Additive manufacturing method for producing three-dimensional objects

Abstract

The present disclosure relates to an additive manufacturing (AM) method for producing three-dimensional (3D) objects using a part material (M) comprising at least one PEEK-PEoEK copolymer, in particular a 3D object obtainable from this part material (M) by fused deposition modeling (FDM) or fused filament fabrication (FFF).

Description

[Technical Field]

[0001] Related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 119,171 filed November 30, 2020, and European Patent Application Publication No. 21155706.1 filed February 8, 2021, the entire contents of each of these applications being incorporated herein by reference for any purpose.

[0002] This disclosure relates to an additive manufacturing (AM) method for producing a three-dimensional (3D) object using a component material (M) comprising at least one copolymer including poly(etheretherketone) (PEEK) repeating units and poly(etherorthoetherketone) (PEoEK) repeating units, and more particularly to a 3D object that can be obtained from this component material (M) by fused deposition modeling (FDM) or fused filament manufacturing (FFF). [Background technology]

[0003] Additive manufacturing systems are used to print or otherwise construct 3D parts from a digital representation of a 3D part using one or more additive manufacturing techniques. Examples of commercially available additive manufacturing techniques include extrusion-based techniques, selective laser sintering, powder / binder jetting, electron beam melting, and stereolithography processes. For each of these techniques, the digital representation of the 3D part is first sliced ​​into multiple horizontal layers. For each sliced ​​layer, a tool path is subsequently generated, which instructs a specific additive manufacturing system to print a given layer.

[0004] For example, in an extrusion-based additive manufacturing system, a 3D part can be printed from a digital representation of the 3D part in a layer-by-layer manner by extruding strips of part material adjacent to each other. The part material is extruded through an extrusion chip carried by the system's print head and deposited as a series of paths on a printing plate in the x and y planes. The extruded part material fuses with the previously deposited part material and solidifies as the temperature decreases. At that time, the position of the print head relative to the substrate is incremented along the z axis (perpendicular to the x and y planes), and this process is then repeated to form a 3D part that resembles the digital representation. An example of an extrusion-based additive manufacturing system starting from a filament is called fused filament manufacturing (FFF), also known as fused deposition modeling (FDM). Pellet additive manufacturing (PAM) is another example of an extrusion-based 3D printing method in which raw materials can be printed in pellet form.

[0005] Poly(aryletherketone) polymers (PAEKs), such as poly(etheretherketone) polymers (PEEK), are known for their high-temperature performance and excellent chemical resistance. Their use in manufacturing 3D objects / articles / parts is documented in the literature. For some semi-crystalline polymers, such as PEEK, degradation and / or crosslinking occur due to processing temperatures that are too high. This is known to negatively impact the processability and recyclability of the material by selective laser sintering (SLS), another commonly used 3D printing process that uses polymer powder as a part material.

[0006] The printability drawbacks of PEEK in extrusion-based 3D printing processes have been addressed in various ways in the patent literature. International Publication No. 2019 / 055737A1 (Arkema) specifically describes the PEKK70 / 30 copolymer, which crystallizes more slowly than PEEK and is easier to print, having a favorable property profile and the option to use a post-print annealing process to further improve some mechanical properties and chemical resistance. International Publication No. 2015 / 081009A1 (Stratasys) describes a substantially miscible polymer blend of one semicrystalline polymer and a second polymer having the function of slowing the crystallization rate of the first semicrystalline polymer.

[0007] Also described are PEEK-PEDEK copolymers (containing PEDEK units of formula: -Ph-Ph-O-Ph-C(O)-Ph- (where -Ph- is a 1,4-phenylene unit) and more than 65% PEEK units of formula: -Ph'-O-Ph'-C(O)-Ph'-O- (where -Ph'- is a 1,4-phenylene group)) for manufacturing articles formed using melting and extrusion molding of raw materials. International Publication No. 2017 / 051202A1 (Victrex) describes PEEK-PEDEK75 / 25 copolymers that offer slower crystallization rates than PEEK. Although these materials exhibit lower melting temperatures, their mechanical properties were inferior to those of PEEK.

[0008] The object of the present invention is to provide a PAEK-based polymer material for use in extrusion-based 3D printing processes that has a lower melting temperature, a slower crystallization rate, and high mechanical properties and chemical resistance. As described below, a PEEK-PEoEK copolymer comprising PEEK repeating units and PEoEK repeating units provides a suitable technical solution for this purpose.

[0009] PEEK-PEoEK copolymers have been described in the art. Japanese Patent Publication No. 01-221426 specifically describes, in Examples 5 and 6, a PEEK-PEoEK copolymer prepared from hydroquinone, catechol, and difluorobenzophenone having an elevated glass transition temperature and simultaneously excellent heat resistance. Similarly, A. Ben-Haida et al., in Macromolecules, 2006, 39, 6467-6472, describe 50 / 50 and 70 / 30 copolymers of PEEK and PEoEK prepared by stepwise polycondensation of hydroquinone and catechol with 4,4'-difluorobenzophenone in diphenyl sulfone. However, these documents do not describe PEEK-PEoEK filaments or pellets for use in extrusion-based 3D manufacturing. [Overview of the project]

[0010] The present invention relates to a method for manufacturing a 3D object using an additive manufacturing system such as an extrusion-based additive manufacturing system (e.g., FFF or FDM).

[0011] 3D objects or articles obtained by such manufacturing methods can be used in a variety of end applications. In particular, these include implantable devices, medical devices, dental prosthetics, brackets and complex-shaped parts in the aerospace industry, and under-hood components in the automotive industry.

[0012] The method of the present invention comprises the step of printing layers of a 3D object from a component material (M). The component material (M) may be in the form of a filament and may be used in an extrusion-based additive manufacturing system starting from a filament, known as fused filament manufacturing (FFF) and also known as fused deposition modeling (FDM). Alternatively, the component material may be in the form of pellets and may be used in a 3D printing technology (PAM) that can print pellet-formed raw materials.

[0013] The present invention generally relates to an AM method for manufacturing a 3D object, which includes extruding a component material (M) containing a polymer component, wherein such a polymer component includes at least one PEEK-PEoEK copolymer, and this copolymer contains, in total, at least 50 mol% of repeating units (R PEoEK , , 2 , , , PEoEK , , , PEEK , PEEK , <00D0005>, , , ,

[0014] , ) and repeating units (R PEoEK ), (a) The repeating unit (R PEEK ) is a repeating unit of formula (A): [Chemical formula] and (b) The repeating unit (R PEoEK ) is a repeating unit of formula (B): [Chemical formula] In these formulas, - Each R 1 and R 2 is the same as or different from each other, and in each occurrence, is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium, - Each a and b is the same as or different from each other, and is independently selected from the group consisting of integers in the range of 0 to 4, - The PEEK-PEoEK copolymer contains repeating units R PEEK / R PEoEK in a molar ratio in the range of 95 / 5 to 5 / 95, and relates to an AM method including repeating units R PEEK and R PEoEK .

