EP4384577A1 - Procédé pour la préparation d'un corps moulé par frittage laser sélectif d'une poudre à fritter (sp) amorphe contenant du polyamide 6i/6t et/ou du polyamide dt/di - Google Patents

Procédé pour la préparation d'un corps moulé par frittage laser sélectif d'une poudre à fritter (sp) amorphe contenant du polyamide 6i/6t et/ou du polyamide dt/di

Info

Publication number
EP4384577A1
EP4384577A1 EP22761153.0A EP22761153A EP4384577A1 EP 4384577 A1 EP4384577 A1 EP 4384577A1 EP 22761153 A EP22761153 A EP 22761153A EP 4384577 A1 EP4384577 A1 EP 4384577A1
Authority
EP
European Patent Office
Prior art keywords
amorphous
polyamide
range
sintering
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22761153.0A
Other languages
German (de)
English (en)
Inventor
Claus Gabriel
Clemens GOTTKE
Bernhard KREN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP4384577A1 publication Critical patent/EP4384577A1/fr
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B29C64/268—Arrangements for irradiation using laser beams; using electron beams [EB]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/321—Feeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0032—Pigments, colouring agents or opacifiyng agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/10—Pre-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • SP amorphous sintering powder
  • the present invention relates to a method for producing a shaped body, wherein in step i) a layer of an amorphous sintering powder (SP) containing at least 70% by weight of at least one amorphous polyamide selected from the group consisting of polyamide 6I/6T and polyamide DT /DI, contains, is provided and in step ii) the layer provided in step i) is selectively sintered. Furthermore, the present invention relates to a method for producing an amorphous sinter powder (SP) and an amorphous sinter powder (SP) obtainable by this method. In addition, the present invention relates to the use of the amorphous sintering powder (SP) in a sintering process and to shaped bodies obtainable by the process according to the invention.
  • SP amorphous sintering powder
  • SLS selective laser sintering
  • Semi-crystalline polymers are usually used in selective laser sintering, since semi-crystalline polymers have a sharp melting point.
  • S. Kloos, M.A. Dechet, W. Peukert, J. Schmidt, Production of spherical semi-crystalline polycarbonate microparticles for Additive Manufacturing by liquid-liquid phase separation, Powder Technology 335 (2016) 275-284 the use of the semi-crystalline polyamides PA12, PA11 and PA6 described for selective laser sintering.
  • amorphous polycarbonates are difficult to process in selective laser sintering and that the use of amorphous polycarbonates is very limited. Due to the amorphous nature of the polycarbonates, they are only used in processes, such as investment casting processes, in which the dimensional accuracy of the moldings produced plays a subordinate role.
  • US10500763B2 and US2020/0048481 A1 also describe the use of originally amorphous polycarbonates in laser sintering processes in which, in order to achieve sinterability, the amorphous polycarbonate is converted to a partially crystalline polycarbonate by suitable methods.
  • US10500763B2 and US2020/0048481 A1 also point out that the use of amorphous polymers in laser sintering processes is difficult because the processes are poorly reproducible and the moldings obtained have poor mechanical properties and low dimensional accuracy.
  • WO 2018/019728 A1 discloses a method for producing a shaped body by selective laser sintering of a sintering powder (SP).
  • SP sintering powder
  • the sintering powder (SP) contains at least one partially crystalline polyamide, at least one polyamide 6I/6T and at least one reinforcing agent.
  • WO 2018/019727 A1 also discloses a method for producing a shaped body by selective laser sintering of a sintering powder (SP).
  • SP sintering powder
  • the sintering powder (SP) contains at least one semi-crystalline polyamide and at least one polyamide 6I/6T.
  • EP 3 491 065 B1 also discloses a method for producing a shaped body by selective laser sintering of a sintering powder (SP).
  • SP sintering powder
  • the sintering powder (SP) contains at least one partially crystalline polyamide and at least one polyamide 6I/6T and at least one polyaryl ether.
  • WO 2019/224016 A1 discloses a method of forming a polymeric article by means of additive forming, which provides means for forming articles at a low processing temperature, with the articles produced exhibiting high dimensional stability.
  • the object on which the present invention is based was therefore to provide a process for the production of shaped bodies by selective laser sintering which does not have the aforementioned disadvantages of the processes described in the prior art, or only does so to a reduced extent.
  • the method should be simple and inexpensive to carry out.
