Filament based on a core material comprising a fibrous filler

Abstract

This invention relates to a filament comprising a core material (CM) containing fiber filler (FF) and a thermoplastic polymer (TP1), wherein the core material (CM) is coated with a shell material (SM) containing a thermoplastic polymer (TP2). Furthermore, this invention relates to a method for preparing the filament, and to a three-dimensional object and a method for preparing the same.

Description

[0001] This invention relates to a filament comprising a core material (CM) containing fiber filler (FF) and a thermoplastic polymer (TP1), wherein the core material (CM) is coated with a shell material (SM) containing a thermoplastic polymer (TP2). Furthermore, this invention relates to a method for preparing the filament, and to a three-dimensional object and a method for preparing the same.

[0002] One of the most commonly used 3D printing or additive manufacturing technologies is fused deposition modeling (FDM), also known as fused filament fabrication (FFF). To create a three-dimensional object, a filament of thermoplastic material, typically provided on a spool, is deposited layer by layer onto a substrate through heated nozzles. Therefore, the thermoplastic material is heated to a temperature exceeding its melting and / or glass transition temperature. The thermoplastic material and temperature gradient are selected so that it solidifies substantially immediately upon contact with the substrate or extrusion of the previous layer of thermoplastic material.

[0003] To form the layers, a drive motor is provided to move the substrate and / or extrusion nozzles (dispensing heads) relative to each other along the x, y, and z axes in a predetermined pattern. Fused deposition modeling (FDM) was first described in US 5,121,329.

[0004] In industry, thermoplastic materials are generally of particular importance due to their excellent mechanical properties. Specifically, they possess high strength, hardness, and toughness, good chemical resistance, and high abrasion resistance and arc track resistance. However, for some applications, such as in the automotive industry, there is a need to further improve the chemical resistance, hardness, and dimensional stability of thermoplastic materials. Therefore, they are often reinforced with fiber fillers.

[0005] However, it is possible to produce three-dimensional objects containing fiber fillers by molten filaments only when the fiber filler content in the filament does not exceed 15% by weight. Otherwise, the filaments cannot be wound onto a spool and are difficult to feed into the nozzle of a 3D printer due to their rough surface and lack of lubrication.

[0006] WO 2017 / 009190 A1 discloses a filament comprising a core material coated with a shell material, wherein the core material comprises an inorganic powder and a binder and the shell material comprises a thermoplastic polymer. This filament can be used to produce three-dimensional metallic or ceramic objects.

[0007] However, the application of filaments comprising a core material (CM) containing fiber filler and a first thermoplastic polymer and coated with a shell material containing a second thermoplastic polymer is not disclosed.

[0008] WO 2015 / 077262 A9 discloses 3D printer feeds comprising filaments containing separated layers or portions. The feeds, particularly the filaments, can be prepared by co-extrusion, microlayer co-extrusion, or multi-component / fragment co-extrusion.

[0009] However, the filaments comprising a core material coated with a shell material are not described, wherein the core material (CM) comprises fiber filler and a first thermoplastic polymer and the shell material comprises a second thermoplastic polymer.

[0010] Therefore, the fundamental objective of this invention is to provide a new filament for extrusion-based additive manufacturing systems that overcomes the aforementioned disadvantages.

[0011] This objective is achieved through filaments comprising a core material (CM) coated with a shell material (SM), wherein

[0012] The core material (CM) comprises components a) to c).

[0013] a) At least one fiber filler (FF),

[0014] b) at least one thermoplastic polymer (TP1), and

[0015] c) Optionally, at least one additive (A),

[0016] Furthermore, the shell material (SM) contains components d) to f).

[0017] d) At least one thermoplastic polymer (TP2),

[0018] e) Optionally at least one fiber filler (FF), and

[0019] f) Optionally, at least one additive (A).

[0020] One advantage of the filaments of the present invention compared to filaments made from the same core material (CM) but without a shell material (SM) is their higher mechanical stability. In particular, the filaments of the present invention can be wound on a spool, while filaments of the shell material (SM) (monofilaments) are generally too brittle to be suitable for winding.

[0021] Since the mechanical properties and therefore the processability of the filaments of the present invention in conventional machines for fused filament manufacturing (FFF) are mainly determined by the shell material (SM), the composition of the core material (CM) has more freedom of variation compared to filaments without a shell material (SM).

[0022] For example, the shell material (SM)-core material (CM) configuration of the present invention allows for a significantly higher fiber filler (FF) load in the core material (CM), which could potentially result in a more brittle core. In practice, a fiber filler (FF) load of up to 50% by weight of the total weight of the core material (CM) can be applied. According to the present invention, without a shell material (SM), it is impossible to continuously feed highly brittle materials into conventional machines used in fused filament manufacturing processes (FFF).

[0023] In other words, the breaking bending radius of the filament of the present invention is smaller than that of the single filament. The breaking bending radius is the radius at which the (single) filament breaks. The smaller the breaking bending radius of the (single) filament, the more flexible it is and the better it can be wound on a spool.

[0024] Furthermore, the filaments of the present invention may also exhibit a sticky or extremely sticky core material (CM), which can clog the feeding mechanism in the presence of a shell-less material (SM). Therefore, the method of the present invention enables the production of filaments for melt filament manufacturing processes (FFF) with an ultra-low viscosity or extremely sticky core material (CM).

[0025] Furthermore, in the fused filament manufacturing process (FFF), the shell material (SM) of the filament of the present invention acts as an adhesive between the layers of the three-dimensional body. Therefore, the three-dimensional body of the present invention exhibits increased mechanical strength along the z-axis and thus greater dimensional stability.

[0026] Furthermore, the three-dimensional body of the present invention is already a finished component. No further processing steps are required. Therefore, by using the filaments of the present invention, a three-dimensional body with a high fiber filler load can be prepared in an extremely rapid and simple manner.

[0027] For the purposes of this invention, the term "fiber filler (FF)" refers to a filler whose length is significantly greater than its width and has a fibrous shape. Preferably, the aspect ratio of the fiber filler (FF) in the filament is from 3:1 to 2000:1, more preferably from 10:1 to 1000:1, and most preferably from 20:1 to 500:1.

[0028] In a preferred embodiment, the fiber filler (FF) in the filament has a length of 50 to 2000 μm, more preferably 100 to 800 μm, and most preferably 150 to 400 μm. Furthermore, the fiber filler (FF) in the filament preferably has a diameter of 4 to 60 μm, more preferably 8 to 40 μm, and most preferably 10 to 20 μm.

[0029] The present invention will be described in more detail below.

[0030] The filament consists of a core material (CM) coated with a shell material (SM).

[0031] The filaments may be of any length and / or diameter that a person skilled in the art deems appropriate.

[0032] Preferably, the diameter of the filament is 1 to 3 mm, more preferably 1.2 to 2.8 mm, and most preferably 1.4 to 2.6 mm.

[0033] The shell material (SM) can have any thickness that a person skilled in the art would deem appropriate.

[0034] Preferably, the thickness of the shell material (SM) is 0.04 to 0.6 mm, more preferably 0.06 to 0.3 mm.

[0035] The core material (CM) may have any diameter that is deemed appropriate by those skilled in the art.

[0036] Preferably, the diameter of the core material (CM) is 1 to 2 mm, more preferably 1.2 to 1.8 mm, and most preferably 1.4 to 1.6 mm.

[0037] The core material (CM) comprises components a) to c).

[0038] As component a), the core material (CM) includes at least one fiber filler (FF).

[0039] For the purposes of this invention, the terms "component a)" and "fiber filler (FF)" are synonymous and interchangeable throughout the invention. "Fiber filler (FF)" specifically refers to one fiber filler (FF) or a mixture of two or more fiber fillers (FF).