[0014] The applicant's achievement is remarkable in identifying that the PEEK-PEoEK copolymer, either alone or in blends with other polymers (e.g., PEEK), possesses both a slow crystallization rate and a lower percentage of crystallinity than pure PEEK. The reduced crystallinity allows these properties to enable not only more reliable printing of objects compared to pure PEEK, but also its use in 3D printing of larger and more complex objects. Interestingly, the crystallization rate is not so slow that crystallinity is completely lost from the 3D printed objects. Parts 3D printed from these compositions retain some degree of crystallinity after printing, and, unexpectedly, when printed at heating chamber temperatures close to the polymer's glass transition temperature (Tg), parts printed from these compositions exhibit little to no warping.

[0015] The terms “polymer” or “copolymer” are used herein to refer to homopolymers containing substantially 100 mol% of the same repeating units and copolymers containing at least 50 mol%, for example, at least about 60 mol%, at least about 65 mol%, at least about 70 mol%, at least about 75 mol%, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, at least about 95 mol%, or at least 98 mol% of the same repeating units.

[0016] The term "part material" in this specification means a material, in particular a blend of polymeric compounds, intended to form a 3D object or a part of a 3D object. Part material (M) is used as a feedstock used for the manufacture of a 3D object or a part of a 3D object in accordance with the present invention.

[0017] The method of the present invention employs a PEEK-PEoEK copolymer as the main component of a part material that can be molded, for example, into a filament to construct a 3D object (e.g., a 3D model, 3D article, or 3D part). The polymer can also be printed in the form of pellets, for example, pellets of a polymer blend.

[0018] In this application, - Any description, even if it is described in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present invention. - Where it is said that an element or component is included in and / or selected from the enumerated list of elements or components, in the relevant embodiments expressly contemplated herein, the element or component may be any one of the individual enumerated elements or components, or may be selected from any group of two or more of the expressly enumerated elements or components, and any element or component enumerated in the list of elements or components may be omitted from such list, and - Any enumeration of numerical ranges by endpoints in this specification includes all numbers contained within the enumerated range, as well as the endpoints and equivalents of the range.

[0019] According to one embodiment, the component material is in the form of a filament. The term "filament" according to the present invention means a thread-like object, fiber, or strand formed from a material or blend of materials containing at least the PEEK-PEoEK copolymer described herein.

[0020] The filament may have a cylindrical or substantially cylindrical shape, or a non-cylindrical shape such as a ribbon filament shape. Furthermore, the filament may have a hollow shape, or a core-shell shape, in which another polymer composition is used to form either the core or the shell.

[0021] According to one embodiment of the present invention, a method for manufacturing a 3D object using an AM system includes a step of extruding a part material (M). This step may be performed, for example, when printing or depositing strips or layers of the part material (M). Methods for manufacturing 3D objects using extrusion-based additive manufacturing systems are also known as fused filament manufacturing (FFF), fused deposition modeling (FDM), and pellet additive manufacturing (PAM).

[0022] FFF / FDM 3D printers are commercially available from companies such as Apium, Roboze, Hyrel, or Stratasys, Inc. (trade name Fortus®). SLS 3D printers are available from companies such as EOS Corporation (trade name EOSINT®P). FRTP 3D printers are available from companies such as Markforged.

[0023] PAM 3D printers are commercially available, for example, from Pollen. BAAM (Bulk Additive Manufacturing) is an industrial-scale additive manufacturing device commercially available from Cincinnati Inc.

[0024] Parts and materials The component material (M) used in the method of the present invention comprises a polymer component, which comprises at least one PEEK-PEoEK copolymer, and this copolymer comprises at least 50 mol% of repeating units (R) in total relative to the total number of repeating units in the PEEK-PEoEK copolymer. PEEK ) and repeating unit (R PEoEK ) and include, (a) Repeating unit (R PEEK ) is equation (A): [ka] It is a repeating unit, (b) Repeating unit (R PEoEK ) is equation (B): [ka] It is a repeating unit, and in these formulas, - Each R 1 and R 2These are either the same as or different from each other, and in each presence, are independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. - Each a and b is either the same or different from each other, and is independently selected from the group of integers in the range of 0 to 4. - PEEK-PEoEK copolymer has a molar ratio R in the range of 95 / 5 to 5 / 95. PEEK / R PEoEK Repeating unit R PEEK and R PEoEK Includes.

[0025] The applicant has found that a part material (M) based on the PEEK-PEoEK copolymer, sometimes blended with other polymers (e.g., PEEK), has a slow crystallization rate, which enables 3D printing of large and complex objects / articles. Parts 3D printed from part materials containing the PEEK-PEoEK copolymer, sometimes blended with other polymers (e.g., PEEK), exhibit some degree of crystallinity after printing, but with little to no warping when printed at heating chamber temperatures close to Tg.

[0026] The component material (M) of the present invention may contain other components. For example, the component material may contain at least one additive, particularly selected from the group consisting of fillers, colorants, lubricants, plasticizers, stabilizers, flame retardants, nucleating agents, flow promoters, and combinations thereof. The filler may, in this regard, be inherently reinforcing or non-reinforcing. For example, the component material may contain at least one additive in an amount of 0.1% to 60% by weight relative to the total weight of the component material (M). For example, the amount of additive in the material (M) may be in the range of 0.5% to 50% by weight, 1% to 40% by weight, or 5% to 30% by weight, or 10% to 20% by weight relative to the total weight of the material (M).

[0027] In embodiments including a filler, the concentration of the filler in the component material (M) is in the range of 0.1% to 60% by weight relative to the total weight of the component material (M). Suitable fillers include calcium carbonate, magnesium carbonate, glass fiber, graphite, carbon black, carbon fiber, carbon nanofiber, graphene, graphene oxide, fullerene, talc, wollastonite, mica, alumina, silica, titanium dioxide, kaolin, silicon carbide, zirconium tungstate, boron nitride, and combinations thereof. For example, the amount of filler in the material (M) may be in the range of 0.5% to 50% by weight, 1% to 40% by weight, 5 to 30% by weight, or 10 to 20% by weight relative to the total weight of the material (M).

[0028] According to the first embodiment, the component material (M) of the present invention comprises at least one PEEK-PEoEK copolymer in an amount of 20-100% by weight, 30-99% by weight, 40-95% by weight, or 50-90% by weight, based on the total weight of the polymer components.