  • a method for producing a shaped body by selective laser sintering comprising the steps: i) providing a layer of an amorphous sintering powder (SP) that contains the components
  • step ii) laser sintering of the layer provided in step i), the volume-related energy density (Ev) in step ii) being at least 1000 mJ/mm 3 , the volume-related energy density (Ev) being according to the following formula is calculated in the
  • P is the laser power of the laser used in step ii) in watts
  • v is the scanning speed of the laser used in step ii) in m/s
  • h is the scanning distance in mm in step ii)
  • d is the layer thickness of those provided in step i).
  • layer is in mm and n is the number of laser scans performed in step ii), where for step i) and ii) the following laser sintering parameters apply:
  • P ranges from 15 to 40 watts
  • v ranges from 2 to 10 m/s
  • h ranges from 0.05 to 0.3 mm
  • d ranges from 0.03 to 0.15 mm
  • n ranges from 1 to 3.
  • amorphous sintering powders which have an amorphous polymer component which, based on the total weight of the amorphous polymer component, contain at least 70% by weight of at least one amorphous polyamide selected from the group consisting of polyamide 6I/6T and polyamide DT/DI, can be used in processes for selective laser sintering.
  • Shaped bodies that have been produced using the process according to the invention have good mechanical properties. Shaped bodies that have been produced using the process according to the invention also have constant mechanical properties over a wide temperature range.
  • the method according to the invention can also be carried out on conventional laser sintering systems and, among other things, on the newer desktop machines in which lasers with a shorter wavelength are used and which are operated at a limited installation space temperature. Moldings produced by the process according to the invention exhibit a good barrier against oxygen, carbon dioxide and moisture. They also have good solvent resistance to aliphatic and aromatic hydrocarbons.
  • step i a layer of the amorphous sintering powder (SP) is provided.
  • the layer of sintering powder (SP) can be provided by any of the methods known to those skilled in the art.
  • the layer of sintering powder (SP) is usually provided in a construction space on a construction platform. If necessary, the installation space can be tempered.
  • the installation space has, for example, a temperature which is in the range from 1 to 20 K (Kelvin), preferably in the range from 1 to 15 K and particularly preferably in the range from 1 to 10 K, above the glass transition temperature (Tg) of the amorphous polyamide 6I/ 6T or the amorphous polyamide DT/DI, preferably above the glass transition temperature (Tg) of the amorphous polymer component and particularly preferably above the glass transition temperature (Tg) of the amorphous sinter powder (SP).
  • K Kelvin
  • the installation space has, for example, a temperature in the range from 125 to 164.degree. C., preferably in the range from 125 to 159.degree. C. and particularly preferably in the range from 125 to 154.degree.
  • the construction space has a temperature in the range from 125 to 145.degree. C., preferably in the range from 125 to 140.degree. C. and particularly preferably in the range from 125 to 135.degree.
  • the installation space has, for example, a temperature in the range from 144 to 164.degree. C., preferably in the range from 144 to 159.degree. C. and particularly preferably in the range from 144 to 154.degree.
  • the layer of amorphous sintering powder (SP) can be provided in process step i) using any of the methods known to those skilled in the art.
  • the layer of amorphous sintering powder (SP) is provided in the installation space in the thickness to be achieved by a doctor blade or a roller.
  • the layer thickness (d) of the layer of the amorphous sintering powder (SP), which is provided in step i), is generally in the range from 0.03 to 0.15 mm, preferably in the range from 0.04 to 0.13 mm and particularly preferably in the range from 0.05 to 0.11 mm.
  • SP Amorphous sintering powder
  • the amorphous sinter powder (SP) contains an amorphous polymer component as component (A), optionally as component (B) at least one additive and optionally as component (C) at least one reinforcing agent.
  • component (A) and “an amorphous polymer component” are used synonymously and therefore have the same meaning.
  • component (B) and “at least one additive”. These terms are also used synonymously within the scope of the present invention and therefore have the same meaning.
  • component (C) and “at least one reinforcing agent” are also used synonymously in the context of the present invention and have the same meaning.
  • the amorphous sintering powder (SP) can contain components (A) and optionally (B) and (C) in any desired amounts.
  • the amorphous sintering powder (SP) contains in the range from 50 to 100% by weight of component (A), in the range from 0 to 50% by weight of component (B) and in the range from 0 to 50% by weight the component (C), each based on the sum of Percentages by weight of components (A) and optionally (B) and (C), preferably based on the total weight of the amorphous sinter powder (SP).