[0040] The core material (CM) may contain at least one fiber filler (FF) in any amount as deemed suitable by those skilled in the art. Preferably, the core material (CM) contains 10 to 50% by weight, more preferably 15 to 45% by weight, and most preferably 20 to 40% by weight of at least one fiber filler (FF) based on the total weight of the core material (CM).

[0041] As component a), any known fiber filler (FF) may be used. Preferably, at least one fiber filler (FF) is selected from the group consisting of natural fibers, synthetic fibers and inorganic fibers.

[0042] Examples of suitable natural fibers include cellulose fibers, protein fibers, and polylactide fibers.

[0043] Examples of suitable synthetic fibers are aramid fibers, polyacrylic fibers, and polyester fibers, such as polyethylene terephthalate fibers or polybutylene terephthalate fibers.

[0044] Examples of suitable inorganic fibers include ceramic fibers, glass fibers, carbon fibers, and basalt fibers.

[0045] When the fiber filler (FF) is glass fiber, the glass fiber is preferably made of E, A, or C glass. The glass fiber can be used in commercially available forms, either as roving (continuous filament fiber) or as shredded glass fiber (segment fiber).

[0046] Preferably, at least one fiber filler (FF) is selected from synthetic fibers and inorganic fibers. More preferably, at least one fiber filler (FF) is selected from aramid fibers, glass fibers, and carbon fibers, most preferably glass fibers and carbon fibers made of E, A, or C glass, and particularly preferably carbon fibers.

[0047] In one embodiment of the invention, when the fiber filler (FF) is carbon fiber, the carbon fiber does not contain any metals and / or metal alloys and / or ceramic materials. Preferably, in this embodiment, the carbon fiber does not contain any metals, metal alloys, or ceramic materials.

[0048] To improve the compatibility between at least one thermoplastic polymer (TP1) or at least one thermoplastic polymer (TP2) and at least one fiber filler (FF), the surface of the fiber filler may be treated with a silane compound.

[0049] Suitable silanes are those based on general formula (I):

[0050] (X-(CH2) g ) k -Si-(OC h H 2h+1 ) 4-k (I)

[0051] in

[0052] g is 2 to 10, preferably 3 to 4.

[0053] h is 1 to 5, preferably 1 to 2.

[0054] k can be 1 to 3, preferably 1, and

[0055] X is an amino, glycidyl, or hydroxyl group.

[0056] Preferably, the silane compound is selected from the group consisting of: aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and the corresponding silane compound containing a glycidyl group as a substituent X.

[0057] Preferably, the fiber filler (FF) contains 0.01 to 2% by weight, preferably 0.025 to 1% by weight, and especially 0.05 to 0.5% by weight, of a silane compound based on the total weight of the fiber filler (FF).

[0058] Suitable carbon fiber can be branded Purchased, suitable fiberglass can be branded. Purchased.

[0059] Thermoplastic polymers reinforced with fiber fillers (FF) are also available. For example, polyamides reinforced with glass fibers or carbon fibers are available from BASF SE under the trademark Ultramid.

[0060] As component b), the core material (CM) comprises at least one thermoplastic polymer (TP1).

[0061] For the purposes of this invention, the terms "component b)" and "thermoplastic polymer (TP1)" are synonymous and interchangeable throughout the invention. "Thermoplastic polymer (TP1)" specifically refers to one thermoplastic polymer (TP1) and a mixture of two or more thermoplastic polymers (TP1).

[0062] At least one thermoplastic polymer (TP1) may comprise thermoplastic homopolymers, thermoplastic copolymers, and blends of thermoplastic polymers.

[0063] The core material (CM) may contain at least one thermoplastic polymer (TP1) in any amount as deemed suitable by those skilled in the art. Preferably, the core material (CM) contains 50 to 90% by weight, more preferably 55 to 85% by weight, and most preferably 60 to 80% by weight, of at least one thermoplastic polymer (TP1) based on the total weight of the core material (CM).

[0064] As component b), any known thermoplastic polymer can be used. Preferably, at least one thermoplastic polymer (TP1) of the core material (CM) is selected from the group consisting of: impact-modified vinyl aromatic copolymers, styrene-based thermoplastic elastomers (S-TPE), polyolefins (PO), aliphatic-aromatic copolyesters, polycarbonates, thermoplastic polyurethanes (TPU), polyamides (PA), polyphenylene sulfide (PPS), polyaryl ether ketones (PAEK), polysulfones, and polyimides (PI), more preferably selected from impact-modified vinyl aromatic copolymers, polyolefins (PO), aliphatic-aromatic copolyesters, and polyamides (PA).

[0065] At least one thermoplastic polymer (TP1) of the core material (CM) may be selected from an impact-modified vinyl aromatic copolymer.

[0066] Impact-modified vinyl aromatic copolymers are known and commercially available.

[0067] Preferred impact-modified vinyl aromatic copolymers are impact-modified copolymers composed of vinyl aromatic monomers and vinyl cyanide (styrene-acrylonitrile copolymer (SAN)). The preferred impact-modified SAN used preferably comprises an acrylonitrile-styrene acrylate (ASA) polymer and / or an acrylonitrile-butadiene-styrene (ABS) polymer, or a (meth)acrylate-acrylonitrile-butadiene-styrene polymer (“MABS”, transparent ABS), or blends of SAN, ABS, ASA, and MABS with other thermoplastic materials, such as polycarbonate, polyamide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), or polyolefin (PO).

[0068] The tensile strain values ​​at break of ASA and ABS that can be used as component b) are generally 10% to 300%, preferably 15% to 250%, and particularly preferably 20% to 200%.

[0069] In tensile testing, the fracture tensile strain is determined on a 1BA type test specimen (referring to Annex A of the standard: “small test specimen”) in accordance with ISO 527-2:1996.

[0070] ASA polymers are generally impact-modified SAN polymers that contain vinyl aromatic compounds, especially styrene and vinyl cyanide, elastomeric graft copolymers of vinyl aromatic compounds, especially styrene and vinyl cyanide, especially acrylonitrile, on polyalkyl acrylate rubber in a copolymer matrix, particularly composed of styrene and / or α-methylstyrene and acrylonitrile.

[0071] At least one thermoplastic polymer (TP1) of the core material (CM) may also be selected from styrene-based thermoplastic elastomers (S-TPE).

[0072] Styrene-based thermoplastic elastomers (S-TPE) are also known and commercially available.

[0073] Preferred styrene-based thermoplastic elastomers (S-TPEs) are those with a tensile strain at break exceeding 300%, particularly preferably exceeding 500%, and especially exceeding 500% to 600%. Blended S-TPEs particularly preferably comprise linear or star-shaped styrene-butadiene block copolymers having outer polystyrene blocks (S) and a random styrene-butadiene distribution (S / B) between said blocks. 无规 Or it may have a styrene gradient (S / B). 递变 Styrene-butadiene copolymer blocks (e.g. from BASF SE) or K-Resin from CPC TM ).

[0074] The total butadiene content is preferably in the range of 15 to 50% by weight, particularly preferably in the range of 25 to 40% by weight, and the total styrene content is correspondingly preferably in the range of 50 to 85% by weight, particularly preferably in the range of 60 to 75% by weight.

[0075] The styrene-butadiene block (S / B) is preferably composed of 30 to 75% by weight of styrene and 25 to 70% by weight of butadiene. The (S / B) block is particularly preferably composed of 35 to 70% by weight of butadiene and 30 to 65% by weight of styrene.