[0029] The polymer component of component material (M) may include polymers other than the PEEK-PEoEK described herein. These may include, for example, poly(aryl ether ketone) (PAEK) different from such PEEK-PEoEK. The PAEK used herein is Ar'-C(=O)-A r* Base (where Ar' and Ar * (R) is a repeating unit containing an aromatic group that is either equal to or different from each other. PAEK This means any polymer containing more than 50 mol% of ). Advantageously, the PEAK polymer is a poly(etheretherketone)(PEEK) homopolymer or copolymer (hereinafter referred to as PEEK(co)polymer).

[0030] According to the second embodiment, the component material (M) of the present invention is based on the total weight of the polymer components, - At least one PEEK-PEoEK copolymer in an amount of 20-99% by weight, 30-98% by weight, 40-95% by weight, or 50-90% by weight, - At least one PEEK(co)polymer in an amount of 1-80% by weight, 2-70% by weight, 5-60% by weight, or 10-50% by weight, Includes.

[0031] According to the third embodiment, the component material (M) of the present invention is based on the total weight of the component material (M), - At least one PEEK-PEoEK copolymer in an amount of 20-99% by weight, 30-98% by weight, 40-95% by weight, or 50-90% by weight, - At least one PEEK(co)polymer in an amount of 1-80% by weight, 2-70% by weight, 5-60% by weight, or 10-50% by weight, - Up to 60% by weight of at least one additive optionally selected from the group consisting of fillers, colorants, lubricants, plasticizers, stabilizers, flame retardants, nucleating agents, flow promoters, and combinations thereof, It includes or consists of these.

[0032] In some embodiments, the polymer component of the component material (M) comprises at least 80% by weight of PEEK-PEoEK copolymer based on the total weight of the polymer component of the component material (M). For example, the polymer component comprises at least 85% by weight of PEEK-PEoEK copolymer, at least 90% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight of PEEK-PEoEK copolymer based on the polymer component of the component material (M).

[0033] In some embodiments, the polymer component of the component material (M) consists of a PEEK-PEoEK copolymer.

[0034] In some embodiments, the component material (M) contains at least 80% by weight of PEEK-PEoEK copolymer based on the total weight of the component material (M). For example, the component material (M) contains at least 85% by weight of PEEK-PEoEK copolymer, at least 90% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight of PEEK-PEoEK copolymer based on the total weight of the component material (M).

[0035] In some embodiments, the component material (M) consists of or is essentially derived from a PEEK-PEoEK copolymer. As used herein, the expression "essentially derived from a PEEK-PEoEK copolymer" means that the component material (M) may contain other components in amounts up to 2% by weight, up to 1% by weight, or up to 0.5% by weight relative to the total weight of the component material (M), such that the advantageous properties of the material are not substantially altered.

[0036] PEEK-PEoEK copolymer In this specification, "PEEK-PEoEK copolymer" refers to a PEEK-PEoEK copolymer containing at least 50 mol% of repeating units (R) relative to the total number of moles of repeating units. PEEK ) and repeating units (R PEoEK ) includes. In some embodiments, the PEEK-PEoEK copolymer contains at least 51 mol%, at least 55 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, and most preferably at least 99 mol% of repeating units (R) relative to the total number of moles of repeating units of the PEEK-PEoEK copolymer. PEEK ) and (R PEoEK ) includes.

[0037] Repeating unit (R PEEK ) is equation (A): [ka] It is represented as, Repeating unit (RPEoEK ) is equation (B): [ka] It is represented as, Each R 1 and R 2 These are either the same as or different from each other, and in each presence, are independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. Each a and b is either the same or different from each other, and is independently selected from the group of integers in the range of 0 to 4. PEEK-PEoEK copolymer has a molar ratio R in the range of 95 / 5 to 5 / 95. PEEK / R PEoEK Repeating unit R PEEK and R PEoEK Includes.

[0038] In some embodiments, each a is zero, and therefore the repeating unit (R PEEK ) is equation (A-1): [ka] It is a repeating unit.

[0039] In some preferred embodiments, each b is zero, and therefore the repeating unit (R PEoEK ) is equation (B-1): [ka] It is a repeating unit.

[0040] Preferably, a repeating unit (R PEEK ) is the repeating unit of equation (A-1), and the repeating unit (R PEoEK ) is the repeating unit of equation (B-1).

[0041] The PEEK-PEoEK copolymer of the present invention has repeating units (R) as detailed above. PEEK ) and (R PEoEK ) and different repeating units (R PAEK ) may further include. In such cases, the repeating unit (R PAEK The amount of ) may be 0.1 mol% to less than 50 mol%, preferably less than 10 mol%, more preferably less than 5 mol%, and more preferably less than 2 mol%, relative to the total number of moles of repeating units of the PEEK-PEoEK copolymer.

[0042] The PEEK-PEoEK copolymer of the present invention contains repeating units (R PEEK ) and (R PEoEK ) and different repeating units (R PAEK If the above units (R) exist, PEEK ) and (R PEoEK These repeating units (R) are different from the others. PAEK ) is usually expressed by the following formula (KA)~(KM): [ka] [ka] [ka] (In the above formulas (KA) to (KM), each of R' is either equal to or different from one another, and in each instance, C1 to C optionally contain one or more heteroatoms.) 12 (Independently selected from sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of j' is equal to or different from one another, and in each presence independently selected from integers 0 and 1 to 4, preferably j' is equal to zero) Follow one of the following rules.

[0043] However, the PEEK-PEoEK copolymer of the present invention has the repeating units (R) described in detail above. PEEK ) and (R PEoEKIt is usually preferable that the PEEK-PEoEK copolymer is essentially composed of ). Therefore, in some preferred embodiments, the PEEK-PEoEK copolymer is composed of repeating units R PEEK and R PEoEK Essentially composed of. The repeating unit R used herein PEEK and R PEoEK The expression "essentially composed of" refers to the repeating unit R described in detail above. PEEK and R PEoEK This means that any additional repeating units different from those present may be present in the PEEK-PEoEK copolymer in amounts of up to 2 mol%, up to 1 mol%, or up to 0.5 mol%, relative to the total number of moles of repeating units of the PEEK-PEoEK copolymer, and in such a manner that they do not substantially alter the favorable properties of the PEEK-PEoEK copolymer.

[0044] Repeating unit R PEEK and R PEoEK R is in the range of 95 / 5 to 5 / 95. PEEK / R PEoEK It is present in the PEEK-PEoEK copolymer in molar ratio. Preferably, the PEEK-PEoEK copolymer suitable for the powder of the present invention is the majority R PEEK Those that include units, i.e., R PEEK / R PEoEK The copolymer has a molar ratio in the range of 95 / 5 to over 50 / 50, more preferably 95 / 5 to 60 / 40, even more preferably 90 / 10 to 65 / 35, and most preferably 85 / 15 to 70 / 30.