  • the present invention is therefore also a method in which the amorphous sintering powder (SP) in the range from 50 to 100% by weight of component (A), in the range from 0 to 50% by weight of component (B) and in the range from 0 to 50% by weight of component (C), in each case based on the total weight of the amorphous sintering powder (SP).
  • SP amorphous sintering powder
  • the percentages by weight of components (A) and optionally (B) and (C) usually add up to 100% by weight.
  • the amorphous sinter powder (SP) has particles. These particles have, for example, a size in the range from 10 to 250 ⁇ m, preferably in the range from 15 to 200 ⁇ m, particularly preferably in the range from 20 to 120 ⁇ m and particularly preferably in the range from 20 to 110 ⁇ m.
  • the amorphous sintering powder (SP) according to the invention has, for example, a D10 value in the range from 10 to 60 ⁇ m, a D50 value in the range from 25 to 90 ⁇ m and a D90 value in the range from 50 to 150 ⁇ m.
  • the amorphous sintering powder (SP) according to the invention preferably has a D10 value in the range from 20 to 50 ⁇ m, a D50 value in the range from 40 to 80 ⁇ m and a D90 value in the range from 80 to 125 ⁇ m.
  • the present invention is therefore also a method in which the sinter powder (SP) has a D10 value in the range from 10 to 60 pm, a D50 value in the range from 25 to 90 pm and a D90 value in the range from 50 to 150 pm.
  • the “D10 value” means the particle size at which 10% by volume of the particles, based on the total volume of the particles, are less than or equal to the D10 value and 90% by volume of the particles on the total volume of the particles, are greater than the D10 value.
  • the "D50 value” is the particle size at which 50% by volume of the particles, based on the total volume of the particles, are less than or equal to the D50 value and 50% by volume of the particles, based on the total volume of particles greater than the D50 value.
  • the "D90 value” is understood to mean the particle size at which 90% by volume of the particles, based on the total volume of the particles, are less than or equal to the D90 value and 10% by volume of the particles, based on the total volume of the Particles larger than the D90 value.
  • the amorphous sinter powder SP is suspended dry using compressed air or in a solvent such as water or ethanol, and this suspension is measured.
  • the D10, D50 and D90 values are determined by means of laser diffraction using a Master Sizer 3000 from Malvern. The evaluation is carried out using Fraunhofer diffraction.
  • the amorphous sinter powder (SP) preferably has no melting point.
  • the sintering powder (SP) preferably has no crystallization temperature (T c ).
  • amorphous means that the amorphous sinter powder (SP) has no melting point in differential scanning calorimetry (DSC), measured in accordance with ISO 11357.
  • No melting point means that the enthalpy of fusion of the amorphous sinter powder (SP) AH2 ( S p) is less than 10 J/g, preferably less than 8 J/g and particularly preferably less than 5 J/g, each measured using differential scanning calorimetry (DDK; Differential Scanning Calorimetry, DSC) according to ISO 1 1357-4: 2014.
  • DK Differential Scanning Calorimetry
  • the amorphous sintering powder (SP) according to the invention therefore usually has an enthalpy of fusion AH2 (Sp ) of less than 10 J/g, preferably less than 8 J/g and particularly preferably less than 5 J/g, measured in each case by means of differential scanning calorimetry (DDK; Differential Scanning Calorimetry, DSC) according to ISO 1 1357-4: 2014.
  • DDK differential scanning calorimetry
  • the amorphous sintering powder (SP) according to the invention usually has a glass transition temperature (T G ⁇ SP)), the glass transition temperature (T G ⁇ SP)) usually being in the range from 90 to 150° C., preferably in the range from 92 to 148° C. and particularly preferably in the range from 94 to 146 ° C, determined using ISO 1 1357-2: 2014.
  • the amorphous sintering powder (SP) can be produced by any of the methods known to those skilled in the art. For example, the sinter powder is produced by grinding or by precipitation.
  • the amorphous polymer component (A) or its components and any additives and/or additives are usually first mixed with a solvent and the amorphous polymer component or its components are optionally heated in the solvent Obtaining a solution resolved.
  • the sintering powder (SP) is then precipitated, for example, by the solution being cooled, the solvent being distilled off from the solution or a precipitating agent being added to the solution.
  • Milling can be carried out by any of the methods known to those skilled in the art, for example components (A) and, if appropriate, (B) and (C) are placed in a mill and ground therein.