[0076] The content of polystyrene block (S) is preferably in the range of 5 to 40% by weight, particularly in the range of 25 to 35% by weight, based on the total block copolymer. The content of copolymer block (S / B) is preferably in the range of 60 to 95% by weight, particularly in the range of 65 to 75% by weight.

[0077] Particularly preferred are linear styrene-butadiene block copolymers with a generalized S-(S / B)-S structure, having one or more (S / B) components with a random styrene / butadiene distribution. 无规 The block is located between two S blocks. This type of block copolymer can be obtained by anionic polymerization in a nonpolar solvent with the addition of a polar cosolvent or potassium salt, as described, for example, in WO 95 / 35335 or WO 97 / 40079.

[0078] The vinyl content is the relative content of 1,2-bonds in the diene unit, calculated based on all 1,2-cis, 1,4-cis, and 1,4-trans bonds. The 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably less than 20%, particularly in the range of 10% to 18%, and especially preferably in the range of 12% to 16%.

[0079] At least one thermoplastic polymer (TP1) of the core material (CM) may also be selected from polyolefin (PO).

[0080] Polyolefins (PO) are known and commercially available. They are typically prepared by polymerization of C2-C8 olefin monomers, preferably by polymerization of C2-C4 olefin monomers.

[0081] In the context of this invention, C2-C8 olefins refer to unsubstituted or at least monosubstituted hydrocarbons having 2 to 8 carbon atoms and at least one carbon-carbon double bond (CC double bond). "At least one carbon-carbon double bond" precisely refers to one carbon-carbon double bond and two or more carbon-carbon double bonds.

[0082] In other words, C2-C8 olefins refer to unsaturated hydrocarbons having 2 to 8 carbon atoms. The hydrocarbons can be branched or unbranched. Examples of C2-C8 olefins with one C-C double bond include ethylene, propylene, 1-butene, 2-butene, 2-methyl-propylene (= isobutene), 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-hexene, 3-hexene, and 4-methyl-1-pentene. Examples of C2-C8 olefins with two or more C-C double bonds include propadiene, 1,3-butadiene, 1,4-pentadiene, 1,3-pentadiene, and 2-methyl-1,3-butadiene (= isoprene).

[0083] If a C2-C8 olefin has one C-C double bond, the polyolefin (PO) prepared from those monomers is linear. If a C2-C8 olefin has more than one double bond, the polyolefin (PO) prepared from those monomers can be crosslinked. Linear polyolefins (PO) are preferred.

[0084] Polyolefin (PO) copolymers can also be used, which are prepared by using different C2-C8 olefin monomers during the preparation of polyolefin (PO).

[0085] The polyolefin (PO) is preferably selected from the group consisting of: polymethylpentene, poly-1-butene, polyisobutylene, polyethylene, and polypropylene. Polyethylene and polypropylene are particularly preferred, as well as copolymers thereof as known to those skilled in the art and available commercially.

[0086] Polyolefins (PO) can be prepared by any polymerization method known to those skilled in the art, preferably by free radical polymerization, such as by emulsion, bead, solution, or bulk polymerization. Depending on the monomer and the type of polymerization, possible initiators are free radical initiators, such as peroxides and azo compounds, wherein the amount of initiator is typically in the range of 0.001 to 0.5% by weight based on the monomer.

[0087] At least one thermoplastic polymer (TP1) of the core material (CM) may also be selected from polycarbonate.

[0088] Polycarbonate itself is known and available.

[0089] The polycarbonates that can be used generally have a tensile strain at break of 20% to 300%, preferably 30% to 250%, and especially preferably 40% to 200%.

[0090] For example, it can be obtained by interfacial polycondensation according to the method of DE-B-1 300 266, or by the reaction of diphenyl carbonate with bisphenol according to the method of DE-A-1495 730. The preferred bisphenol is 2,2-bis(4-hydroxyphenyl)propane, which is generally and also referred to below as bisphenol A.

[0091] Instead of bisphenol A, other aromatic dihydroxy compounds may be used, especially 2,2-bis(4-hydroxyphenyl)pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylthione, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfite, 4,4'-dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloane, preferably dihydroxydiphenylcyclohexane or dihydroxycyclopentane, especially 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane or mixtures of the above-mentioned dihydroxy compounds.

[0092] Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aforementioned aromatic dihydroxy compounds.

[0093] Particularly suitable as component b) is a polycarbonate comprising units derived from resorcinol esters or alkyl resorcinol esters, such as the polycarbonates described in WO 00 / 61664, WO 00 / 15718, or WO 00 / 26274. Such polycarbonates are, for example, sold by General Electric under the trademark [trademark name missing].

[0094] Copolycarbonates according to US-A 3 737 409 may also be used, with particular interest here for copolycarbonates based on bisphenol A and di(3,5-dimethyldihydroxyphenyl) sulfone, characterized by high heat resistance. Mixtures of different polycarbonates may also be used.

[0095] The polycarbonate used can be in the form of regrinding or pelletizing.

[0096] At least one thermoplastic polymer (TP1) of the core material (CM) may be selected from thermoplastic polyurethane (TPU).

[0097] Thermoplastic polyurethane (TPU) is a polymer containing urethane units. Thermoplastic polyurethane and its preparation are known to those skilled in the art.

[0098] Within the scope of this invention, aliphatic thermoplastic polyurethane (TPU) is preferred. It can be prepared, for example, by addition polymerization of an aliphatic polyisocyanate with an aliphatic polyhydroxy compound. Among the polyisocyanates, diisocyanates of general formula (II) are preferred.

[0099] OCN-R 7 -NCO (II),

[0100] in

[0101] R 7 C1-C, whether substituted or unsubstituted 20Alkylene or C4-C 20 Cycloalkylene compounds, wherein the substituents are selected from the group consisting of F, Cl, Br and C1-C6 alkyl groups.

[0102] R 7 Preferably substituted or unsubstituted C2-C 12 Alkylene or C6-C 15 Cycloalkylene.

[0103] Within the context of this invention, for example, C1-C 20 The definition of alkylene refers to C1-C 20 Alkyl. C1-C 20 Alkylenes are hydrocarbons having two free valences and having 1 to 20 carbon atoms. According to the invention, C1-C... 20 Alkylenes can be branched or unbranched.

[0104] Within the context of this invention, for example, C4-C 20 The definition of cycloalkylene refers to C4-C 20 Cycloalkyldiyl. C4-C 20 Cycloalkylene compounds are cyclic hydrocarbons with two free valences and 4 to 20 carbon atoms. Hydrocarbons with two free valences, cyclic or straight-chain components, and 4 to 20 carbon atoms also fall within this definition.

[0105] The preferred diisocyanate is selected from the group consisting of: hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,2-diisocyanomethylcyclohexane, 1,4-diisocyanomethylcyclohexane, and isoflurone diisocyanate (IUPAC name: 5-isocyano-1-(isocyanomethyl)-1,3,3-trimethyl-cyclohexane).

[0106] Diisocyanates can also be used as oligomers, such as dimers or trimers. Alternatively, conventional block polyisocyanates, obtained from the isocyanate via addition reactions of phenol or caprolactam, can also be used.

[0107] Suitable polyhydroxy compounds for preparing aliphatic polyurethanes are, for example, polyesters, polyethers, polyesteramides, or polyacetals or mixtures thereof.

[0108] Suitable chain extenders for the preparation of thermoplastic polyurethanes are low molecular weight polyols, especially diols and polyamines, especially diamines or water.

[0109] Thermoplastic polyurethane (TPU) is preferably substantially non-crosslinked, meaning it can be repeatedly melted without significant signs of decomposition. The specific viscosity reduction measured in dimethylformamide at 30°C is typically from 0.5 dl / g to 3 dl / g, preferably from 1 dl / g to 2 dl / g.

