. Examples of diameters commonly used in FFF processes have diameters d of 1.75 mm or 2.85 mm.

[0031] Preferably, the filaments have a circular cross section.

[0032] The term "filament" refers to a formed thread-like body or fiber or strand.

[0033] Preferably, the filaments are whole filaments. The term "whole" is used in comparison to hollow shapes and refers to filaments that are not hollow.

[0034] According to a preferred embodiment, the filaments do not exhibit a core / shell geometry with different polymer compositions. "Core / shell geometry" refers to filaments having an elongated core radially surrounded by an outer shell. The core and shell are usually made of two different polymer compositions or two polymers of the same composition but with different physicochemical properties.

[0035] The core / shell geometry requires the use of a more complex co-extrusion system than a simple extrusion system. Moreover, during the 3D printing process, the shell material is mixed with the core material, which gives rise to several anticipated technical difficulties (inhomogeneity of the composition of the 3D object, contamination by the shell material, etc.).

[0036] To avoid the above-mentioned inhomogeneity, the components of the composition (P) are preferably blended together. The term "blend" is intended to denote a homogeneous (or uniform) physical mixture. The term "blended" is intended to mean that the components of the polymer composition (P) form a homogeneous (or uniform) physical mixture.

[0037] Preferably, the composition of the filaments is composed of a polymer composition (P).

[0038] The length L of the filament is usually at least 200 mm.

[0039] The filaments may be in the form of a spool. The invention therefore also relates to a spool of the filaments of the invention, said spool being made from or comprising the polymer composition (P).

[0040] Regarding the polymer composition (P) The polymer composition (P) comprises at least 50.0 wt. % (based on the total weight of the polymer composition (P)) of at least one polyamide (PA) as disclosed herein.

[0041] The polymer composition (P) may comprise one or more polyamides (PA) as described herein. It may comprise two or more polyamides (PA), in which case the polyamides (PA) are blended together.

[0042] Preferably, the polymer composition (P) comprises only one polyamide (PA) as described herein.

[0043] Preferably, the polymer composition (P) does not contain aromatic polyamides. Preferably, the polymer composition (P) does not contain amorphous polyamides. Aromatic polyamides are polyamides that contain repeat units with aromatic moieties. Amorphous polyamides are polyamides that have a heat of fusion Hm lower than 2.0 J / g. The expression "free of X" means that the polymer composition (P) does not contain X, or, if it does contain X, the proportion of X in the composition (P) is less than 1.0% by weight, preferably less than 0.5% by weight, preferably less than 0.1% by weight.

[0044] Preferably, the polymer composition (P) does not comprise any polyamide other than the polyamide (PA). Preferably, the polymer composition (P) does not comprise any polyamide other than the polyamide (PA).

[0045] The proportion of polyamide (PA) in the polymer composition (P) is at least 50.0% by weight. This proportion may be at least 60.0% by weight, preferably at least 70.0% by weight, preferably at least 80.0% by weight. The proportion of polyamide (PA) may be between 50.0% by weight and 100.0% by weight.

[0046] The polymer composition (P) may also contain at least one thermoplastic polymer other than polyamide (PA). In this case, polyamide (PA) and thermoplastic polymer are blended together. The thermoplastic polymer may be selected from the group consisting of poly(arylene sulfide) (PAS) polymers, such as homopolymers of poly(phenylene sulfide) (PPS) polymers, poly(aryl ether sulfone) (PAES) polymers, such as poly(biphenyl ether sulfone) (PPSU) polymers or polysulfone (PSU) polymers, polyetherimide (PEI), and poly(aryl ether ketone) (PAEK) polymers, such as poly(ether ether ketone) (PEEK) polymers.

[0047] The polymer composition (P) may also comprise at least one additive selected from the group consisting of fillers, colorants, dyes, pigments, lubricants, plasticizers, flame retardants, reinforcing agents, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, electromagnetic absorbers, and combinations thereof.

[0048] The filler may more specifically be selected from the group consisting of continuous or chopped carbon fibers, continuous or chopped glass fibers, crushed carbon fibers, crushed glass fibers, glass beads, glass microspheres, wollastonite, silica beads, talc, calcium carbonate, bio-based fibers, polymeric fibers, and combinations thereof.

[0049] Synthetic polymeric fibers are, for example, aramid fibers, rock wool fibers, natural fibers (eg, flax, hemp, cellulose, or nanocellulose), and any combination of two or more thereof.

[0050] The filler is more particularly carbon fiber, in particular selected from the group consisting of continuous carbon fiber, chopped carbon fiber and crushed carbon fiber.

[0051] The flame retardant may be a halogen-based flame retardant or a phosphorus-based flame retardant. The phosphorus-based flame retardant may be selected from the group consisting of metal alkyl phosphinates. An example of a metal alkyl phosphinate is aluminum diethylphosphinate, for example known under the trade name Exolit® from Clariant. Another example of a phosphorus-based flame retardant that allows to obtain high quality 3D objects while ensuring an excellent level of flame retardancy is disclosed below: [ka]

[0052] The heat stabilizer may more specifically be selected from the group consisting of monovalent or divalent copper, stabilizers based on aromatic secondary amines, stabilizers based on sterically hindered phenols, phosphites, phosphonites, metal salts, metal oxides, and combinations thereof.

[0053] According to one embodiment, the polymer composition (P) comprises at least one additive selected from the group consisting of fillers that are not fibrous fillers, colorants, dyes, pigments, lubricants, plasticizers, flame retardants, reinforcing agents, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, electromagnetic absorbers, and combinations thereof.

[0054] According to another embodiment, the polymer composition (P) comprises at least one additive selected from the group consisting of colorants, dyes, pigments, lubricants, plasticizers, flame retardants, toughening agents, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, electromagnetic absorbers, and combinations thereof.

[0055] The polymer composition (P) is more particularly at least one polyamide (PA) as defined herein; - optionally at least one filler as defined herein; and - optionally at least one additive other than a filler as defined herein; It may comprise or consist of:

[0056] Additives (eg fillers and / or non-filler additives) are usually blended with the polyamide (PA) of the polymer composition (P).