[0045] In some embodiments, the PEEK-PEoEK copolymer has a melting temperature (Tm) of 340°C or less, preferably 335°C or less. The melting temperature described herein is measured as the peak temperature of the endothermic melting temperature on the second heating scan of a differential scanning calorimeter (DSC) in accordance with ASTM D3418-03 and E794-06, and using heating and cooling rates of 20°C / min.

[0046] In some embodiments, the PEEK-PEoEK copolymer has a glass transition temperature (Tg) of at least 135°C and up to 155°C, preferably at least 140°C, as measured by a second heating scan according to ASTM D3418-03, E1356-03, E793-06, and E794-06.

[0047] In some embodiments, the PEEK-PEoEK copolymer has a heat of fusion (ΔH) of at least 1 J / g, preferably at least 2 J / g, and at least 5 J / g. The heat of fusion described herein is determined as the area under endothermic fusion in the second heating scan on a differential scanning calorimeter (DSC) using heating and cooling rates of 20 °C / min, in accordance with ASTM D3418-03 and E793-06. In some embodiments, the PEEK-PEoEK copolymer may have a heat of fusion (ΔH) of up to 65 J / g, preferably up to 60 J / g.

[0048] According to a specific embodiment, the PEEK-PEoEK copolymer is heated on polymer powder in ATR mode at 600-1,000 cm². -1 The FT-IR spectrum recorded by the device has a fine structure that satisfies the following inequality: (i)

number

number

[0049] The PEEK-PEoEK copolymer may have a calcium content of less than 5 ppm, measured by inductively coupled plasma optical emission spectrometry (ICP-OES) calibrated with a standard of known calcium content. Such a particularly low controlled Ca content is particularly beneficial when the PEEK-PEoEK copolymer is used for metal bonding that requires very strict dielectric properties. According to these preferred embodiments, the PEEK-PEoEK copolymer may have a calcium content of less than 4 ppm, less than 3 ppm, more preferably less than 2.5 ppm.

[0050] In these preferred embodiments, the PEEK-PEoEK copolymer may have a sodium content of less than 1,000 ppm, measured by inductively coupled plasma optical emission spectrometry (ICP-OES) calibrated with a standard of known sodium content. Preferably, the PEEK-PEoEK copolymer may have a sodium content of less than 900 ppm, less than 800 ppm, more preferably less than 500 ppm.

[0051] In some embodiments, the PEEK-PEoEK copolymer may have a phosphorus content of at least 6 ppm, as measured by inductively coupled plasma atomic emission spectroscopy (ICP-OES) calibrated to a known phosphorus content standard. Preferably, the PEEK-PEoEK copolymer has a phosphorus content of at least 10 ppm, at least 15 ppm, and more preferably at least 20 ppm.

[0052] In the powder of the present invention, it may be advantageous to select a PEEK-PEoEK copolymer with improved thermal stability, which may be particularly beneficial in certain application areas, such as for manufacturing 3D objects by additive manufacturing. The PEEK-PEoEK copolymer may have a peak decomposition temperature of at least 550°C, more preferably at least 551°C, and even more preferably at least 552°C, as measured as TGA according to ASTM D3850.

[0053] Methods adapted for producing PEEK-PEoEK copolymers are generally known in the art. These are described in particular in concurrently pending European Patent Applications No. 2020 / 065154 and No. 2020 / 066177 (unpublished).

[0054] PAEK copolymer As used herein, poly(aryl ether ketone) (PAEK) refers to a repeating unit (R) containing an Ar'-C(=O)-Ar* group (where Ar' and Ar* are equal to or different from each other and are aromatic groups). PAEK This refers to any polymer containing more than 50 mol% of ).

[0055] Repeating unit (R PAEK The units can be selected from the group consisting of the following equations (JA) to (JD): [ka] (In the formula, Each of R', which may be equal to or different from one another, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; j' is zero or an integer in the range of 1 to 4).

[0056] In the repeating unit (R PAEK ), each phenylene moiety may independently have a 1,2-, 1,4-, or 1,3-bond to another moiety different from R' in the repeating unit (R PAEK ). Preferably, the phenylene moiety has a 1,3- or 1,4-bond, more preferably a 1,4-bond.

[0057] Within the repeating unit (R PAEK ), j' is preferably zero in each occurrence so that the phenylene moiety has no other substituents other than the substituent connecting the polymer backbone.

[0058] In some embodiments, the PAEK is poly(ether ether ketone) (PEEK). Poly(ether ether ketone) (PEEK) as used herein refers to any polymer containing more than 50 mol% of the repeating unit (J'-A):

Chemical formula

[0059] Preferably, at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol%, most preferably all of the repeating units (R PAEK ) are the repeating unit (J'-A).

[0060] Method for manufacturing a three-dimensional (3D) object The additive manufacturing (AM) method for producing a three-dimensional (3D) object according to the present invention includes a step of extruding a part material (M).

[0061] The method of the present invention is typically carried out using an additive manufacturing system, or a printer also known as a 3D printer.

[0062] The method of the present invention, in relation to a 3D printer, may also include at least one of the following steps: - A process of supplying component material (M) to a discharge head member having a through hole ending at the discharge tip and a circumferential heater for melting the material (M) within the through hole. - A step of heating the part material (M) to a temperature of at least 350°C before extrusion. - A process of compressing the component material (M) with a piston, for example, with an unmelted filament that functions as a piston in a through hole. - A process of forming a cross-sectional shape by discharging a component material (M) onto a receiving platform while ensuring relative movement of the discharge tip and the receiving platform in the X and Y directions. - A process of forming a 3D object or part in the height direction by discharging a part material (M) onto the receiving platform while ensuring relative movement of the discharging tip and the receiving platform in the Z direction.

[0063] 3D objects / articles / parts can be constructed on a substrate, such as a horizontal substrate and / or a planar substrate. The substrate may be movable in all directions, such as horizontally or vertically. During the 3D printing process, the substrate can be lowered, for example, to extrude the part material onto the previous layer of polymer material.

[0064] According to one embodiment, the process further includes a step of manufacturing a support structure. According to this embodiment, the 3D object / article / part is constructed on the support structure, and both the support structure and the 3D object / article / part are manufactured using the same AM method. The support structure may be useful in several situations. For example, especially if the 3D object / article / part is not planar, the support structure may be useful in providing sufficient support to the printed or in-print 3D object / article / part to avoid distortion of the shape of the 3D object / article / part. This is especially true when the temperature used to maintain the printed or in-print 3D object / article / part is lower than the powder re-solidification temperature.

[0065] While not strictly required, 3D objects / articles / parts can also undergo post-manufacturing heat treatment (also known as annealing or tempering). In this case, the 3D objects / articles / parts can be placed in an oven set to a temperature in the range of 170°C to 260°C, preferably 180°C to 220°C, for a period of approximately 30 minutes to 24 hours, preferably 1 hour to 8 hours.