[0110] At least one thermoplastic polymer (TP1) of the core material (CM) may also be selected from polyamide (PA).

[0111] Polyamide (PA) itself is known and commercially available.

[0112] Polyamide (PA) preferably contains at least one unit selected from the group consisting of: -NH-(CH2) x -NH- unit, where x is 4, 5, 6, 7, or 8; -CO-(CH2) y -NH- units, where y is 3, 4, 5, 6, or 7; and -CO-(CH2) units. z -CO- unit, where z is 2, 3, 4, 5 or 6.

[0113] Polyamide (PA) more preferably contains at least one unit selected from the group consisting of: -NH-(CH2) x -NH- unit, where x is 5, 6, or 7; -CO-(CH2) y -NH- unit, where y is 4, 5, or 6; and -CO-(CH2) z -CO- unit, where z is 3, 4 or 5.

[0114] Polyamide (PA) particularly preferably contains at least one unit selected from the group consisting of: -NH-(CH2)6-NH- unit, -CO-(CH2)5-NH- unit and -CO-(CH2)4-CO- unit.

[0115] If the polyamide (PA) contains at least one component selected from -CO-(CH2) y If the unit is a group consisting of -NH- units, then the unit is generally derived from a lactam having 5 to 9 ring members, preferably from a lactam having 6 to 8 ring members, and particularly preferably from a lactam having 7 ring members.

[0116] Lactams are generally well known to those skilled in the art. For the purposes of this invention, lactams should be understood to refer to cyclic amides. Preferably, the lactam used to prepare polyamide (PA) contains 4 to 8 cyclic carbon atoms, more preferably 5 to 7 cyclic carbon atoms, and particularly preferably 6 cyclic carbon atoms.

[0117] Suitable lactams are selected from the following groups: but-4-lactam (γ-lactam, γ-butyrolactam), 2-piperidinone (δ-lactam, δ-pentanolactam), hex-6-lactam (ε-lactam, ε-caprolactam), hepta-7-lactam (δ-lactam, δ-heptanolactam), and oct-8-lactam (ε-lactam, ε-octanolactam).

[0118] The lactams are preferably selected from the group consisting of: 2-piperidinone (δ-lactam, δ-pentanolactam), hex-6-lactam (ε-lactam, ε-caprolactam) and hepta-7-lactam (δ-lactam, δ-heptanolactam).

[0119] If the polyamide (PA) contains at least one unit selected from the group consisting of -NH-(CH2)x-NH- units, then the unit is typically derived from a diamine. The polyamide (PA) is then preferably obtained via a diamine conversion, more preferably via the conversion of a diamine with a dicarboxylic acid.

[0120] Suitable diamines are generally known to those skilled in the art and contain 4 to 8 carbon atoms, preferably 5 to 7 carbon atoms and more preferably 6 carbon atoms.

[0121] Suitable amines are selected from the group consisting of: 1,4-diaminobutane (but-1,4-diamine, tetramethylenediamine, putrescine), 1,5-diaminopentane (pentamethylenediamine, pent-1,5-diamine, cadaverine), 1,6-diaminohexane (hexamethylenediamine, hexane-1,6-diamine), 1,7-diaminoheptane, and 1,8-diaminooctane. The diamine is preferably selected from the group consisting of 1,5-diaminopentane, 1,6-diaminohexane, and 1,7-diaminoheptane. 1,6-diaminohexane is particularly preferred.

[0122] In addition, polyamides (PAs) may contain units derived from m-xylenediamine, bis-(4-aminophenyl)methane, bis-(4-aminocyclohexyl)methane, 2,2-bis-(4-aminophenyl)propane, 2,2-bis-(4-aminocyclohexyl)propane and / or 1,5-diamino-2-methylpentane.

[0123] If the polyamide (PA) contains at least one component selected from -CO-(CH2) z If the unit is a group consisting of -CO- units, then the unit is typically derived from a dicarboxylic acid. Then at least one polyamide (A) is preferably obtained via a dicarboxylic acid conversion, more preferably via a diamine conversion of the dicarboxylic acid.

[0124] Suitable dicarboxylic acids are generally known to those skilled in the art and contain 4 to 8 carbon atoms, preferably 5 to 7 carbon atoms and more preferably 6 carbon atoms.

[0125] Suitable dicarboxylic acids are selected from the group consisting of: succinic acid, glutaric acid, adipic acid, pimelic acid, and octanoic acid. The dicarboxylic acids are preferably selected from the group consisting of glutaric acid, adipic acid, and pimelic acid. Adipic acid is particularly preferred.

[0126] Polyamides (PAs) may additionally contain other units, such as units derived from lactams having 10 to 13 ring members, such as octyl lactam and / or laurolactam.

[0127] Furthermore, polyamides (PAs) may contain units derived from aliphatic dicarboxylic acids having 9 to 36 carbon atoms, preferably 9 to 12 carbon atoms, and more preferably 9 to 10 carbon atoms. Aromatic dicarboxylic acids are also suitable.

[0128] Examples of such dicarboxylic acids are azelaic acid, sebacic acid, dodecanoic acid, isophthalic acid, and / or terephthalic acid.

[0129] The following non-exhaustive list includes the polyamides mentioned above, as well as other polyamides (monomers are indicated in parentheses) suitable as component b) to achieve the objectives of this invention:

[0130] PA 4 (pyrrolidone)

[0131] PA 6 (ε-caprolactam)

[0132] PA 7 (ethanolamide)

[0133] PA 8 (Octinamide)

[0134] PA 9 (9-Aminononanoic acid)

[0135] PA 11 (11-Aminoundecanoic acid)

[0136] PA 12 (Lauryl lactam)

[0137] PA 46 (Tetramethylenediamine, Adipic acid)

[0138] PA 66 (hexamethylenediamine, adipic acid)

[0139] PA 69 (hexamethylenediamine, azelaic acid)

[0140] PA 610 (hexamethylenediamine, sebacic acid)

[0141] PA 612 (hexamethylenediamine, decanedicarboxylic acid)

[0142] PA 613 (hexamethylenediamine, undecanedicarboxylic acid)

[0143] PA 1212 (1,12-dodecanediamine, decanedicarboxylic acid)

[0144] PA 1313 (1,13-diaminotridecane, undecanedicarboxylic acid)

[0145] PA 6T (hexamethylenediamine, terephthalic acid)

[0146] PA 9T (nonadiamine, terephthalic acid)

[0147] PA MXD6 (m-xylenediamine, adipic acid)

[0148] PA 6I (hexamethylenediamine, isophthalic acid)

[0149] PA 6-3-T (Trimethylhexanediamine, terephthalic acid)

[0150] PA 6 / 6T (see PA 6 and PA 6T)

[0151] PA 6 / 66 (see PA 6 and PA 66)

[0152] PA 6 / 12 (see PA 6 and PA 12)

[0153] PA 66 / 6 / 610 (see PA 66, PA 6 and PA 610)

[0154] PA 6I / 6T (see PA 6I and PA 6T)

[0155] PA PACM 12 (Diaminodicyclohexylmethane, laurolactam)

[0156] PA 6I / 6T / PACM (see PA 6I / 6T and diaminodicyclohexylmethane)

[0157] PA 12 / MACMI (Lauryl lactam, dimethyldiaminodicyclohexylmethane, isophthalic acid)

[0158] PA 12 / MACMT (Lauryl lactam, dimethyldiaminodicyclohexylmethane, terephthalic acid)

[0159] PA PDA-T (phenylenediamine, terephthalic acid)

[0160] Therefore, the present invention also provides a filament in which at least one thermoplastic polymer (TP1) of the core material (CM) is a polyamide (PA), preferably a polyamide (PA) selected from the group consisting of: polyamide 4, polyamide 6, polyamide 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 69, polyamide 610, polyamide 612, polyamide 613, polyamide 1212, polyamide 1313, polyamide 6T, polyamide 9T, polyamide MXD6, polyamide 6I, polyamide 6-3-T, polyamide 6 / 6T, polyamide 6 / 66, polyamide 6 / 12, polyamide 66 / 6 / 610, polyamide 6I / 6T, polyamide PACM12, polyamide 6I / 6T / PACM, polyamide 12 / MACMI, polyamide 12 / MACMT and polyamide PDA-T.