[0057] The proportion of additives (e.g. fillers and / or additives other than fillers) in the polymer composition (P) is usually less than 50.0% by weight, further less than 40.0% by weight, or even less than 30.0% by weight. The proportion of additives in the polymer composition (P) is usually 0.01 to 50.0% by weight, further 0.10 to 40.0% by weight, or 0.50 to 40.0% by weight.

[0058] More specifically, the present invention also relates to a polymer composition (P*) comprising at least one polyamide (PA) as defined herein, at least one filler and, optionally, at least one additive other than the filler. The total proportion of the filler and the optional additive is usually less than 50.0% by weight, even less than 40.0% by weight, or even less than 30.0% by weight. The proportion of the optional additive is usually between 0.01% and 20.0% by weight, preferably between 0.1% and 10.0% by weight. The filler may be one of the fillers disclosed above.

[0059] According to a particular embodiment (E), the filament of the invention has at least one polyamide (PA) as defined herein; - optionally at least one filler as defined herein; and - optionally at least one additive other than a filler as defined herein; It is produced from a polymer composition (P) consisting of:

[0060] The components of the polymer composition (P) are preferably blended together.

[0061] About Polyamide (PA) The polyamide (PA) is as disclosed in the claims. The polyamide (PA) comprises repeating units (R PA ) including: [ka] (wherein n is an integer from 7 to 11).

[0062] The polyamide (PA) advantageously has the following properties: A glass transition temperature (Tg) greater than 120°C; and / or · Melting point (Tm) below 280°C; Shows.

[0063] In formula (I), n varies from 7 to 11. n is an integer that can take any value within the range of 7 to 11.

[0064] More specifically, n may be selected from the group consisting of {7, 8, 9, 10, 11, and combinations of two or more of the foregoing values}.

[0065] More specifically, n can be selected from the group consisting of {7, 8, 9, 10, 11}.

[0066] More specifically, n can take any value disclosed in one of the embodiments.

[0067] More specifically, n may be 11 or an integer from 7 to 9.

[0068] The polyamide (PA) is one in which at least 30.0 mole percent of the 4,4'-diaminodicyclohexylmethane derived moieties (present in the polyamide) are in the trans / trans configuration, based on the total number of moles of 4,4'-diaminodicyclohexylmethane derived moieties in the PA, which makes it possible to obtain a semi-crystalline polyamide.

[0069] A trans / trans ratio of more than 30.0 mol% makes it possible to obtain semicrystalline polyamides (PA) that are highly suitable for additive manufacturing (3D printing). In particular, the polyamides (PA) of the present invention exhibit suitable thermal properties, in particular a high glass transition temperature and a low melting point that ensure good processability during printing, and are advantageously different from most of the commercially available polyamides, such as PA12 (Tg<50°C) and PA6 (Tg<60°C, hydrophilic). The PAs described herein also advantageously exhibit a low water absorption that contributes to maintaining a high glass transition temperature.

[0070] The proportion of 4,4'-diaminodicyclohexylmethane moieties in trans / trans configuration is preferably at least 40.0 mol%, more preferably at least 50.0 mol%. This proportion may be less than 70.0 mol%, preferably less than 65.0 mol%, preferably less than 60.0 mol%, even more preferably less than 55.0 mol%.

[0071] The proportion of 4,4'-diaminodicyclohexylmethane moieties in the trans / trans configuration may be between 30.0 mol % and 50.0 mol % (this latter value being excluded).

[0072] The PA described herein comprises at least 50.0 mol % (R PA The percentage of repeat units is expressed as mole % and is relative to the total number of repeat units in the polyamide (PA). PA ) may be at least about 60.0 mol%, more specifically at least about 75.0 mol%, more specifically at least about 80.0 mol%, more specifically at least about 85.0 mol%, more specifically at least about 90.0 mol%, more specifically at least about 95.0 mol%, or at least about 98.0 mol%. This percentage may be at least 99.0 mol%, or even at least 99.5 mol%.

[0073] Homopolyamide: According to one embodiment, the polyamide (PA) is a homopolyamide. The repeating units of the polyamide (PA) are the repeating units (R PA Such polyamides consist of or essentially consist of repeating units (RPA). 1) Formula (II): [ka] wherein at least 30.0 mole percent of the PACM is in a trans / trans configuration, based on the total moles of PACM in the reaction mixture; 2) Formula (III): [ka] with at least one diacid of 3) with optional water; The compound is prepared by polycondensation in the presence of a reaction mixture comprising

[0074] The proportion of trans / trans isomers in the monomeric PACM can be controlled by chromatography (e.g. gas chromatography, such as GC-FID (Flame Ionization Detector)). Depolymerization of the polyamide under acidic or basic conditions and analysis of the monomers makes it possible to determine the proportion of trans / trans moieties in the polyamide.

[0075] The condensation mixture preferably also contains a catalyst, for example a catalyst that contains at least one phosphorus atom, such as sodium hypophosphite.

[0076] The condensation mixture must be heated to an elevated temperature, preferably at least Tm+10°C, where Tm is the melting point of the polyamide. The temperature at which the condensation is carried out is usually at least 200°C.

[0077] The polycondensation is advantageously carried out in the melt, in particular in the absence of a solvent.

[0078] The polycondensation is advantageously carried out in a well-stirred vessel, such as a stirred reactor. The vessel is also advantageously equipped with means for removing volatile products of the reaction. Stirred vessels can conveniently be used to carry out the polycondensation.

[0079] The conditions used in the examples can be followed and adjusted as necessary for the preparation of other homopolyamides.