  • mills known to the person skilled in the art are suitable as mills, for example classifier mills, opposed jet mills, hammer mills, ball mills, vibratory mills or rotor mills such as pinned mills and eddy current mills.
  • the grinding can take place under an inert gas and/or with cooling using liquid nitrogen. Cooling with liquid nitrogen is preferred.
  • the grinding can be at any temperature, but grinding is preferably carried out at temperatures of liquid nitrogen, for example at a temperature in the range from -210 to -195.degree. The temperature of the components during grinding is then, for example, in the range from -40 to -30.degree.
  • the components are preferably first mixed with one another and then ground.
  • the process for producing the sinter powder (SP) then preferably comprises the steps a) mixing the components (A) and optionally (B) and (C) b) grinding the mixture obtained in step a) to obtain the sinter powder (SP).
  • the subject matter of the present invention is therefore also a method for producing an amorphous sintering powder (SP), comprising the steps a) mixing the components A) an amorphous polymer component which, based on the total weight of the amorphous polymer component, contains at least 70% by weight of at least one amorphous polyamide selected from the group consisting of polyamide 6I/6T and polyamide DT/DI,
  • step a) optionally at least one reinforcing agent, b) grinding the mixture obtained in step a) to obtain the sinter powder (SP).
  • step a) Processes for compounding (for mixing) in step a) are known per se to the person skilled in the art.
  • the mixing can take place in an extruder, particularly preferably in a twin-screw extruder.
  • a further object of the present invention is therefore also the sintering powder (SP) obtainable by the process according to the invention.
  • Component (A) is an amorphous polymer component containing at least 70% by weight, based on the total weight of the amorphous polymer component, of at least one amorphous polyamide selected from the group consisting of polyamide 6I/6T and polyamide DT/DI.
  • polyamide 6I/6T means both precisely one polyamide 6I/6T and a mixture of two or more different polyamides 6I/6T.
  • Component (A) preferably contains exactly one polyamide 6I/6T.
  • polyamide DT/DI means both precisely one polyamide DT/DI and a mixture of two or more different polyamides DT/DI.
  • Component (A) preferably contains exactly one polyamide DT/DI.
  • amorphous means that the amorphous polymer component (component (A)) has no melting point in differential scanning calorimetry (DSC), measured according to ISO 11357.
  • DSC differential scanning calorimetry
  • No melting point means that the enthalpy of fusion of the amorphous polymer component AH2 ( A) is less than 10 J/g, preferably less than 8 J/g and particularly preferably less than 5 J/g, each measured using differential scanning calorimetry (DDK; Differential Scanning Calorimetry (DSC) according to ISO 11357-4:2014.
  • Suitable amorphous polymer components usually have an enthalpy of fusion AH2 ( A) of less than 10 J/g, preferably less than 8 J/g and particularly preferably less than 5 J/g, each measured using differential scanning calorimetry (DDK; differential scanning Calorimetry, DSC) according to ISO 11357-4: 2014.
  • DDK differential scanning Calorimetry
  • the component (A) according to the invention usually has a glass transition temperature ( TG (A)), the glass transition temperature (TG(A)) usually being in the range from 90 to 150° C., preferably in the range from 92 to 148° C. and particularly preferred is in the range of 94 to 146 °C, determined using ISO 11357-2: 2014.
  • the polyamide 6I/6T that can be used according to the invention usually has a glass transition temperature (TG (6 I/6T)), the glass transition temperature (TG (6 I/6T)) usually being in the range from 120 to 130° C., preferably in the range from 122 to 129 °C and more preferably in the range of 123 to 128 °C, determined by ISO 11357-2: 2014.
  • the polyamide DT/DI that can be used according to the invention usually has a glass transition temperature (TG(DT/DI>), the glass transition temperature (TG(DT/DI>) usually being in the range from 140 to 150° C., preferably in the range from 141 to 148° C and more preferably in the range of 142 to 147 °C, determined by ISO 11357-2: 2014.
  • Suitable polyamides 6I/6T can contain any proportion of 6I and 6T structural units.
  • the molar ratio of 6I structural units to 6T structural units is preferably in the range from 1:1 to 3:1, particularly preferably in the range from 1.5:1 to 2.5:1 and particularly preferably in the range from 1.8 to 1 to 2.3 to 1 .
  • the MVR (275° C./5 kg) (melt volume flow rate, MVR) of suitable polyamides 6I/6T is preferably in the range from 10 ml/10 min to 200 ml/10 min, particularly preferably in the range of 40ml/10min to 150ml/10min.