[0161] The polyamide and its preparation are known. Details regarding its preparation can be found by those skilled in the art in the following: “Ullmanns” "der Technischen Chemie", 4th edition, Vol. 19, pp. 39-54, Verlag Chemie, Weinheim 1980; "Ullmanns Encyclopedia of Industrial Chemistry", Vol. A21, pp. 179-206, VCH Verlag, Weinheim 1992; and Stoeckhert, Kunststofflexikon, pp. 425-428, Hanser Verlag, Munich 1992 (keywords "polyamide" and below).

[0162] Preferably, the polyamide (PA) is selected from the group consisting of: polyamide 6, polyamide 46, polyamide 66, polyamide 610, polyamide 6 / 12, polyamide 6 / 66, polyamide 6T, polyamide 9T, polyamide 6I, polyamide 6 / 6T and polyamide 6I / 6T.

[0163] Polyamide (PA) generally has a viscosity number in the range of 30 to 350 ml / g, preferably in the range of 90 to 240 ml / g, and particularly preferably in the range of 100 to 130 ml / g. The viscosity number is determined according to ISO 307 in a solution of 0.5 wt% polyamide (PA) in 100 ml of 96 wt% strong sulfuric acid at 25°C.

[0164] The weight-average molecular weight (M) of polyamide (PA) wThe weight-average molecular weight (M) is typically in the range of 500 to 2,000,000 g / mol, preferably in the range of 5,000 to 500,000 g / mol, and particularly preferably in the range of 10,000 to 100,000 g / mol. The weight-average molecular weight (M) is determined according to ASTM D4001. w ).

[0165] The melting temperature T of polyamide (PA) is determined by differential scanning calorimetry (DSC) or by dynamic mechanical thermometry (DMTA). M Typically, the temperature range is 80 to 330°C, preferably 150 to 250°C, and particularly preferably 180 to 230°C. For amorphous polyamides, T M Defined as at least one polyamide (A) (with a minimum solution viscosity of 80 mL / g in sulfuric acid according to ISO 307) having a zero-shear viscosity of at least 5000 Pa·s and therefore being molten at a temperature that is treatable (measured on a DHR-1 rotational rheometer from TA Instruments, disk / disk geometry, disk diameter 25 mm and sample height 1.0 mm. Deformation 1.0%, preheating time 1.5 min, and the material pre-dried under reduced pressure at 80 °C for 7 days).

[0166] Polyamides (PAs) typically have a glass transition temperature (T0). g The glass transition temperature (T) of polyamide (PA) g The temperature is typically in the range of 0 to 160°C, and preferably in the range of 40 to 105°C.

[0167] Glass transition temperature (T) g The glass transition temperature (Tg) is determined by differential scanning calorimetry (DSC). g The measurements were performed in a nitrogen atmosphere using hot / cold / hot cycles at 20 °C / min, 20 °C / min, and 20 °C / min, respectively. For the measurements, approximately 0.006 to 0.010 g of the material was sealed in an aluminum crucible. In the first heating cycle, the sample was heated to 340 °C, then rapidly cooled to 0 °C, and then in the second heating cycle, heated to 340 °C. The corresponding T was measured from the second heating cycle. g Values. Those skilled in the art know of values ​​used to determine the glass transition temperature (T). g This program.

[0168] As component c), the core material (CM) may contain at least one additive (A).

[0169] For the purposes of this invention, the terms "component (c)" and "additive (A)" are synonymous and interchangeable throughout this invention. "Additive (A)" specifically refers to one additive (A) or a mixture of two or more additives (A).

[0170] The core material (CM) may contain at least one additive (A) in any amount as deemed suitable by those skilled in the art. Preferably, the core material (CM) contains at least one additive (A) in 0 to 20% by weight, more preferably 0 to 15% by weight, and most preferably 0 to 10% by weight, based on the total weight of the core material (CM).

[0171] As component c), any known additive (A) may be used. Preferably, additive (A) is selected from the group consisting of dispersants, stabilizers, pigments and thickeners.

[0172] The dispersant itself is known and available for purchase.

[0173] Examples of suitable dispersants are low molecular weight oligomeric polyethylene oxide, stearic acid, stearamide, hydroxystearic acid, fatty alcohol, fatty alcohol esters, fatty acid esters, sulfonates, and block copolymers of ethylene oxide and propylene oxide, with a molecular weight of 200 to 600 g / mol, and polyisobutylene is particularly preferred.

[0174] In addition, additive (A) may be selected from stabilizers and / or antioxidants such as UV stabilizers.

[0175] Additive (A) may be selected from pigments such as organic dyes and / or inorganic pigments.

[0176] Additive (A) may be a self-tackifier, such as a polymer having a glass transition temperature below room temperature (preferably below 25°C), and / or a terpene derivative.

[0177] Additive (A) may also be selected from tackifiers disclosed in WO 2013 / 117428 A1. An example of a commercially available tackifier is... A107.

[0178] According to WO 2013 / 117428 A1 and applying the definition of the components of the thickener in WO 2013 / 117428 A1, it is preferred to use a dispersion containing at least one of the following monomers in a water-soluble dispersion polymer as a thickener, wherein the polymer has a weighted average molecular weight of less than 50,000 and a glass transition temperature greater than or equal to -40°C and less than or equal to 0°C, preferably greater than or equal to -35°C or equal to 0°C:

[0179] (a) at least 40% by weight of at least one C1 to C20 alkyl ester of (meth)acrylate

[0180] (b) 0 to 30% by weight of at least one vinyl aryl compound

[0181] (c) at least 0.1% by weight of at least one acid monomer

[0182] (d) 0 to 50% by weight of other monomers,

[0183] The amount of monomers is calculated as the sum of all monomers.

[0184] In addition, thickeners as disclosed in US 4,767,813 and as specified in the following three paragraphs may be used.

[0185] According to US 4,767,813, the tackifier may be rosin or a rosin derivative having a ring and ball softening temperature of about 25°C to 110°C (preferably about 50°C to 110°C).

[0186] Suitable tackifiers include rosin, hydrogenated rosin, glyceryl rosin such as triglyceride, and C-type rosin such as triethylene glycol rosin and tripropylene glycol rosin. 2-3 Alkylene rosinates; rosin salts, disproportionated rosin salts, pentaerythritol, and polyterpene resins including α and β pinenes. Suitable resins are sold under the trademarks Staybelite Ester 3, Staybelite Ester 10, Pentalyn H, and Hercolyn D.

[0187] The tackifier resin may be a C5 or C9 synthetic tackifier resin having a ring and ball softening point of about 10 to 100°C, preferably about 50 to 100°C. Suitable resins are sold under the trade names Piccovar, Hercotac, Picconal, and Piccolyte. The tackifier is polymerized from a C9 monomer, preferably aryl, and a C5 monomer, preferably aliphatic.