[0080] Copolyamide: According to another embodiment, the polyamide (PA) comprises repeating units (R PA ) and containing repeat units according to formula (IV) and / or formula (V) (R* PA ) also includes: [ka] (In the formula, R1 optionally contains one or more heteroatoms (e.g., O, N, or S) and can be any of halogen (e.g., fluorine, chlorine, bromine, or iodine), hydroxy (-OH), sulfo (-SO3M) (e.g., where M is H, Na, K, Li, Ag, Zn, Mg, or Ca), C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C 15 Aryloxy and C6-C 15 C2-C optionally substituted with one or more substituents selected from the group consisting of aryl 15 Alkylene and C6-C 30 arylene; R2 optionally contains one or more heteroatoms (e.g., O, N, or S) and can be any of halogen (e.g., fluorine, chlorine, bromine, or iodine), hydroxy (-OH), sulfo (-SO3M) (e.g., where M is H, Na, K, Li, Ag, Zn, Mg, or Ca), C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C 15 Aryloxy and C6-C 15 C1-C optionally substituted with one or more substituents selected from the group consisting of aryl 20 Alkylene and C6-C30 arylene; R3 optionally contains one or more heteroatoms (e.g., O, N, and S) and can be any of halogen (e.g., fluorine, chlorine, bromine, and iodine), hydroxy (-OH), sulfo (-SO3M) (e.g., where M is H, Na, K, Li, Ag, Zn, Mg, or Ca), C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C 15 Aryloxy and C6-C 15 A straight or branched C2-C alkyl group optionally substituted with one or more substituents selected from the group consisting of aryl 14 alkylene).

[0081] More specifically, R1 is C2 to C 15 Alkylene and C6-C 30 arylene; R2 is selected from the group consisting of C1-C 20 Alkylene and C6-C 30 arylene; R3 is a linear or branched C 14 It is alkylene.

[0082] Preferably, R2 is -(CH2) n -, n is a repeating unit (R PA ) is the same as

[0083] Preferably, the repeating unit (R* PA ) does not contain an aromatic ring.

[0084] Polyamide (PA) consists of repeating units (R PA ) and derived from the condensation of at least one dicarboxylic acid with at least one diamine, PA ) may also be included in the copolyamide.

[0085] Polyamide (PA) consists of repeating units (R PA ) and derived from at least one aminocarboxylic acid and / or at least one lactam,PA ) may also be included in the copolyamide.

[0086] According to one embodiment, the repeating units of the copolyamide are the repeating units (R PA ) and (R* PA )

[0087] According to one embodiment, the repeating units (R*) in the copolyamide PA The proportion of the repeating unit (R*) is usually 1.0 mol % to 25.0 mol %. This proportion is preferably 5.0 mol % to 20.0 mol %. According to one embodiment, the repeating unit (R*) PA ) is less than 2.0 mol%, further less than 1.0 mol%, or even less than 0.5 mol%.

[0088] Copolyamides are also prepared by polycondensation. In such cases, the condensation mixture disclosed above is at least one dicarboxylic acid and at least one diamine, and / or at least one aminocarboxylic acid, and / or - at least one lactam Further comprising at least one component selected from the group consisting of:

[0089] The amino carboxylic acid may have 3 to 15 carbon atoms, for example 4 to 13 carbon atoms. The amino carboxylic acid may more specifically be selected from the group consisting of 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminoundecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 13-aminotridecanoic acid, and mixtures thereof.

[0090] The lactam may have 3 to 15 carbon atoms, for example 4 to 13 carbon atoms. The lactam may more particularly be selected from the group consisting of caprolactam, laurolactam, dodecanolactam, and mixtures thereof.

[0091] The dicarboxylic acids may be aliphatic or aromatic. Non-limiting examples of aliphatic dicarboxylic acids include oxalic acid (HOOC-COOH), malonic acid (HOOC-CH2-COOH), succinic acid [HOOC-(CH2)2-COOH], glutaric acid [HOOC-(CH2)3-COOH], 2,2-dimethylglutaric acid [HOOC-C(CH3)2-(CH2)2-COOH], adipic acid [HOOC-(CH2)4-COOH], 2,4,4-trimethyl Adipic acid [HOOC-CH(CH3)-CH2-C(CH3)2-CH2-COOH], pimelic acid [HOOC-(CH2)5-COOH], suberic acid [HOOC-(CH2)6-COOH], azelaic acid [HOOC-(CH2)7-COOH], sebacic acid [HOOC-(CH2)8-COOH], undecanedioic acid [HOOC-(CH2)9-COOH], dodecanedioic acid [HOOC-(CH2) 10 -COOH], tridecanedioic acid [HOOC-(CH2) 11 -COOH], tetradecanedioic acid [HOOC-(CH2) 12 -COOH], pentadecanedioic acid [HOOC-(CH2) 13 -COOH], hexadecanedioic acid [HOOC-(CH2) 14 -COOH], octadecanedioic acid [HOOC-(CH2) 16-COOH]. This category also includes alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. Non-limiting examples of aromatic diacids are phthalic acids, such as isophthalic acid (IPA) and terephthalic acid (TPA), naphthalenedicarboxylic acids (e.g., naphthalene-2,6-dicarboxylic acid), 4,4'-bibenzoic acid, 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, bis(4-carboxyphenyl)methane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)ketone, 4,4'-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, bis(3-carboxyphenyl)methane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)ketone, bis(3-carboxyphenoxy)benzene, among others.

[0092] The diamines may be either aliphatic or aromatic. Non-limiting examples of aromatic diamines (NNar) are m-phenylenediamine (MPD), p-phenylenediamine (PPD), 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diaminodiphenyl ether (4,4'-ODA), p-xylylenediamine (PXDA), and m-xylylenediamine (MXDA), among others. Non-limiting examples of aliphatic diamines include 1,2-diaminoethane, 1,2-diaminopropane, propylene-1,3-diamine, 1,3-diaminobutane, 1,4-diaminobutane (putrescine), 1,5-diaminopentane (cadaverine), 2-methyl-1,5-diaminopentane, hexamethylenediamine (i.e., 1,6-diaminohexane), 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4-dimethyl ... ,4-trimethyl-hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 2,5-diamonotetrahydrofuran, and N,N-bis(3-aminopropyl)methylamine. This category also includes cycloaliphatic diamines such as isophorone diamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis-p-aminocyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis-(2-methylcyclohexylamine). The aliphatic diamines can also be selected from the group of polyether diamines. The polyether diamines can be based on ethoxylated (EO) and / or propoxylated (PO) backbones and they can be ethylene oxide, propylene oxide or butylene oxide terminated diamines.Such polyether diamines are sold, for example, under the trade names Jeffamine® and Elastamine® (Hunstman).