[0066] The 3D object of the present invention preferably exhibits a level of crystallinity corresponding to an enthalpy of fusion or heat of fusion of at least 30 J / g, measured in a differential scanning calorimeter (DSC) in accordance with ASTM D3418 using a heating rate of 20°C / min, in a second heating scan before annealing heat treatment, and calculated as the difference between the absolute value of the fusion endothermic area and the absolute value of the crystallization endothermic area that may be detected during the first heating scan. In some embodiments, the heat of fusion of a 3D object printed before heat treatment and measured according to the above description is at least 32 J / g, at least 33 J / g, or at least 34 J / g.

[0067] The 3D object of the present invention preferably exhibits a tensile stress in the Z direction at the yield point or fracture point that is about 50% greater than the tensile stress in the x and y directions at the yield point or fracture point, preferably at least 55%, and more preferably 60% greater.

[0068] Parts material (M) The component material (M) of the present invention can be manufactured by methods well known to those skilled in the art. For example, such methods include, but are not limited to, a melt-mixing process. The melt-mixing process is typically carried out by heating the polymer components above the melting temperature of the thermoplastic polymer, thereby forming a molten thermoplastic polymer. In some embodiments, the processing temperature is in the range of about 280 to 450°C, preferably about 290 to 440°C, about 300 to 430°C, or about 310 to 420°C. Suitable melt-mixing apparatuses are, for example, kneaders, Banbury mixers, single-screw extruders, and twin-screw extruders. Preferably, an extruder is used that has means for feeding all of the desired components into the extruder, either into the feed port or into the molten material. In the component material preparation process, the components of the component material, e.g., PEEK-PEoEK polymer, optionally other polymers, e.g., PEEK polymer, and optionally additives, are fed into a melt-mixing apparatus and melt-mixed in the apparatus. The ingredients may be supplied together as a powder mixture or granule mixer, also known as a dry blend, or separately.

[0069] The order in which the components are combined during melt mixing is not particularly limited. In one embodiment, the components can be mixed in a single batch, such that desired amounts of each component are added together and then mixed. In other embodiments, the first subset of components may be mixed together first, and one or more remaining components may be added to the mixture for further mixing. For clarity, the total desired amount of each component does not need to be mixed as a single amount. For example, for one or more components, a partial amount may be added and mixed first, and then some or all of the remainder may be added and mixed.

[0070] The component material can be used, for example, in the form of pellets in pellet additive manufacturing (PAM) 3D printing.

[0071] If the component material is in pellet form, the pellets may have sizes ranging from 1 mm to 1 cm, for example, 2 mm to 5 mm, or 2.5 mm to 4.5 mm.

[0072] Filament material The present invention also relates to a filament material (F) comprising a polymer component containing at least one of the above-mentioned PEEK-PEoEK copolymers.

[0073] According to this aspect of the present invention, the PEEK-PEoEK copolymer is as described above.

[0074] According to one embodiment, the filament material further comprises one or more other polymers, for example, at least one PEEK polymer.

[0075] This filament material is suitable for use in the manufacturing of three-dimensional objects.

[0076] The filament may have a cylindrical or substantially cylindrical shape, or a non-cylindrical shape such as a ribbon filament shape. Furthermore, the filament may have a hollow shape or a core-shell shape, and the support material of the present invention is used to form either the core or the shell.

[0077] If the filament has a cylindrical shape, its diameter can vary from 0.5 mm to 5 mm, for example, 0.8 to 4 mm or 1 mm to 3.5 mm. The filament diameter can be selected to supply a specific FFF 3D printer. Examples of filament diameters widely used in the FFF process are 1.75 mm or 2.85 mm. The accuracy of the filament diameter is + / - 200 microns, for example, + / - 100 microns or + / - 50 microns.

[0078] The filament of the present invention can be manufactured from a two-step process in which a compound is first manufactured to form the component material into pellets, and then the pellets are extruded to produce the filament. Alternatively, the filament of the present invention can be manufactured from an integrated process in which the compound and filament are manufactured in a single step.

[0079] The filaments of the present invention can be manufactured from component materials by methods such as, but not limited to, a melt-mixing process. The melt-mixing process is typically carried out by heating the polymer components above the maximum melting temperature and glass transition temperature of the thermoplastic polymer, thereby forming a molten thermoplastic polymer. In some embodiments, the processing temperature is in the range of about 280 to 450°C, preferably about 290 to 440°C, about 300 to 430°C, or about 310 to 420°C.

[0080] The filament manufacturing process can be carried out in a melt-mixing apparatus, and therefore any melt-mixing apparatus known to those skilled in the art in the technique of preparing polymer compositions by melt-mixing can be used. Suitable melt-mixing apparatuses include, for example, kneaders, Banbury mixers, single-screw extruders, and twin-screw extruders. Preferably, an extruder is used that has means for dispensing all the desired components into the extruder's feed port or into the molten material. In the filament manufacturing process, the components of the component material are supplied to a melt-mixing apparatus and melt-mixed within the apparatus. The components may be supplied simultaneously or separately as a powder mixture or granular mixer, also known as a dry blend.

[0081] The order in which the components are combined during melt mixing is not particularly limited. In one embodiment, the components can be mixed in a single batch, such that desired amounts of each component are added together and then mixed. In other embodiments, the first subset of components may be mixed together first, and one or more remaining components may be added to the mixture for further mixing. For clarity, the total desired amount of each component does not need to be mixed as a single amount. For example, for one or more components, a partial amount may be added and mixed first, and then some or all of the remainder may be added and mixed.

[0082] Methods for manufacturing filaments include, for example, an extrusion process using a die. For this purpose, any standard molding technique can be used, and standard techniques involving shaping a polymer composition in a molten / softened form can be advantageously applied, including, in particular, compression molding, extrusion molding, injection molding, and transfer molding. Extrusion molding is preferred. For example, if the article is a cylindrical filament, the article can be molded using a die such as one having an annular orifice.

[0083] In some embodiments, the filament is obtained by a melt-mixing process, which is carried out by heating the polymer components above their melting temperature and melt-mixing the components of the component material.

[0084] This method may include several sequential steps of melting, mixing, or extrusion under various conditions, if necessary.

[0085] The process itself, or any related process, may further include steps that include cooling the molten mixture.

[0086] supporting material The method of the present invention may also support a 3D object during assembly using a different polymer component. This polymer component, which is similar to or different from the part material used to construct the 3D object, is referred to herein as the support material. During 3D printing, the support material may be needed to provide vertical and / or lateral support to the part material being constructed. The support material needs to have similar thermal properties to the part material to the extent that it can maintain hardness and rigidity to provide the necessary support to the part material in hollow or overhanging regions of the part.