[0188] Shell material (SM) comprises components d) to f).

[0189] As component d), the shell material (SM) contains at least one thermoplastic polymer (TP2).

[0190] For the purposes of this invention, the terms "component d)" and "thermoplastic polymer (TP2)" are synonymous and interchangeable throughout the invention. "Thermoplastic polymer (TP2)" specifically refers to one thermoplastic polymer (TP2) and a mixture of two or more thermoplastic polymers (TP2).

[0191] At least one thermoplastic polymer (TP2) may comprise thermoplastic homopolymers, thermoplastic copolymers, and blends of thermoplastic polymers.

[0192] The shell material (SM) may contain at least one thermoplastic polymer (TP2) in any amount as deemed suitable by those skilled in the art. Preferably, the shell material (SM) contains 75 to 100% by weight, more preferably 80 to 98% by weight, and most preferably 90 to 95% by weight of at least one thermoplastic polymer (TP2) based on the total weight of the shell material (SM).

[0193] Those skilled in the art may select any technically appropriate thermoplastic polymer as component d).

[0194] Thermoplastic polymer (TP2) in shell material (SM) can

[0195] i) identical to at least one thermoplastic polymer (TP1) of the core material (CM), or

[0196] ii) Different from at least one thermoplastic polymer (TP1) of the core material (CM).

[0197] Preferably, at least one thermoplastic polymer (TP2) of the shell material (SM) is selected from the group consisting of: polyoxymethylene (POM), impact-modified vinyl aromatic copolymers, styrene-based thermoplastic elastomers (S-TPE), polyolefins (PO), thermoplastic polyurethanes (TPU), polyamides (PA), polyethers (PETH), polycarbonates (PC), polyesters (PES), polyphenylene sulfide (PPS), polyaryl ether ketones (PAEK), polysulfones, and polyimides (PI), preferably selected from polyolefins (PO), thermoplastic polyurethanes (TPU), polyamides (PA), polycarbonates (PC), polyesters (PES), polyphenylene sulfide (PPS), polyaryl ether ketones (PAEK), polysulfones, and polyimides (PI).

[0198] At least one thermoplastic polymer (TP2) of the shell material (SM) may be selected from polyether (PETH).

[0199] Polyethers contain repeating units of formula (III).

[0200]

[0201] in

[0202] R 11 To R 14 Each is independently selected from the group consisting of: H, C1-C4 alkyl and halogen-substituted C1-C4 alkyl;

[0203] R 15 Choose from the following groups: chemical bonds, (-CR) 15a R 15b -) group and (-CR 15a R 15bO-) group, in which

[0204] R 15a and R 15b Each is independently selected from the group consisting of H and unsubstituted or at least monosubstituted C1-C4 alkyl groups.

[0205] The substituents are selected from the group consisting of F, Cl, Br, OH and C1-C4 alkyl groups;

[0206] n can be 0, 1, 2, or 3.

[0207] If n is 0, then R 15 This is a chemical bond between adjacent carbon and oxygen atoms. If R 15 For (-CR) 15a R 15b O-) group, then (-CR 15a R 15b The oxygen atom (O) of the O- group is bonded to another carbon atom (C) of formula (III) instead of the oxygen atom (O) of formula (III). That is, formula (III) does not contain peroxide compounds. The same applies to formula (IV).

[0208] Typical polyethers and their preparation are known to those skilled in the art.

[0209] The preferred polyether according to the invention is, for example, poly(alkylene glycol), also known as poly(olefin oxide).

[0210] Polyoxyalkylene and its preparation are known to those skilled in the art. They are typically synthesized by the interaction of water and divalent or polyvalent alcohols with cyclic ethers of general formula (IV), i.e., epoxides. The reaction is catalyzed by acidic or basic catalysts. The reaction is a so-called ring-opening polymerization of cyclic ethers of general formula (IV).

[0211]

[0212] in

[0213] R 11 To R 15 It has the same meaning as that defined above for formula (III).

[0214] The preferred poly(oxyene oxide) according to the invention is derived from monomers of general formula (IV) having 2 to 6 carbon atoms in the ring. That is, preferably, the poly(oxyene oxide) is a poly(C2-C6 oxide). Particularly preferred are poly(oxyene oxide) derived from monomers selected from the group consisting of: 1,3-dioxacyclopentane, 1,3-dioxacycloheptane, and tetrahydrofuran (lUPAC name: oxacyclopentane). That is, the poly(oxyene oxide) is particularly preferably selected from the group consisting of: poly-1,3-dioxacyclopentane, poly-1,3-dioxacycloheptane, and polytetrahydrofuran.

[0215] In one embodiment, the poly(oxyene oxide) may include OH-terminal groups. In another embodiment, at least some of the OH-terminal groups of the poly(oxyene oxide) may be capped. Methods for capping OH-terminal groups are known to those skilled in the art. For example, OH-terminal groups may be capped by etherification or esterification.

[0216] The weight-average molecular weight of the poly(oxyolefin) is preferably in the range of 1,000 to 150,000 g / mol, particularly preferably in the range of 1,500 to 120,000 g / mol and even more preferably in the range of 2,000 to 100,000 g / mol.

[0217] As component e), the shell material (SM) may contain at least one fiber filler (FF).

[0218] The shell material (SM) may contain at least one fiber filler (FF) in any amount as deemed suitable by those skilled in the art. Preferably, the shell material (SM) contains 0 to 15% by weight, more preferably 0 to 10% by weight, and most preferably 0 to 5% by weight of the total weight of the shell material (SM).

[0219] At least one fiber filler in the shell material (SM) is consistent with the fiber filler (FF) defined for the core material (CM).

[0220] In a preferred embodiment, the shell material (SM) comprises at least one fiber filler (FF) at 0% by weight of the total weight of the shell material (SM), and therefore preferably, component e is not present in the shell material (SM).

[0221] As component f), the shell material (SM) may contain at least one additive (A).

[0222] The shell material (SM) may contain at least one additive (A) in any amount as deemed suitable by those skilled in the art. Preferably, the shell material (SM) contains at least one additive (A) in 0 to 20% by weight, more preferably 0 to 15% by weight, and most preferably 0 to 10% by weight, based on the total weight of the shell material (SM).

[0223] At least one additive in the shell material (SM) is consistent with the additive (A) defined for the core material (CM).

[0224] In one embodiment of the invention, the core material (CM) comprises components a), b) and c).

[0225] a) at least one fiber filler (FF) comprising 10 to 50% by weight, preferably 15 to 45% by weight, and more preferably 20 to 40% by weight, based on the total weight of the core material (CM).

[0226] b) at least one thermoplastic polymer (TP1) comprising 50 to 90% by weight, preferably 55 to 85% by weight, and more preferably 60 to 80% by weight, based on the total weight of the core material (CM).

[0227] c) at least one additive (A) comprising 0 to 20% by weight, preferably 0 to 15% by weight, and more preferably 0 to 10% by weight, based on the total weight of the core material (CM).

[0228] and / or the shell material (SM) contains components d) and f).

[0229] d) at least one thermoplastic polymer (TP2) comprising 75 to 100% by weight, preferably 80 to 98% by weight, and more preferably 90 to 95% by weight, based on the total weight of the shell material (SM).

[0230] e) at least one fiber filler (FF) comprising 0 to 15% by weight, preferably 0 to 10% by weight, and more preferably 0 to 5% by weight, based on the total weight of the shell material (SM).

[0231] f) at least one additive (A) comprising 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, based on the total weight of the shell material (SM).

[0232] In another embodiment of the invention, the core material (CM) comprises components a), b) and c).