[0093] Copolyamides are also prepared by polycondensation. Everything disclosed above for the preparation of homopolyamides is also valid for copolyamides.

[0094] Polyamide (PA) end groups The end groups of the polyamide (PA) are selected from the group of -NH2, -COOH and amide end groups. In fact, the end groups of the polyamide (PA) may be -NH2 or -COOH. However, if the polycondensation is accompanied by the addition of an end-capping agent, these end groups may be partially or totally converted into amide end groups.

[0095] The amide end groups are of the formula -NH-C(=O)-R, where R is an alkyl, aryl, or cycloalkyl group, and / or of the formula -C(=O)-NH-R', where R' is an alkyl or cycloalkyl group. R is more specifically a linear or branched C2-C 18 Alkyl group or C5-C 10 R' is more specifically a linear or branched C2-C cycloalkyl group. 18 It is an alkyl group.

[0096] Amide end groups of the formula -NH-C(=O)-R result from the reaction of the end group -NH2 with a monocarboxylic acid (endcapping agent) of the formula R-COOH.

[0097] The monocarboxylic acid (endcapping agent) is preferably benzoic acid, cyclohexanoic acid, R-COOH (R is a linear or branched C2-C 18 R is an alkyl group, and combinations of two or more of these acids. R is a radical derived from an acid of formula R-COOH.

[0098] The monocarboxylic acid (endcapping agent) may more specifically be selected from the group consisting of acetic acid, propanoic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, and combinations of two or more of these acids.

[0099] The monocarboxylic acid (endcapping agent) is more specifically represented by the formula CH3-(CH2) m -COOH, where m is an integer from 0 to 16. In that case, the amide end group has the formula -NH-C(=O)-(CH2) m -CH3.

[0100] Amide end groups of the formula -C(=O)-NH-R' result from the reaction of the end group -COOH with a primary amine of the formula R'-NH2 (an endcapping agent).

[0101] The primary amine (endcapping agent) is advantageously of the formula R'-NH2, where R' is a linear or branched C2-C 18 R' is a radical derived from an amine of formula R'-NH2.

[0102] The primary amine (endcapping agent) is more specifically represented by the formula CH3-(CH2) m’ -NH2 (m' is an integer from 2 to 18). In that case, the amide end group has the formula -C(=O)-NH-(CH2) m’ -CH3.

[0103] The primary amine (endcapping agent) can more specifically be selected from the group consisting of propylamine, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, and combinations of two or more of these amines.

[0104] The proportion of terminal groups is 1Quantitation can be achieved by 1 H NMR or potentiometry.

[0105] Polyamide (PA) is semi-crystalline.

[0106] The polyamide (PA) preferably exhibits a heat of fusion of at least 15.0 J / g or at least 18.0 J / g. Hm is determined in the second heating scan in a differential scanning calorimeter (DSC) using a heating rate of 20° C. / min according to ISO 11357.

[0107] The polyamide (PA) preferably exhibits a melting point (Tm) below 280°C. Tm may be between 200°C and 280°C, preferably between 220°C and 270°C, preferably between 225°C and 270°C. Tm may be at least 230°C. Tm is determined in a second heating scan in a differential scanning calorimeter (DSC) using heating and cooling rates of 20°C / min according to ISO11357. Tm can be determined according to the conditions of the protocol given in the experimental section.

[0108] The polyamide (PA) may also exhibit a glass temperature (Tg) above 120° C. The Tg may be at least 130° C. The Tg may be between 120° C. and 160° C., preferably between 130° C. and 170° C. The glass temperature is determined in the second heating scan in a differential scanning calorimeter (DSC) using heating and cooling rates of 20° C. / min according to ISO 11357. The Tg can be determined according to the conditions of the protocol given in the experimental section.

[0109] The polyamide (PA) may have a number average molecular weight Mn in the range of 5,000 g / mol to 40,000 g / mol, such as 7,000 g / mol to 35,000 g / mol or 9,000 to 30,000 g / mol.

[0110] Mn can be determined using the following formula (1): Mn = 2,000,000 / [EG] (1), more precisely using known methods for measuring amine and acid end group concentrations, where [EG] is the percentage of end groups in the PA expressed in mmol / kg. The end groups in polyamides (PA) are usually amine and / or acid sites. However, when the polycondensation involves the addition of an end-capping agent, the amine end groups are partially or completely converted to modified end groups. For example, when the end-capping is an acid such as benzoic acid or acetic acid, the remaining amine groups can be completely or partially converted to benzamide or acetamide end groups.

[0111] The concentration of end groups is determined according to techniques well known to those skilled in the art: amine and acid groups are usually determined by potentiometric titration. 1 1 H NMR may also be conveniently used.

[0112] The polyamide (PA) preferably has a water absorption at saturation by immersion in water at 23° C. of less than 6.0% by weight, preferably less than 5.0% by weight, less than 4.0% by weight.

[0113] The polymer composition (P) also preferably has a water absorption at saturation by immersion in water at 23° C. of less than 6.0% by weight, preferably less than 5.0% by weight, less than 4.0% by weight.

[0114] The water absorption at 23°C is determined by (i) preparing dry (less than 0.2% moisture by weight) test specimens molded according to ISO 527, (ii) immersing the test specimens in deionized water at 23°C until a constant weight is reached, and (iii) calculating the water absorption using the following formula:

number

[0115] Biobased Content In addition to the need for better thermal and thermo-mechanical performance, there is also a recent need to develop polyamide filaments made from renewable resources, particularly bio-based raw materials.

[0116] The polyamide (PA) may exhibit a biobased content of at least 40.0% by weight, preferably at least 45.0% by weight, where the biobased content is expressed as the % of organic carbon of renewable origin in the polyamide (PA) and is measured according to ASTM D6866-22. A polymer with 100% biobased content has all of its carbon atoms derived from renewable resources.