  • o (zero shear rate viscosity) of suitable polyamides 6I/6T at 240° C. is, for example, in the range from 300 to 5000 Pas, preferably in the range from 500 to 3500 Pas.
  • o is determined using a “DHR-1” rotational viscometer from TA Instruments and a plate-plate geometry with a diameter of 25 mm and a gap spacing of 1 mm. Samples of the polyamide 6I/6T are dried under vacuum at 80 °C for 7 days and then time-dependent frequency sweep (sequence test) with an angular frequency range of 500 to 0.5 rad/s. The following additional measurement parameters were used: deformation: 1.0%, measurement temperature: 240° C., measurement time: 20 min, preheating time after sample preparation: 1.5 min.
  • Suitable polyamides 6I/6T have, for example, an amino end group concentration (AEG) which is preferably in the range from 30 to 50 mmol/kg and particularly preferably in the range from 35 to 45 mmol/kg.
  • AEG amino end group concentration
  • AEG amino end group concentration
  • Suitable polyamides 6I/6T have, for example, a carboxyl end group concentration (CEG) which is preferably in the range from 60 to 155 mmol/kg and particularly preferably in the range from 80 to 135 mmol/kg.
  • CEG carboxyl end group concentration
  • CEG carboxyl end group concentration
  • Suitable polyamides DT/DI can contain any proportion of DT and DI units.
  • the molar ratio of DT structural units to DI structural units is preferably in the range from 1:1 to 3:1, particularly preferably in the range from 1.5:1 to 2.5:1 and particularly preferably in the range from 1.8 to 1 to 2.3 to 1 .
  • o (zero shear rate viscosity) of suitable polyamides DT/DI at 240° C. is, for example, in the range from 500 to 10,000 Pas, preferably in the range from 1000 to 5000 Pas.
  • o is determined using a “DHR-1” rotational viscometer from TA Instruments and a plate-plate geometry with a diameter of 25 mm and a gap spacing of 1 mm.
  • Samples of the polyamide DT/DI are dried in vacuo at 80 °C for 7 days and then measured with a time-dependent frequency sweep (sequence test) with an angular frequency range of 500 to 0.5 rad/s. The following additional measurement parameters were used: deformation: 1.0%, measurement temperature: 240° C., measurement time: 20 min, preheating time after sample preparation: 1.5 min.
  • Suitable polyamides DT/DI have, for example, an amino end group concentration (AEG) which is preferably in the range from 20 to 60 mmol/kg and particularly preferably in the range from 25 to 50 mmol/kg.
  • AEG amino end group concentration
  • 1 g of the polyamide DT/DI is dissolved in 30 ml of a phenol/methanol mixture (volume ratio phenol:methanol 75:25) and then titrated potentiometrically with 0.2N hydrochloric acid in water.
  • Suitable polyamides DT/DI have, for example, a carboxyl end group concentration (CEG) which is preferably in the range from 60 to 155 mmol/kg and particularly preferably in the range from 80 to 135 mmol/kg.
  • CEG carboxyl end group concentration
  • CEG carboxyl end group concentration
  • Polyamide DT/DI is derived from the monomers isophthalic acid, terephthalic acid and 2-methylpentamethylenediamine and is sold by the company Shakespeare, among others, under the trade name Novadyn® DT/DI.
  • the polymer component (component (A)) can contain up to 30% by weight of at least one polymer (P) which is derived from polyamide 6I/6T and polyamide DT/DI is different.
  • At least one polymer (P) means both precisely one polymer (P) and a mixture of two or more polymers (P).
  • component (A) thus contains at least 70% by weight of at least one amorphous polyamide selected from the group consisting of polyamide 6I/6T and polyamide DT/DI, and 0 to 30% by weight of at least one polymer (P) , each based on the total weight of component (A).
  • component (A) consists of at least one polyamide selected from the group consisting of polyamide 6I/6T and polyamide DT/DI.
  • the amorphous sintering powder (SP) in the range of 50 to 100% by weight of component (A), in the range of 0 to 50% by weight of component (B) and im range from 0 to 50% by weight of component (C), based in each case on the total weight of the amorphous sintering powder (SP), and component (A) of at least one polyamide selected from the group consisting of polyamide 6I/6T and Polyamide DT/DI, which contains 50 to 100% by weight of polyamide 6I/6T and/or polyamide DT/DI for sintering powder (SP), based on the total weight of the amorphous sintering powder (SP).