[0087] The support material, which may be used in connection with this method, advantageously has a high melting temperature (i.e., above 260°C) to withstand high-temperature applications. The support material may also have water-absorbing behavior or solubility in water at temperatures below 110°C to swell or deform sufficiently upon exposure to moisture.

[0088] According to embodiments of the present invention, a method for manufacturing a three-dimensional object using an additive manufacturing system is: - A process of printing layers of a support structure from a support material, and - A step of removing at least a portion of the supporting structure from a three-dimensional object. It also includes.

[0089] Various polymer components can be used as support materials. In particular, the support material may include polyamides or copolyamides, for example, those described in PCT application international publication brochures 2017 / 167691 and 2017 / 167692.

[0090] Purpose The present invention also relates to the use of component material (M) containing the polymer components described above for the manufacture of three-dimensional objects.

[0091] The present invention also relates to the use of filament materials containing the polymer components described above for the manufacture of three-dimensional objects.

[0092] All of the embodiments described above regarding component materials apply equally to the use of component materials or filament materials.

[0093] The present invention also relates to the use of a component material (M) containing the polymer component described above for the manufacture of a filament for use in the manufacture of a three-dimensional object.

[0094] The present invention also relates to 3D objects or articles that can be obtained, at least partially, from the manufacturing method of the present invention using the component materials described herein. These 3D objects or articles preferably exhibit a density comparable to that of injection-molded objects or articles. They also exhibit comparable improved mechanical properties.

[0095] 3D objects or articles obtained by such manufacturing methods can be used in a variety of end applications. In particular, these include implantable devices, medical devices, dental prostheses, brackets and complex-shaped parts in the aerospace industry, under-hood components in the automotive industry, oil and gas applications, and electronic components.

[0096] 3D objects or articles obtained by such manufacturing methods can be used in many aircraft applications, including, for example, passenger service units, stairs, window frames, ceiling panels, information displays, window covers, ceiling panels, side wall panels, wall partitions, display cases, mirrors, sun visors, blinds, storage boxes, storage doors, overhead storage lockers, serving trays, backrests, cabin partitions, and ducts.

[0097] 3D objects or articles obtained by such manufacturing methods can be used in many automotive applications, including, for example, connectors, fittings, discharge control systems, and injection-molded parts.

[0098] 3D objects or articles obtained by such manufacturing methods can be used in oil and gas applications, such as offshore solutions for protection against corrosion, chemical attack, and aging.

[0099] 3D objects or articles obtained by such manufacturing methods can be used, for example, in wire and cable applications requiring highly superior heat and chemical resistance, as well as good flame, smoke, and toxicity properties, and as electronic components including parts that require dimensional stability.

[0100] If any disclosure of patents, patent applications, and published materials incorporated herein by reference conflicts with any description of this application to such an extent that it could obscure any term, the description herein shall prevail. [Examples]

[0101] The present disclosure will now be described in more detail in relation to the following embodiments, but these are for illustrative purposes only and are not intended to limit the scope of the present disclosure.

[0102] Starting material Hydroquinone, photo grade, was sourced from Eastman, USA. It contains 0.38% by weight of water, which was used to adjust the added weight. All weights shown include water. Resorcinol, ACS reagent grade, was sourced from Aldrich, USA. 4,4'-biphenol, polymer grade, was sourced from SI, USA. Pyrocatechol, in flake form, was sourced from Solvay, USA. Its purity was 99.85% by GC. It contained 680 ppm of moisture, which was used to adjust the additive weight. All weights shown include moisture. 4,4'-Difluorobenzophenone, polymer grade (99.8%+), was sourced from Malwa, India. Diphenyl sulfone (polymer grade) was sourced from Proviron (99.8% purity). The light soda ash, sodium carbonate, was sourced from Solvay SA, France. Potassium carbonate with a d90 < 45 μm was sourced from Armand Products. The lithium chloride (anhydrous grade) was sourced from Acros.

[0103] Resin preparation PEEK A 500 ml four-neck reaction flask equipped with a stirrer, an N2 injection tube, a Claisen adapter with a thermocouple placed in the reaction medium, and a Dean-Stark trap with a condenser and dry eye trap contained 127.82 g of diphenylsulfone, 28.685 g of hydroquinone, and 57.326 g of 4,4'-difluorobenzophenone. The flask contents were degassed under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to a constant nitrogen purge (60 mL / min).

[0104] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 28.481 g of Na2CO3 and 0.180 g of K2CO3 was added to the reaction mixture from a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 320°C at a rate of 1°C / min. After 14 minutes at 320°C, the reaction was completed in three steps: 6.818 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.444 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 2.273 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0105] Next, the contents of the reactor were poured from the reactor into an SS receiving dish and cooled. The solid material was crushed and ground through a 2 mm screen using an attrition mill. Diphenyl sulfone and salt were extracted from the mixture using acetone and water.

[0106] Next, the powder was dried under vacuum at 120°C for 12 hours to obtain 65 g of white powder.

[0107] The melt viscosity, measured by capillary rheology at 400°C and 1000 s⁻¹, was 0.30 kN-s / m².

[0108] PEEK-PEoEK copolymer 80 / 20 A 1000 mL four-neck reaction flask equipped with a stirrer, an N2 injection tube, a Claisen adapter with a thermocouple placed in the reaction medium, and a Dean-Stark trap with a condenser and dry eye trap contained 343.63 g of diphenylsulfone, 61.852 g of hydroquinone, 15.426 g of pyrocatechol, and 153.809 g of 4,4'-difluorobenzophenone. The flask contents were degassed under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to a constant nitrogen purge (60 mL / min).

[0109] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 76.938 g of Na2CO3 and 0.484 g of K2CO3 was added to the reaction mixture from a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 320°C at a rate of 1°C / min. After 25 minutes at 320°C, the reaction was completed in three steps: 18.329 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 2.388 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 6.110 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0110] Next, the contents of the reactor were poured from the reactor into an SS receiving dish and cooled. The solid material was crushed and ground through a 2 mm screen using an attrition mill. Diphenyl sulfone and salt were extracted from the mixture using acetone and water.

[0111] Next, the powder was dried under vacuum at 120°C for 12 hours to obtain 191 g of white powder.

[0112] The repeating units of a polymer are: [ka] That is the case.

[0113] The melt viscosity, measured by capillary rheology at 400°C and 1000 s⁻¹, was 0.37 kN-s / m².