[0117] This biobased content can be achieved by using a biobased diacid of formula (III), for example sebacic acid (commonly obtained industrially from castor oil) or azelaic acid (see Polymers (Basel), 2021 13(23), p. 4091. doi:10.3390 / polym13234091).

[0118] Biobased content is defined as the % of organic carbon measured in a sample that comes from renewable sources. 14 It corresponds to the amount of C calculated from the C percent and then corrected for isotopic proportions.

[0119] According to one embodiment, bio-based PACM can be used for the preparation of polyamides (PA). Bio-based PACM can be prepared from bio-based toluene and aniline by hydrogenation of the corresponding aromatic diamines according to EP 0618188. Bio-based aromatics (BTX) can be prepared from black liquor formed during papermaking by cooking of pulpwood according to ACS Sustainable Chem. Eng. 2018, 6, 3472-3480. Thus, the general scheme for the production of bio-based PACM can be black liquor => bio-based toluene => bio-based aniline => PACM.

[0120] By using the bio-based PACM, the bio-based content of the polyamide (PA) can be at least 80.0 wt%, preferably at least 85.0 wt%, preferably at least 90.0 wt%, preferably at least 99.5 wt%.

[0121] By using bio-based monomers and amide end groups, the bio-based content of polyamide (PA) can be 100% by weight, so the bio-based content can be 80.0 to 100.0% by weight.

[0122] Method for producing the filament of the present invention The filaments of the present invention are produced by extruding the polymer composition (P). An extruder can be used to melt and extrude the polymer composition (P). The diameter of the filaments can be altered by adjusting the size of the die or nozzle and / or by adjusting the draw ratio of the filaments after they leave the die.

[0123] As mentioned above, the filaments of the present invention preferably do not exhibit a core / shell morphology, and therefore the filaments are preferably not produced by coextrusion.

[0124] The polymer composition (P) can be prepared by mixing the components of the composition, the polymer components being in molten form.

[0125] The melt mixing process is typically carried out by heating the polymeric components above a suitable temperature to melt them. Suitable melt mixing equipment are, for example, kneaders, Banbury mixers, single screw extruders, and twin screw extruders. Preferably, an extruder is used that is equipped with a means for dosing all the desired components into the extruder, either at the extruder feed throat or into the melt.

[0126] The order of combining the components during melt mixing is not particularly limited. In one embodiment, the components can be mixed in a single batch, so that the desired amount of each component is added together and then mixed. In another embodiment, an initial subset of the components can be mixed together first, and one or more remaining components can be added to the mixture for further mixing. For clarity, it is not necessary that the entire desired amount of each component is mixed as a single amount.

[0127] The components of the polymer composition (P) are mixed until the polymer composition (P) is homogeneous.

[0128] According to one embodiment, the method for producing the filaments is an integrated process in which the polymer composition (P) and the filaments are produced in a one-step process.

[0129] To produce the filaments according to the invention, the conditions given in the examples can be followed.

[0130] How to make 3D objects The present invention also relates to a method for manufacturing a 3D object using an additive manufacturing (AM) system, such as an extrusion-based additive manufacturing system (e.g., FFF or FDM).

[0131] The 3D objects or articles obtainable by such manufacturing methods can be used in a variety of end applications, including implantable devices, medical devices, dental prostheses, brackets and complex shaped parts in the space industry, and under-the-hood parts in the automotive industry where high temperature resistance is required, among others.

[0132] More specifically, the method includes the following steps: - advancing the inventive filament to a print head; - heating the filament in the print head to a molten state, preferably the filament is heated to a temperature of at least Tm+10°C; - The process of forcing molten material out of the nozzles of the print head; - ensuring relative movement of the print head in X and Y directions to form the cross-sectional shape of the 3D object; and / or - A process that ensures relative movement of the print head in the Z direction to form a 3D object in the height direction.

[0133] According to one embodiment, a method for manufacturing a 3D object using an AM system includes a step of extruding a composition (P) into a filament, which may occur, for example, when printing or depositing a strip or layer of filament. The method for manufacturing a 3D object using an extrusion-based AM system is also known as Fused Filament Fabrication (FFF) or Fused Deposition Modeling (FDM).

[0134] FFF / FDM 3D printers are commercially available, for example, from Apium, from Roboze, from Hyrel, or from Stratasys, Inc. (under the trade name Fortus®).

[0135] The present invention also relates to an AM method for producing a three-dimensional (3D) article, part, or composite material, comprising extruding the filaments described above.

[0136] The AM process of the present invention is preferably a Fused Filament Fabrication (FFF) process, also known as Fused Deposition Modeling (FDM).

[0137] In some embodiments, the method further comprises at least one of the following steps in connection with the 3D printer: - feeding the filament into an extrusion head member having a threaded bore terminating in an extrusion tip and a circumferential heater for melting the filament within the threaded bore; - heating the filament to a temperature of at least Tm+10°C before extrusion; - compressing the filament with a piston, for example with the unmelted filament acting as a piston in a through hole; - dispensing filament onto the receiving platform to form a cross-sectional shape while ensuring relative movement of the dispensing tip and the receiving platform in the X and Y directions; and / or - dispensing filament onto the receiving platform while ensuring relative movement of the dispensing tip and the receiving platform in a Z direction to form a 3D object or part in a height direction.

[0138] The 3D object can be built on a substrate, such as a horizontal substrate and / or a planar substrate. The substrate can be movable in any direction, such as horizontally or vertically. During the 3D printing process, the substrate can be lowered, for example, to deposit successive layers of polymeric material on top of the previous layer of polymeric material.

[0139] In some embodiments, the AM method for manufacturing a 3D object further comprises a step of manufacturing a support structure using a support material. According to such embodiments, the 3D object is built on the support structure, and the support structure and the 3D object are both manufactured using the same AM method.

[0140] The 3D printer may include a chamber for maintaining the filament at a specific predetermined temperature, which may be approximately the same as the Tg of the polyamide (PA), for example, Tg±10° C.