  • the present invention therefore also relates to a method in which the sintering powder (SP) contains 50 to 100% by weight of polyamide 6I/6T and/or polyamide DT/DI, based on the total weight of the amorphous sintering powder (SP).
  • SP sintering powder
  • component (A) consists of polyamide 6I/6T.
  • amorphous sintering powder (SP) contains in the range of 50 to 100% by weight of component (A), in the range of 0 to 50% by weight of component (B) and contains in the range from 0 to 50% by weight of component (C), based in each case on the total weight of the amorphous sintering powder (SP), and component (A) consists of polyamide 6I/6T, the sintering powder (SP) 50 to 100 % by weight of polyamide 6I/6T, based on the total weight of the amorphous sintering powder (SP).
  • the at least one polymer (P), if present, can be present in component (A) as a blend or as a powder mixture.
  • the at least one polymer (P), if present, is preferably present in component (A) as a blend.
  • the at least one polymer (P) is preferably a polyamide that differs from polyamide 6I/6T and polyamide DT/DI.
  • the polyamide can be amorphous or semi-crystalline.
  • the polymer (P) can be, for example, an amorphous, partially aromatic polyamide that is different from polyamide P6I/6T and polyamide DT/DI.
  • amorphous, partially aromatic polyamides are known to the person skilled in the art and are selected, for example, from the group consisting of PA 6I, PA 6/3T and PA PACM12.
  • the polymer (P) can also be a partially crystalline polyamide, for example.
  • the polymer (P) is preferably present as a blend with polyamide 6I/6T and/or polyamide DT/DI, so that component (A) has no melting point.
  • partially crystalline means that the polymer (P) has an enthalpy of fusion AH2 (P) of greater than 45 J/g, preferably greater than 50 J/g and particularly preferably greater than 55 J/g, each measured by differential scanning calorimetry (DSC) according to ISO 1 1357-4:2014.
  • DSC differential scanning calorimetry
  • Partially crystalline polyamides which are derived from lactams with 4 to 12 ring members are suitable, for example, as the partially crystalline polyamide.
  • Partially crystalline polyamides obtained by reacting dicarboxylic acids with diamines are also suitable.
  • As at least one partially crystalline polyamide derived from lactam are polyamides which are derived from polycaprolactam, polycapryllactam and/or polylaurolactam are mentioned as examples.
  • a partially crystalline polyamide which can be obtained from dicarboxylic acids and diamines
  • alkanedicarboxylic acids having 6 to 12 carbon atoms can be used as dicarboxylic acids.
  • aromatic dicarboxylic acids are suitable.
  • dicarboxylic acids examples include adipic acid, azelaic acid, sebacic acid and dodecanedioic acid.
  • suitable diamines are alkanediamines having 4 to 12 carbon atoms and aromatic or cyclic diamines, such as m-xylylenediamine, di-(4-aminophenyl)methane, di-(4-aminocyclohexyl)methane, 2,2-di-(4 -aminophenyl)propane or 2,2-di-(4-aminocyclohexyl)propane.
  • aromatic or cyclic diamines such as m-xylylenediamine, di-(4-aminophenyl)methane, di-(4-aminocyclohexyl)methane, 2,2-di-(4 -aminophenyl)propane or 2,2-di-(4-aminocyclohexyl)propane.
  • Copolyamide 6/66 preferably has a proportion of 5 to 95% by weight of caprolactam units, based on the total weight of the copolyamide 6/66.
  • polyamides which are obtainable by copolymerization of two or more of the monomers mentioned above and below, or mixtures of several polyamides, the mixing ratio being arbitrary. Mixtures of polyamide 6 with other polyamides, in particular copolyamide 6/66, are particularly preferred. Polyamide 66 and polyamide 6.10 are also preferred as partially crystalline polyamide.
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic acid
  • PA 610 hexamethylenediamine, sebacic acid
  • PA 612 hexamethylenediamine, decanedioic acid
  • PA 613 hexamethylenediamine, undecanedioic acid
  • PA 1212 1,12-dodecanediamine, decanedioic acid
  • PA 1313 1,13-diaminotridecane, undecanedicarboxylic acid
  • PA 6T hexamethylenediamine, terephthalic acid
  • PA MXD6 m-xylyenediamine, adipic acid
  • PA 6/66 (see PA 6 and PA 66)
  • PA 6/12 see PA 6 and PA 12
  • PA 6T/6 (see PA 6T and PA 6)
  • polyamide (polymer (P)) that differs from polyamide 6I/6T and polyamide DT/DI is preferred, selected from the group consisting of PA 4, PA 6, PA 7, PA 8, PA 9, PA 11 , PA 12, PA 46, PA 66, PA 69, PA 6.10, PA 6.12, PA 6.13, PA 6/6.36, PA 6T/6, PA 12.12, PA 13.13, PA 6T, PA MXD6, PA 6/66, PA 6 /12 and copolyamides from these.