[0114] The PEEK / PEEK-PEoEK blend (Formulation 3 in Table 1) was prepared by first tumbling the polymers to be blended in resin form for approximately 20 minutes. The blend was then melt-kneaded using a 26 mm diameter Coperion® ZSK-26 co-rotating partial-mesh twin-screw extruder with an L / D ratio of 48:1. Barrel sections 2-12 and the die were heated to the following setpoint temperatures: barrels 2-12: 350°C, die: 350°C. The resin blend was fed into barrel section 1 using a gravimetric feeder at a rate in the range of 30-40 pounds / hour. The extruder was operated at a screw speed of approximately 200 RPM. Vacuum was applied to barrel zone 10 using a mercury vacuum level of approximately 27 inches. A single-hole die was used for all of the formulation to produce filaments with a diameter of approximately 2.4–2.5 mm. The polymer filaments exiting the die were cooled in water and fed into a pelletizer to produce pellets approximately 2.0 mm in length. Before filament extrusion, the pellets were annealed as follows: at 200°C for 2 hours.

[0115] Filament manufacturing The feedstock for filament production consisted of either pure polymer (PEEK or PEEK-PEoEK) or a dry blend of polymer resin. The polymer, extruded into filament in resin form, was tumbled for approximately 20 minutes. 1.80 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, a heated capillary die attachment, a 3 / 32-inch diameter nozzle with a 1.5-inch land, and a downstream custom-designed filament transport. Other downstream equipment included a belt puller and a dual-station coiler, both manufactured by 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. The setpoint temperatures for the Brabender® zones were as follows: Zone 1, 395°C; Zones 2 and 3, 400°C; Die, 340°C. The Brabender® speed ranged from 35 to 45 rpm, and the puller speed was 33 to 36 feet / min (10.058 to 10.973 meters / min).

[0116] 3D printing The filaments described above were printed using a commercially available F900 extrusion-based additive manufacturing system from Stratasys, Inc., Eden Prarie, Minnesota, USA. While the filaments were used as the model material, Stratasys SUP8000B detachable support material was used as the support material. A high-temperature (PPSU) build sheet was used as the substrate for the printed object. During the printing tests, the model extruder temperature was set to 400-420°C, the support extruder temperature to approximately 400°C, and the heating chamber to 155°C. A Stratasys T20D chip with a layer thickness of 0.013 inches was used as the model material, and a Stratasys T16 chip was used as the support material. The model material was extruded in layers as a series of loads within the heated chamber to print the structure. Using 100% filler and alternating 45° / -45° rasters, 6-inch x 6-inch x 2mm plaques were printed for each formulation, and the objects were promptly removed from the heating chamber and build sheet after printing.

[0117] Test method DSC (Tg, Tc, heat of fusion) Tg is determined by the second heating scan using a differential scanning calorimeter (DSC) with heating and cooling rates of 20°C / min in accordance with ASTM D3418.

[0118] Tc is determined by the first cooling scan using a differential scanning calorimeter (DSC) with heating and cooling rates of 20°C / min in accordance with ASTM D3418.

[0119] The heat of fusion is determined by a second heating scan using a differential scanning calorimeter (DSC) with a heating rate of 20°C / min in accordance with ASTM D3418.

[0120] result Table 1 shows an overview of the filament compositions used in Examples 1, 2, and 3.

[0121] [Table 1]

[0122] Table 2 shows the DSC data for the first cooling and second heating for formulations 1, 2, and 3. The last column of Table 2 shows the (Tm-Tc) / (Tm-Tg) parameter. This is a method for comparing crystallization rates between similar types of polymers (i.e., PAEK in this case) with different glass transition temperatures and melting transition temperatures. The closer this value is to 0.0, the closer Tc is to Tm and the faster the crystallization rate; the closer this value is to 1.0, the closer Tc is to Tg and the slower the crystallization rate. This ratio effectively measures the thermal driving force for superhelical formation required to induce crystallization.

[0123] [Table 2]

[0124] PEEK has the highest relative crystallization rate at 0.27, while PEEK-PEoEK is the slowest at 0.45, and the 50 / 50 blend halves the difference at 0.33. In the enthalpy of melting column (ΔHm), the PEEK-PEoEK copolymer has a lower absolute crystallinity than PEEK, at 41 J / g vs. 52 J / g, respectively, while the 50 / 50 blend has a crystallinity similar to pure PEEK, at 55 vs. 52 J / g.

[0125] The melting points of both pure PEEK-PEoEK copolymer (303°C) and its 50 / 50 blend with PEEK (333°C) are advantageously lower than those of pure PEEK (343°C). This makes it easier to melt-process compared to pure PEEK and reduces the chance of thermal decomposition. This is because all of these polymers have similar decomposition temperatures due to essentially the same ether and ketone bonds, and the resulting bond dissociation energies.

[0126] Using the materials described above, 6-inch x 6-inch x 2mm plaques were printed. For the PEEK material, there was an undesirable slight warp at the left front corner of the object, which curled upwards during the printing process. The central defect in all three printed objects is a cutout used for DSC analysis of the printed parts, which will be further described later. The PEEK-PEoEK copolymer did not warp during the 3D printing process. After peeling from the PPSU build sheet, it showed a slight downward curvature. Plaques 3D printed from the 50 / 50 blend material remained flat without curling or warping, both during the 3D printing process and after peeling from the PPSU build sheet.

[0127] Table 3 shows the DSC temperature transitions of the first heating of cutouts from 3D printed objects. The heating chamber is used for all of these polymers. g It is maintained at 155°C, which is very close to the normal temperature.

[0128] [Table 3]

[0129] As indicated by the absence of a low-temperature crystallization peak during the first heating scan of the DSC, the printed parts of PEEK crystallize completely during the printing process. Pure PEEK-PEoEK copolymer has a low-temperature crystallization enthalpy (ΔH) of 27 J / g. c ) has a lower ΔH of 15 J / g, while the 50 / 50 blend has a lower ΔH of 15 J / g. c This indicates that the 50 / 50 blend crystallized more during the printing process compared to the PEEK-PEoEK copolymer.

[0130] In summary, all the above results clearly show that PEEK-PEoEK and its blend with PEEK have the advantage of both lower crystallinity and slower crystallination rates than PEEK, while retaining crystallinity from the 3D printing process. Although PEEK-PEoEK and its blend with PEEK partially crystallized during the 3D printing process, surprisingly, they did not warp during printing. This is in contrast to pure PEEK, which did warp during the 3D printing process. This retained crystallinity of PEEK-PEoEK and its blend with PEEK is advantageous not only for the thermal, mechanical, and chemical resistance properties of the printed parts, but also for maintaining the part shape if the end user decides to perform a post-printing annealing process to further enhance the crystallinity of the part.