[0141] Although not strictly necessary, the 3D object can also be subjected to a post-fabrication heat treatment (also called annealing or tempering) in which case the 3D object can be placed in an oven set at a temperature ranging from 80° C. to 200° C., preferably 100° C. to 180° C., for a time ranging from about 30 minutes to 24 hours, preferably 1 hour to 8 hours.

[0142] The conditions of the 3D printing method presented in the experimental section can be followed.

[0143] 3D object The filaments of the present invention allow the production of 3D objects comprising the polyamides (PA) described herein. The present invention also relates to the use of the filaments described herein for the production of 3D objects using additive manufacturing, preferably FFF or FDM.

[0144] The present invention further relates to the use of the polyamide (PA) as described herein for the manufacture of filaments for use in the manufacture of three-dimensional objects. EXAMPLES

[0145] Experimental section raw materials PACM: 4,4'-methylene-bis-cyclohexylamine, containing 47 mole % trans / trans isomer, commercially available from BASF under the name Dicykan® PACM*: 4,4'-methylene-bis-cyclohexylamine, containing 20 mole % trans / trans isomer, commercially available from Evonik under the name Vestamin® PACM C6 diacid: adipic acid, commercially available from Invista C9 diacid: Azelaic acid, available from Matrica. This diacid is bio-based from sunflower oil. C10 diacid: Sebacic acid, available from Jayant Agro Organics Ltd. This diacid is bio-based derived from castor oil. C12 diacid: dodecanedioic acid, commercially available from Sigma-Aldrich. The C12 diacid may be fossil-based or bio-based. C13 diacid: Brassylic acid, commercially available from Sigma-Aldrich. C13 diacids can be fossil-based or bio-based. PA6: Commercially available from DOMO Chemicals.

[0146] Preparation of Example Polyamides The polyamides were prepared by melt polycondensation of PACM or PACM* with either C6, C9, C10, C12, or C13 diacids.

[0147] Preparation of PACM.12 95.5 g (0.45 mol) of PACM, 102.3 g (0.44 mol) of C12 diacid, and 4.16 g (5 wt %, 2 mmol) of aqueous sodium hypophosphite monohydrate solution were introduced into a stainless steel reactor equipped with a mechanical stirrer. The reactor was purged with nitrogen and the temperature in the reactor was gradually increased to 275° C. The reaction proceeded at atmospheric pressure. The water of condensation as well as the water from the catalyst solution were distilled off. The reaction mixture was maintained at 275° C. for 30 minutes. The resulting polymer was then discharged as strands and pelletized.

[0148] Preparation of PACM.9, PACM.10, PACM.13, PACM.6 (comparison), PACM*.10 (comparison), PACM*.9 (comparison): The preparation of these polyamides applied the same procedure as for PACM.12, but starting from different monomers. The preparation of PACM.6 was unsuccessful because the polyamide crystallized during the reaction and did not melt at 275 °C. It cannot be used for 3D printing, since it cannot be processed in the molten state at the appropriate temperature. For all other polyamides, there were no problems in production and all were possible to melt process to extrude from the reactor.

[0149] Polyamide characterization

[0150] [Table 1]

[0151] DSC DSC Protocol The protocol used was as follows: 1st heating cycle from 30.00°C to 300.00°C at 20.00°C / min; 5 min isothermal; 1st cooling cycle from 300.00°C to 30.00°C at 20.00°C / min; 2nd heating cycle from 30.00°C to 300.00°C at 20.00°C / min. Melting point (T m ) was recorded during the second heating cycle, and the glass transition temperature (T g ) is recorded during the second heating cycle.

[0152] DSC analysis was performed according to ISO 11357 and data were collected using a two heat and one cool procedure.

[0153] The DSC used was a DSC8000 (Perkin Elmer).

[0154] Water absorption rate The polyamide was molded in its dry state (water content less than 0.2% by weight) according to ISO 527 and then immersed in deionized water at 23° C. until a constant weight was reached.

[0155] Tensile properties Tensile modulus, tensile strength, and tensile elongation at break were measured according to ISO 527-2.

[0156] result The strength, modulus, and elongation at break results in Table 2 were measured from injection molded specimens.

[0157] [Table 2]

[0158] As shown in Table 2, the combination of PACM with C6 diacid does not result in a polyamide that can be processed at suitable temperatures, since it does not melt before 355°C. Conversely, when PACM is combined with C9, C10, C12, and C13 diacids, the polyamides are all semi-crystalline with melting points below 280°C and Tg above 130°C, making them suitable for melt processing in filament form and for applications where the parts are exposed to temperatures above 160°C. It can also be seen that the polyamides of the present invention exhibit high modulus of elasticity, exceeding 1000 MPa, and high elongation at break. Thus, the filaments of the present invention are fully processable, ensuring the thermomechanical properties of the resulting 3D objects.

[0159] The 3D objects produced using the filaments of the present invention are made of repeating units (R PA ) does not contain aromatic moieties, and therefore also exhibits UV resistance.

[0160] When PACM* is used in combination with a C10 diacid or a C9 diacid, the polyamide is amorphous (has no melting point) and only exhibits a Tg. This is undesirable for filament production for 3D printing because it has no mechanical integrity at temperatures above 160° C. Therefore, it is desirable to use a PACM that contains more than 30 mol % trans-trans isomer.

[0161] Filament production and characterization The feedstock for filament production consisted of neat polymer (PA) pellets. 1.75 mm diameter filaments of each composition were produced using a Brabender® Intelli-Torque Plasti-Corder® torque rheometer extruder equipped with a 0.75 inch (1.905 cm) 32 L / D general-purpose single screw, heated capillary die attachment, a 3 / 32 inch diameter nozzle with a 1.5 inch long land, and a downstream custom-designed filament delivery device. Other downstream equipment included a belt puller and a dual station coiler, both from ESI-Extrusion Services. Filament dimensions were monitored using a Beta LaserMike® 5012 with a DataPro 1000 data controller. The molten strands were cooled with air. Brabender® zone set temperatures were just above the melting point of 250-280°C in the barrel zone and 270°C in the die. Brabender® speeds ranged from 25 to 60 rpm, and puller speeds ranged from 20 to 70 feet / min (6.093 to 21.336 meters / min).