  • Component (B) is at least one additive.
  • At least one additive means both precisely one additive and a mixture of two or more additives.
  • the at least one additive is selected from the group consisting of stabilizers, conductive additives, end group functionalizers, dyes, color pigments and flame retardants.
  • component (B) is selected from the group consisting of stabilizers, conductive additives, end-group functionalizers, dyes, color pigments and flame retardants.
  • suitable stabilizers are phenols, phosphites and copper stabilizers.
  • Suitable conductive additives are carbon fibers, metals, stainless steel fibers, carbon nanotubes and carbon black.
  • suitable end-group functionalizers are terephthalic acid, adipic acid and propionic acid.
  • suitable dyes and color pigments are carbon black and iron chromium oxides.
  • the sinter powder contains component (B), it contains at least 0.1% by weight of component (B), preferably at least 50% by weight of component (B), based on the sum of the percentages by weight of components (A) , (B) and optionally (C), preferably based on the total weight of the sinter powder (SP).
  • suitable flow aids are silicic acids or aluminum oxides.
  • Aluminum oxide is preferred as a flow aid.
  • a suitable aluminum oxide is, for example, Aeroxide® Alu C from Evonik.
  • Aluminum hydroxide and/or magnesium hydroxide and/or aluminum oxide hydroxide are therefore preferred mineral flame retardants.
  • Magnesium hydroxide is particularly preferred as a mineral flame retardant.
  • the mineral flame retardant can also be used as a mineral, for example.
  • a suitable mineral is, for example, boehmite.
  • Boehmite has the chemical composition AIO(OH) or y-ALOOH (aluminium oxide hydroxide).
  • Aluminum hydroxide is also referred to as ATH or aluminum trihydroxide.
  • Magnesium hydroxide is also known as MDH or magnesium dihydroxide.
  • the flame retardant has, for example, a D10 value in the range from 0.3 to 1.2 ⁇ m, a D50 value in the range from 1.2 to 2 ⁇ m and a D90 value in the range from 2 to 5 ⁇ m.
  • the flame retardant preferably has a D10 value in the range from 0.5 to 1 ⁇ m, a D50 value in the range from 1.3 to 1.8 ⁇ m and a D90 value in the range from 2 to 4 ⁇ m.
  • the D10, D50 and D90 values are determined as described above for the D10, D50 and D90 values of the sinter powder (SP).
  • the flame retardant can also be surface-modified.
  • the flame retardant is aminosilane-modified.
  • Component (C) is aminosilane-modified.
  • component (C) is at least one reinforcing agent.
  • At least one reinforcing agent means both precisely one reinforcing agent and a mixture of two or more reinforcing agents.
  • a reinforcing agent is understood as meaning a material which improves the mechanical properties of molded articles produced using the method according to the invention compared to molded articles which do not contain the reinforcing agent.
  • the component (C) can, for example, be spherical, platelet-shaped or fibrous.
  • the at least one reinforcing agent is preferably in the form of flakes or fibers.
  • a “fibrous reinforcing agent” is understood to mean a reinforcing agent in which the ratio of the length of the fibrous reinforcing agent to the diameter of the fibrous reinforcing agent is in the range from 2:1 to 40:1, preferably in the range from 3:1 to 30:1 and in particular preferably in the range of 5:1 to 20:1, the length of the fibrous reinforcing agent and the diameter of the fibrous reinforcing agent being determined by microscopy by image analysis on post-ashed samples, wherein at least 70,000 parts of the fibrous reinforcing agent are evaluated after ashing.
  • the length of the fibrous reinforcing agent is then usually in the range from 5 to 1000 ⁇ m, preferably in the range from 10 to 600 ⁇ m and particularly preferably in the range from 20 to 500 ⁇ m, determined by means of microscopy with image analysis after ashing.
  • the diameter is then, for example, in the range from 1 to 30 ⁇ m, preferably in the range from 2 to 20 ⁇ m and particularly preferably in the range from 5 to 15 ⁇ m, determined by means of microscopy with image evaluation after ashing.