[0233] a) at least one fiber filler (FF) comprising 10 to 50% by weight, preferably 15 to 45% by weight, and more preferably 20 to 40% by weight, based on the total weight of the core material (CM).

[0234] b) at least one thermoplastic polymer (TP1) comprising 50 to 90% by weight, preferably 55 to 85% by weight, and more preferably 60 to 80% by weight, based on the total weight of the core material (CM).

[0235] c) at least one additive (A) comprising 0 to 20% by weight, preferably 0 to 15% by weight, and more preferably 0 to 10% by weight, based on the total weight of the core material (CM).

[0236] and / or the shell material (SM) contains components d) and f).

[0237] d) At least one thermoplastic polymer (TP2) comprising 100% by weight of the total weight of the shell material (SM),

[0238] e) At least one fiber filler (FF) comprising 0% by weight of the total weight of the shell material (SM),

[0239] f) At least one additive (A) at 0% by weight of the total weight of the shell material (SM).

[0240] Another subject of the present invention is a method for preparing the filament as described above, wherein a core material (CM) is coated with a shell material (SM) by co-extrusion of the core material (CM) and the shell material (SM).

[0241] Co-extrusion technology is known to those skilled in the art.

[0242] Based on the coating materials used for the core and shell materials, those skilled in the art can select appropriate co-extrusion temperatures and processing parameters for each.

[0243] Another subject of the present invention is a method for producing three-dimensional objects by a fused filament manufacturing process, which includes at least steps a), b), and c):

[0244] a) Supply the filaments from the spool as described above to the nozzle.

[0245] b) Heat the filament to a temperature (T) M ),

[0246] c) The heated filament obtained in step b) is deposited in a build disk using layer-based additive manufacturing techniques to form the three-dimensional object.

[0247] The fused filament manufacturing process used to create three-dimensional objects is well known in the prior art and explained in detail in the literature cited above. The fused filament manufacturing process is also known as 3D printing.

[0248] According to step a), the filament according to the invention is supplied on a spool to a nozzle.

[0249] According to step b), the filament is heated to temperature (T). M Temperature (T) M The melting point of at least one thermoplastic polymer (TP1) exceeds that of at least one thermoplastic polymer (TP1). Methods for determining the melting point of at least one thermoplastic polymer (TP1) are known to those skilled in the art. For example, the melting point of at least one thermoplastic polymer (TP1) can be estimated by differential scanning calorimetry (DSC).

[0250] In a preferred embodiment of the invention, in process step b), the filament is heated to a temperature (T) at least 1°C, preferably at least 5°C, and particularly preferably at least 10°C higher than the melting point of at least one thermoplastic polymer (TP1). M ).

[0251] In another preferred embodiment, the filament is heated to a temperature in the range of 140°C to 400°C, preferably 160°C to 380°C (T M ).

[0252] According to step c), filaments are deposited in a build disk using layer-based additive manufacturing techniques. The temperature of the build disk is typically in the range of 30 to 150°C, preferably 40 to 120°C, and particularly preferably 60 to 100°C.

[0253] That is, in steps a) to c) of the method of the present invention, the filament is generally initially present in a solid state and then melted and printed to form a three-dimensional object containing the filament.

[0254] Another subject of the present invention is three-dimensional objects prepared by the methods described in detail above.

[0255] The following examples further illustrate the present invention.

[0256] The filaments in Examples E1 and E2 (according to the present invention) are prepared by co-extruding a core material (CM) and a shell material (SM) using the following materials, equipment and processing parameters.

[0257] Material:

[0258] Core materials (CM) of Examples E1 and E2 (according to the present invention):

[0259] E1: Nylon 6.6 with 20% carbon fiber (80% polyamide 66, 20% carbon fiber (CF); Trademark name: Ultramid A3WC4)

[0260] E2: Nylon 6.6 with 50% glass fiber (50% polyamide 66, 50% glass fiber (GF); trademark: Ultramid A3WG10)

[0261] Shell material (SM) of Examples E1 and E2 (according to the present invention):

[0262] E1: Nylon 6.6 (100% by weight polyamide 66; trademark name Ultramid A3W)

[0263] E2: Nylon 6.6 (100% by weight polyamide 66; trademark name Ultramid A3W)

[0264] equipment

[0265] Extrusion equipment:

[0266] Core: ZSK 25 twin-screw extruder

[0267] Shell: Teach-Line E20T single-screw extruder, featuring 8 / 6 / 11 polyolefin screws, utilizing a compression ratio of 3.08.

[0268] Nozzle: Modified blow molding die, with a matrix diameter of 3.6mm.

[0269] Other equipment:

[0270] water bath

[0271] BAW130T Conveyor

[0272] Zumbach diameter measurement

[0273] Processing parameters:

[0274] All polymers were dried at 80°C before processing using an air dryer and a conveyor speed of 7 m / min.

[0275] Example E1:

[0276] Core Material (CM):

[0277] Extrusion press with 80 wt% polyamide 66 and 20 wt% carbon fiber (Ultramid A3WC4).

[0278] Temperature characteristics: 260℃ / 270℃ / 270℃ / 280℃ / 280℃, Skin Adapter 280℃, Mold 280℃

[0279] Outer layer of shell material (SM):

[0280] Extruder with 100% by weight polyamide 66 (Ultramid A3W)

[0281] Temperature characteristics: 260℃ / 270℃ / 270℃ / 280℃ / 280℃, Skin Adapter 280℃, Mold 280℃

[0282] Filament characteristics:

[0283] Diameter 1.75mm, ellipticity 0.03mm

[0284] Core diameter: 1.59mm

[0285] Outer layer thickness: 0.08mm

[0286] Example E2:

[0287] Core Material (CM):

[0288] Extruder, with 50 wt% polyamide 66 and 50 wt% glass fiber (Ultramid A3WG10).

[0289] Temperature characteristics: 260℃ / 270℃ / 270℃ / 280℃ / 280℃, Skin Adapter 280℃, Mold 280℃

[0290] Outer layer of shell material (SM):

[0291] Extruder with 100% by weight polyamide 66 (Ultramid A3W)

[0292] Temperature characteristics: 260℃ / 270℃ / 270℃ / 280℃ / 280℃, Skin Adapter 280℃, Mold 280℃

[0293] Filament characteristics:

[0294] Diameter 1.78mm, ellipticity 0.05mm

[0295] Core diameter: 1.46mm

[0296] Outer layer thickness: 0.16mm

[0297] The monofilaments in Examples C3 and C4 (comparative Examples) were prepared by extrusion using the following materials, equipment, and processing parameters.

[0298] Material:

[0299] C3: Nylon 6.6 with 20% carbon fiber (80% polyamide 66, 20% carbon fiber (CF); trademark: Ultramid A3WC4)

[0300] C4: Nylon 6.6 with 50% glass fiber (50% polyamide 66, 50% glass fiber (GF); trademark: Ultramid A3WG10)

[0301] The monofilament is made of the same core material (CM) as in an embodiment according to the invention, but without a shell material (SM).

[0302] equipment:

[0303] Extrusion equipment:

[0304] Extrusion press: Teach-Line E20T single-screw extruder, featuring 8 / 6 / 11 screws for polyolefins, utilizing a compression ratio of 3.08...

[0305] Nozzle: A mold with a diameter of 3.6mm.

[0306] Other equipment:

[0307] water bath

[0308] BAW130T Conveyor

[0309] Zumbach diameter measurement

[0310] Processing parameters:

[0311] All polymers were dried at 80°C before processing using an air dryer and a conveyor speed of 7 m / min.