[0162] 3D printing The filaments were printed on an Argo500 extrusion-based additive manufacturing system available from Roboze Inc., (Houston, Texas, USA or Bara, Italy). A nylon build sheet was used as the substrate for the printed object. During the printing run, the extruder temperature was set at 300-390°C and the heating chamber was set at a temperature approximately equal to the Tg of the material, e.g., 130-150°C. A 0.6 mm Roboze Argo Tip3-HSA tip was used for the model material, with layer thicknesses of 0.1-0.3 mm. The material was extruded as a series of loads in a layer-by-layer format in the heated chamber to print the structures. An ASTM type I, IV, or V tensile bar was printed for each formulation using 100% infill and either alternating 45° / -45° or alternating 0° / 90° rasters, and after printing, the object was quickly removed from the heating chamber and build sheet. It was observed that the PA filaments of the present invention have excellent printing capabilities and exhibit high thermo-mechanical properties.

[0163] [Table 3]

[0164] As can be seen from Table 3, the 3D objects retain excellent mechanical properties.

Claims

1. Formula (I) 【Chemistry 1】 Repeating units (R ＰＡ 1. A filament made from or comprising a polymer composition (P) comprising at least 50.0 wt. % of at least one polyamide (PA) comprising, based on the total weight of the polymer composition (P), Repeating unit (R ＰＡ ) is at least 50.0 mol %, relative to the total number of repeat units in said polyamide (PA); n is an integer from 7 to 11; The proportion of 4,4'-diaminodicyclohexylmethane-derived moieties in a trans / trans configuration is at least 30.0 mol% and at most 60.0 mol%, and this proportion is based on the total number of moles of 4,4'-diaminodicyclohexylmethane-derived moieties in the polyamide (PA). filament.

2. 2. The filament according to claim 1, wherein the proportion of polyamide (PA) in the polymer composition (P) is at least 60.0% by weight, preferably at least 70.0% by weight, preferably at least 80.0% by weight.

3. The polymer composition (P) at least one polyamide (PA); - optionally at least one filler; and at least one optional additive other than a filler, in particular an additive selected from the group consisting of colorants, dyes, pigments, lubricants, plasticizers, flame retardants, reinforcing agents, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, electromagnetic absorbers, and combinations thereof; 10. The filament of claim 1, comprising or consisting of:

4. 2. The filament according to claim 1, wherein the polymer composition (P) comprises or consists of at least one polyamide (PA) and, as additives, i) at least one filler, and ii) at least one optional additive other than a filler, in particular an additive selected from the group consisting of colorants, dyes, pigments, lubricants, plasticizers, flame retardants, reinforcing agents, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, electromagnetic absorbers, and combinations thereof.

5. 2. The filament of claim 1, wherein the polymer composition (P) comprises at least one additive selected from the group consisting of colorants, dyes, pigments, lubricants, plasticizers, flame retardants, toughening agents, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, electromagnetic absorbers, and combinations thereof.

6. 2. The filament of claim 1, wherein the polymer composition (P) comprises at least one filler selected from the group consisting of continuous or chopped carbon fibers, continuous or chopped glass fibers, crushed carbon fibers, crushed glass fibers, glass beads, glass microspheres, wollastonite, silica beads, talc, calcium carbonate, bio-based fibers, polymer fibers, and combinations thereof.

7. 7. The filament according to claim 6, wherein the polymer composition (P) comprises carbon fibers as an additive.

8. 4. The filament according to claim 3, wherein the proportion of the filler and / or additives other than fillers in the polymer composition (P) is less than 50.0% by weight, or from 0.01 to 50.0% by weight, or even from 0.10 to 40.0% by weight, or from 0.50 to 40.0% by weight.

9. 4. The filament according to claim 3, wherein the filler and / or non-filler additives are blended with the polyamide (PA).

10. The polyamide (PA) has the following properties: a glass transition temperature (Tg) greater than 120°C; and / or a melting point (Tm) of less than 280°C; 2. The filament of claim 1, wherein:

11. 2. The filament of claim 1, wherein the proportion of said 4,4'-diaminodicyclohexylmethane moieties in the trans / trans configuration is at least 40.0 mol %, more preferably at least 50.0 mol %.

12. 2. The filament of claim 1, wherein the proportion of said 4,4'-diaminodicyclohexylmethane moieties in the trans / trans configuration is less than 55.0 mole percent.

13. 2. The filament of claim 1, wherein the proportion of said 4,4'-diaminodicyclohexylmethane moieties in trans / trans configuration is between 30.0 mol % and 50.0 mol %, this latter value being excluded.

14. The number of repeating units (R ＰＡ 2. The filament according to claim 1, wherein the proportion of α- and β-amino groups in the polymer is at least 60.0 mol%, preferably at least 75.0 mol%, preferably at least 80.0 mol%, preferably at least 85.0 mol%, preferably at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%, preferably at least 99.5 mol%.

15. The repeating unit of the polyamide (PA) is the repeating unit (R ＰＡ ) or the repeating unit (R ＰＡ 10. The filament of claim 1, consisting essentially of