Claims

1. Additive manufacturing (AM) method for producing a three-dimensional (3D) object, comprising extruding a component material (M) containing a polymer component, wherein the polymer component comprises at least one PEEK-PEoEK copolymer, and the copolymer contains at least 50 mol% of repeating units (R) in total relative to the total number of repeating units in the PEEK-PEoEK copolymer. ＰＥＥＫ ) and repeating unit (R ＰＥｏＥＫ ) and (a) Repeating unit (R ＰＥＥＫ ) is equation (A): 【Chemistry 1】 It is a repeating unit, (b) Repeating unit (R ＰＥｏＥＫ ) is equation (B): 【Chemistry 2】 It is a repeating unit, and in these formulas, - Each R １ and R ２ These are either the same as or different from each other, and in each presence, are independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. - Each a and b is independently selected from a group of integers in the range of 0 to 4. - the PEEK-PEoEK copolymer has a molar ratio R in the range of 95 / 5 to 5 / 95 ＰＥＥＫ / R ＰＥｏＥＫ for the repeating unit R ＰＥＥＫ and R ＰＥｏＥＫ and a method comprising the same.

2. The repeating unit (R ＰＥＥＫ ) is the formula: 【Transformation 3】 The method according to claim 1, wherein the repeating unit is the same.

3. The repeating unit (R ＰＥｏＥＫ ) is the formula: 【Chemistry 4】 The method according to claim 1 or 2, wherein the repeating unit is the same.

4. The PEEK-PEoEK copolymer has repeating units (R ＰＥＥＫ ) and (R ＰＥｏＥＫ It is essentially composed of ) and repeating unit R ＰＥＥＫ and R ＰＥｏＥＫ The method according to any one of claims 1 to 3, wherein any additional repeating units different from those in the PEEK-PEoEK copolymer may be absent or present in an amount of up to 2 mol%, up to 1 mol%, or up to 0.5 mol% of the total number of moles of repeating units in the PEEK-PEoEK copolymer.

5. The repeating unit R ＰＥＥＫ and R ＰＥｏＥＫ However, R is in the range of 95 / 5 to over 50 / 50, preferably 95 to 50 / 5 to 60 / 40, and more preferably in the range of 90 / 10 to 65 / 35. ＰＥＥＫ / R ＰＥｏＥＫ The method according to any one of claims 1 to 4, wherein the PEEK-PEoEK copolymer is present in molar ratio.

6. The method according to any one of claims 1 to 5, wherein the component material (M) further comprises 0.1% to 60% by weight of an additive selected from the group consisting of fluidizers, fillers, colorants, lubricants, plasticizers, stabilizers, flame retardants, nucleating agents, and combinations thereof, based on the total weight of the component material.

7. The method according to any one of claims 1 to 6, wherein the polymer component of the component material (M) further comprises at least one polymer different from the PEEK-PEoEK copolymer, preferably at least one PEEK(co)polymer.

8. The method according to any one of claims 1 to 7, wherein the component material (M) is in the form of a filament having a cylindrical or ribbon-like geometric shape, and its diameter or at least one of its cross-sections has a size that varies from 0.5 mm to 5 mm, preferably from 0.8 mm to 4 mm, and more preferably from 1 mm to 3.5 mm.

9. The method according to any one of claims 1 to 6, wherein the component material (M) is in the form of pellets having a size in the range of 1 mm to 1 cm.

10. The aforementioned component material (M) is a polymer component, - 20 to 99% by weight of at least one PEEK-PEoEK copolymer, - The method according to any one of claims 1 to 9, comprising a polymer component containing at least one PEEK(co)polymer in an amount of 1 to 80% by weight based on the total weight of the polymer component.

11. A filament material having a cylindrical shape and a diameter within 0.5 to 5 mm ± 0.15 mm, comprising a polymer component, wherein such polymer component comprises at least one PEEK-PEoEK copolymer, and the copolymer comprises at least 50 mol% of repeating units (R) in total relative to the total number of repeating units in the PEEK-PEoEK copolymer. ＰＥＥＫ ) and repeating unit (R ＰＥｏＥＫ ) and (a) Repeating unit (R ＰＥＥＫ ) is equation (A): 【Transformation 5】 It is a repeating unit, (b) Repeating unit (R ＰＥｏＥＫ ) is equation (B): 【Transformation 6】 It is a repeating unit, and in these formulas, - Each R １ and R ２ These are either the same as or different from each other, and in each presence, are independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. - Each a and b is independently selected from a group of integers in the range of 0 to 4. - The PEEK-PEoEK copolymer has a molar ratio R in the range of 95 / 5 to 5 / 95. ＰＥＥＫ / R ＰＥｏＥＫ The repeating unit R ＰＥＥＫ and R ＰＥｏＥＫ Filament material containing [this material].

12. A method for forming the filament material according to claim 11, comprising a melt-mixing process carried out by heating the polymer component above its melting temperature.

13. The filament material according to claim 11, wherein the polymer component comprises at least 80% by weight of the PEEK-PEoEK copolymer based on the total weight of the polymer component of the filament.

14. Use of a part material (M), preferably in the form of a filament, containing a polymer component, for manufacturing a 3D object using an extrusion-based 3D printing method, wherein such polymer component contains at least one PEEK-PEoEK copolymer, and the copolymer contains at least 50 mol% of repeating units in total relative to the total number of repeating units in the PEEK-PEoEK copolymer. ＰＥＥＫ ) and repeating unit (R ＰＥｏＥＫ ) and (a) Repeating unit (R ＰＥＥＫ ) is equation (A): 【Chemistry 9】 It is a repeating unit, (b) Repeating unit (R ＰＥｏＥＫ ) is equation (B): 【Chemistry 10】 It is a repeating unit, and in these formulas, - Each R １ and R ２ These are either the same as or different from each other, and in each presence, are independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. - Each a and b is independently selected from a group of integers in the range of 0 to 4. - The PEEK-PEoEK copolymer has a molar ratio R in the range of 95 / 5 to 5 / 95. ＰＥＥＫ / R ＰＥｏＥＫ The repeating unit R ＰＥＥＫ and R ＰＥｏＥＫ Includes, use.

15. A component material (M) for manufacturing a 3D object using an extrusion-based 3D printing method, The material comprises at least one PEEK-PEoEK copolymer, wherein the copolymer contains at least 50 mol% of repeating units (PEEK) and repeating units (RPEoEK) in total, relative to the total number of repeating units in the PEEK-PEoEK copolymer. (a) The repeating unit (R PEEK) is given by formula (A): 【Chemistry 11】 It is a repeating unit, (b) The repeating unit (R PEoEK) is given by equation (B): 【Chemistry 12】 It is a repeating unit, and in these formulas, - Each R1 and R2 is either the same as or different from each other, and in each presence, is independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. - Each a and b is independently selected from a group of integers in the range of 0 to 4. - A component material (M) wherein the PEEK-PEoEK copolymer contains the repeating units R PEEK and R PEoEK in a molar ratio R PEEK / R PEoEK in the range of 95 / 5 to 5 / 95.

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