[0312] Example C3:

[0313] Monofilament:

[0314] Extrusion press with 80 wt% polyamide 66 and 20 wt% carbon fiber (Ultramid A3WC4).

[0315] Temperature characteristics: 260℃ / 270℃ / 270℃ / 280℃ / 280℃, Skin Adapter 280℃, Mold 280℃

[0316] Filament characteristics:

[0317] Diameter 1.75mm, ellipticity 0.05mm

[0318] Example C4:

[0319] Monofilament:

[0320] Extruder, with 50 wt% polyamide 66 and 50 wt% glass fiber (Ultramid A3WG10).

[0321] Temperature characteristics: 260℃ / 270℃ / 270℃ / 280℃ / 280℃, Skin Adapter 280℃, Mold 280℃

[0322] Filament characteristics:

[0323] Diameter 1.75mm, ellipticity 0.05mm

[0324] The breaking bending radius of the filaments in Examples E1 and E2 (according to the present invention) and the monofilaments in Examples C3 and C4 (comparative examples) was measured (Table 1).

[0325] Table 1

[0326] Example core shell Fracture bending radius [cm] E1 Ultramid A3WC4 Ultramid A3W 2.35 C3 Ultramid A3WC4 none 3.45 E2 Ultramid A3WG10 Ultramid A3W 3.70 C4 Ultramid A3WG10 none 11.15

[0327] The breaking bending radius of a (single) filament is the radius at which the (single) filament breaks. The smaller the breaking bending radius of a (single) filament, the more flexible it is, and therefore the better it can be wound onto a spool.

[0328] As shown in Table 1, the filaments in Examples E1 and E2 (according to the present invention) exhibit a lower breaking bend radius than the corresponding monofilaments in Examples C3 and C4 (comparative examples). Therefore, the filaments E1 and E2 of the present invention can be more flexible and wound on a spool without breaking. In other words, the filaments according to the present invention, having the same core material as the corresponding filaments of the comparative examples but with a different outer shell material, exhibit improved flexibility due to their lower breaking bend radius.

Claims

1. A filament comprising a core material (CM) coated with a shell material (SM), wherein... The core material (CM) comprises components a) to c). a) at least one fiber filler (FF) comprising 10 to 50% by weight of the total weight of the core material (CM), b) at least one thermoplastic polymer (TP1) comprising 50 to 90% by weight of the total weight of the core material (CM), and c) at least one additive (A) comprising 0 to 20% by weight of the total weight of the core material (CM), The shell material (SM) comprises components d) to f). d) at least one thermoplastic polymer (TP2) comprising 75 to 100% by weight of the total weight of the shell material (SM), e) at least one fiber filler (FF) comprising 0 to 15% by weight of the total weight of the shell material (SM), and f) at least one additive (A) comprising 0 to 20% by weight of the total weight of the shell material (SM), The at least one thermoplastic polymer (TP2) of the shell material (SM) is the same as the at least one thermoplastic polymer (TP1) of the core material (CM), and the at least one thermoplastic polymer (TP1) is a polyamide (PA) selected from the group consisting of: polyamide 6, polyamide 46, polyamide 66, polyamide 610, polyamide 6 / 12, polyamide 6 / 66, polyamide 6T, polyamide 9T, polyamide 6I, polyamide 6 / 6T and polyamide 6I / 6T.

2. The filament according to claim 1, wherein the at least one fiber filler (FF) is selected from synthetic fibers and inorganic fibers.

3. The filament according to claim 1, wherein the at least one fiber filler (FF) is selected from aramid fibers, glass fibers and carbon fibers.

4. The filament according to claim 1, wherein the at least one fiber filler (FF) is selected from glass fibers and carbon fibers made of E, A or C glass.

5. The filament according to claim 1, wherein the at least one fiber filler (FF) is selected from carbon fiber.

6. The filament according to any one of claims 1 to 5, wherein the surface of the fiber filler (FF) is treated with a silane compound according to general formula (I): (X-(CH2) g ) k -Si-(OC h H 2h+1 ) 4-k (I) in g is between 2 and 10. h is between 1 and 5. k is between 1 and 3, and X is an amino, glycidyl, or hydroxyl group.

7. The filament according to any one of claims 1 to 5, wherein i) The aspect ratio of the fiber filler (FF) is from 3:1 to 2000:1, and / or ii) The fiber filler (FF) has a length of 50 to 2000 μm, and / or iii) The fiber filler (FF) has a diameter of 4 to 60 μm.

8. The filament according to any one of claims 1 to 5, wherein i) The aspect ratio of the fiber filler (FF) is from 10:1 to 1000:1, and / or ii) The fiber filler (FF) has a length of 100 to 800 μm, and / or iii) The fiber filler (FF) has a diameter of 8 to 40 μm.

9. The filament according to any one of claims 1 to 5, wherein i) The aspect ratio of the fiber filler (FF) is from 20:1 to 500:1, and / or ii) The fiber filler (FF) has a length of 150 to 400 μm, and / or iii) The fiber filler (FF) has a diameter of 10 to 20 μm.

10. The filament according to any one of claims 1 to 5, wherein the at least one thermoplastic polymer (TP2) of the shell material (SM) is selected from the group consisting of: polyoxymethylene (POM), impact-modified vinyl aromatic copolymers, styrene-based thermoplastic elastomers (S-TPE), polyolefins (PO), thermoplastic polyurethanes (TPU), polyamides (PA), polyethers (PETH), polycarbonates (PC), polyesters (PES), polyphenylene sulfide (PPS), polyaryl ether ketones (PAEK), polysulfones, and polyimides (PI).

11. The filament according to any one of claims 1 to 5, wherein the at least one thermoplastic polymer (TP2) of the shell material (SM) is selected from the group consisting of: polyolefin (PO), thermoplastic polyurethane (TPU), polyamide (PA), polycarbonate (PC), polyester (PES), polyphenylene sulfide (PPS), polyaryl ether ketone (PAEK), polysulfone, and polyimide (PI).

12. The filament according to any one of claims 1 to 5, wherein i) The diameter of the filament is 1 to 3 mm, and / or ii) The diameter of the core material (CM) is 1 to 2 mm, and / or ii) The thickness of the shell material (SM) is 0.04 to 0.6 mm.

13. The filament according to any one of claims 1 to 5, wherein i) The diameter of the filament is 1.2 to 2.8 mm, and / or ii) The diameter of the core material (CM) is 1.2 to 1.8 mm, and / or ii) The thickness of the shell material (SM) is 0.06 to 0.3 mm.

14. The filament according to any one of claims 1 to 5, wherein i) The diameter of the filament is 1.4 to 2.6 mm, and / or ii) The diameter of the core material (CM) is 1.4 to 1.6 mm, and / or ii) The thickness of the shell material (SM) is 0.06 to 0.3 mm.

15. The filament according to any one of claims 1 to 5, wherein the at least one additive (A) is selected from the group consisting of dispersants, stabilizers, pigments and thickeners.

16. A method for preparing filaments according to any one of claims 1 to 15, wherein the core material (CM) is coated with a layer of the shell material (SM) by co-extruding a core material (CM) and a shell material (SM).

17. A method for preparing a three-dimensional object by a fused filament manufacturing process, comprising at least steps a), b), and c). a) Feeding the filaments from the spool according to any one of claims 1 to 15 to the nozzle. b) Heat the filament to a temperature (T) M ), c) The heated filaments obtained in step b) are deposited in a build disk using layer-based additive manufacturing techniques to form the three-dimensional object.

18. The method of claim 17, wherein the temperature (T) in step b) M The temperature ranges from 140℃ to 400℃.

19. A three-dimensional object prepared by the method according to claim 17 or 18.

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