16. The polyamide (PA) is a polyamide having the repeating unit (R ＰＡ ) and comprising repeat units according to formula (IV) and / or formula (V) (R* ＰＡ 2. The filament of claim 1, which is a copolyamide also comprising: 【Chemistry 2】 (In the formula, R １ is a bond, optionally containing one or more heteroatoms (e.g., O, N, or S) and optionally containing halogen (e.g., fluorine, chlorine, bromine, or iodine), hydroxy (—OH), sulfo (—SO ３ M) (for example, where M is H, Na, K, Li, Ag, Zn, Mg, or Ca), C １ ~C ６ Alkoxy, C １ ~C ６ Alkylthio, C １ ~C ６ Acyl, formyl, cyano, C ６ ~C １５ Aryloxy and C ６ ~C １５ C optionally substituted with one or more substituents selected from the group consisting of aryl ２ ~C １５ Alkylene and C ６ ~C ３０ arylene; R ２ optionally contains one or more heteroatoms (e.g., O, N, or S) and may contain halogen (e.g., fluorine, chlorine, bromine, or iodine), hydroxy (—OH), sulfo (—SO ３ M) (for example, where M is H, Na, K, Li, Ag, Zn, Mg, or Ca), C １ ~C ６ Alkoxy, C １ ~C ６ Alkylthio, C １ ~C ６ Acyl, formyl, cyano, C ６ ~C １５ Aryloxy and C ６ ~C １５ C optionally substituted with one or more substituents selected from the group consisting of aryl １ ~C ２０ Alkylene and C ６ ~C ３０ arylene; R ３ optionally contains one or more heteroatoms (e.g., O, N, and S) and may contain halogen (e.g., fluorine, chlorine, bromine, and iodine), hydroxy (—OH), sulfo (—SO ３ M) (for example, where M is H, Na, K, Li, Ag, Zn, Mg, or Ca), C １ ~C ６ Alkoxy, C １ ~C ６ Alkylthio, C １ ~C ６ Acyl, formyl, cyano, C ６ ~C １５ Aryloxy and C ６ ~C １５ Straight-chain or branched C optionally substituted with one or more substituents selected from the group consisting of aryl ２ ~C １４ alkylene).

17. R １ is C ２ ~C １５ Alkylene and C ６ ~C ３０ arylene; R ２ is C １ ~C ２０ Alkylene and C ６ ~C ３０ arylene, preferably R ２ Ga-(CH ２ ) ｎ - (n is a repeating unit (R ＰＡ ) is the same as ３ is a linear or branched C ２ ~C １４ 17. The filament of claim 16, which is an alkylene.

18. The repeating unit (R*) in the copolyamide ＰＡ 17. The filament according to claim 16, wherein the proportion of hydroxybenzoates is between 1.0 mol% and 25.0 mol%, preferably between 5.0 mol% and 20.0 mol%.

19. The repeating unit of the polyamide (PA) is a unit (R ＰＡ ) and (R* ＰＡ 17. The filament of claim 16, comprising:

20. 2. The filament according to claim 1, wherein said polymer composition (P) comprises only one polyamide (PA).

21. 2. The filament according to claim 1, wherein the polymer composition (P) does not comprise an aromatic polyamide.

22. 2. The filament according to claim 1, wherein the polymer composition (P) does not comprise an amorphous polyamide.

23. 2. The filament according to claim 1, wherein the polymer composition (P) does not contain any polyamide other than the polyamide (PA).

24. The end group of the polyamide (PA) is —NH ２ 2. The filament of claim 1, wherein the end group is selected from the group consisting of -COOH, -COOH, and amide.

25. 25. The filament of claim 24, wherein the amide of the amide end group is of the formula -NH-C(=O)-R, where R is an alkyl group, an aryl group, or a cycloalkyl group, and / or -C(=O)-NH-R', where R' is an alkyl group or a cycloalkyl group.

26. The filament of claim 1 , wherein the components of the polymer composition (P) are blended together.

27. 2. The filament according to claim 1, wherein the polyamide (PA) exhibits a heat of fusion Hm of at least 15.0 J / g, preferably at least 18.0 J / g, Hm being determined by DSC in the second heating scan according to ISO 11357.

28. 2. The filament according to claim 1, wherein the polyamide (PA) has a melting point (Tm) of 200-280°C, preferably 220-270°C, Tm being determined by DSC in the second heating scan according to ISO 11357.

29. 2. The filament according to claim 1, wherein the polyamide (PA) has a glass temperature (Tg) of 120°C to 160°C, preferably 130°C to 170°C, Tg being determined by DSC in the second heating scan according to ISO 11357.

30. 2. The filament according to claim 1, wherein said polyamide (PA) has a number average molecular weight Mn ranging from 5,000 g / mol to 40,000 g / mol.

31. 2. Filaments according to claim 1, wherein the polyamide (PA) has a water absorption at saturation by immersion in water at 23°C of less than 6.0% by weight, preferably less than 5.0% by weight, less than 4.0% by weight.

32. 2. Filaments according to claim 1, wherein the polymer composition (P) has a water absorption at saturation by immersion in water at 23°C of less than 6.0% by weight, preferably less than 5.0% by weight, more preferably less than 4.0% by weight.

33. 10. The filament of claim 1, having a cylindrical or substantially cylindrical shape and a diameter d of 0.5 mm to 5.0 mm.

34. 2. The filament according to claim 1, wherein the composition of said filament consists of said polymer composition (P).

35. The filament described in claim 1, which is a solid filament.

36. 10. The filament of claim 1, which does not exhibit a core / shell geometry.

37. 2. The filament according to claim 1, produced by extruding said composition (P).

38. 10. The filament of claim 1 having a length L of at least 200 mm.

39. 2. The filament according to claim 1, wherein the polyamide (PA) exhibits a bio-based content of at least 40.0 wt.%, preferably at least 80 wt.%, preferably at least 85.0 wt.%, preferably at least 90.0 wt.%, preferably at least 99.5 wt.%, wherein the bio-based content is expressed as % of organic carbon of renewable origin and measured according to ASTM D6866-22.

40. A spool of filament according to any one of claims 1 to 39.

41. A method of manufacturing a 3D object using an additive manufacturing system and a filament according to any one of claims 1 to 39.

42. 42. The method of claim 41, comprising the step of extruding said composition (P) into filaments.

43. - advancing the filament of claim 1 to a print head; - heating the filaments in the print head to a molten state, preferably the filaments are heated to a temperature of at least Tm+10°C, Tm being the melting point of polyamide (PA); - extruding said material in a molten state from the nozzles of said print head; - ensuring relative movement of the print heads in X and Y directions to form the cross-sectional shape of the 3D object; and / or - ensuring relative movement of the print heads in Z direction to form the 3D object in height; 42. The method of claim 41, comprising:

44. Use of the filament according to any one of claims 1 to 39 in 3D printing.

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