  • the at least one reinforcing agent is in the form of flakes.
  • “flake-form” means that the particles of the at least one reinforcing agent have a diameter to thickness ratio in the range from 4:1 to 10:1, determined by means of microscopy with image analysis after ashing.
  • Suitable reinforcing agents are known to those skilled in the art and are selected, for example, from the group consisting of carbon nanotubes, carbon fibers, boron fibers, glass fibers, glass beads, silica fibers, ceramic fibers, basalt fibers, aluminum silicates, aramid fibers and polyester fibers.
  • the at least one reinforcing agent is preferably selected from the group consisting of aluminum silicates, glass fibers, glass beads, silicic acid fibers and carbon fibers.
  • the at least one reinforcing agent is particularly preferably selected from the group consisting of aluminum silicates, glass fibers, glass beads and carbon fibers. These reinforcing agents can also be aminosilane functionalized.
  • Suitable silicic acid fibers are, for example, wollastonite.
  • Aluminum silicates are compounds that contain Al2O3 and SiO2. Structurally, the aluminum silicates have in common that the silicon atoms are tetrahedrally coordinated by oxygen atoms and the aluminum atoms are octahedrally coordinated by oxygen atoms. Aluminum silicates can also contain other elements.
  • Phyllosilicates are preferred as aluminum silicates.
  • Particularly preferred aluminum silicates are calcined aluminum silicates, and calcined sheet silicates are particularly preferred.
  • the aluminum silicate can also be functionalized with aminosilane.
  • the aluminum silicate can be used in any form.
  • it can be used as pure aluminum silicate, it is also possible for the aluminum silicate to be used as a mineral.
  • the aluminum silicate is preferably used as a mineral. Examples of suitable aluminum silicates are feldspar, zeolite, sodalite, sillimanite, andalusite and kaolin. Kaolin is preferred as the aluminum silicate.
  • Kaolin is a clay rock and essentially contains the mineral kaolinite.
  • the molecular formula of kaolinite is AI 2 [(OH)4/Si2O5].
  • Kaolinite is a layered silicate.
  • kaolin usually contains other compounds such as titanium dioxide, sodium oxide and iron oxide.
  • Kaolin which is preferred according to the invention contains at least 98% by weight of kaolinite, based on the total weight of the kaolin. If the sinter powder contains component (C), it contains at least 1% by weight of component (C), based on the sum of the weight percentages of components (A), and optionally (B) and (C), preferably based on the Total weight of sinter powder (SP).
  • step ii) the layer of sintering powder (SP) provided in step i) is exposed.
  • At least part of the layer of sintering powder (SP) becomes free-flowing during exposure.
  • the liquefied sintering powder (SP) flows into one another. After exposure, the liquefied part of the layer of sintering powder (SP) cools down and solidifies again.
  • the exposure in step ii) is preferably carried out with a radiation source.
  • the radiation source is preferably a laser.
  • Suitable lasers are known to those skilled in the art and are, for example, fiber lasers, Nd:YAG lasers (neodymium-doped yttrium aluminum garnet lasers), carbon dioxide lasers or diode lasers.
  • step ii If a laser is used as the radiation source during exposure in step ii), the layer of sintering powder (SP) provided in step i) is usually exposed locally and briefly to the laser beam. Only the parts of the sintering powder (SP) that have been exposed to the laser beam become selectively flowable. This process is called selective laser sintering. Selective laser sintering is known as such to those skilled in the art.
  • the volume-related energy density (Ev) in step ii) is at least 1000 mJ/mm 3 according to the invention.
  • the volume-related energy density (Ev) is calculated using the following formula: In the formula:
  • P is the laser power of the laser used in step ii) in watts
  • v is the scanning speed of the laser used in step ii) in m/s
  • h is the scanning distance in mm in step ii)
  • d is the layer thickness of the layer provided in step i) in mm
  • n is the number of laser scans performed in step ii).
  • the volume-related energy density (Ev) in step ii) is in the range from 1000 to 3000 mJ/mm 3 , more preferably in the range from 1100 to 2750 mJ/mm 3 and particularly preferably in the range from 1200 to 2600 mJ/mm 3 .
  • the power P of the laser used in process step ii) is in the range from 15 to 40 watts, preferably in the range from 20 to 35, more preferably in the range from 22 to 32 watts and particularly preferably in the range from 23 to 30 watts.
  • the scanning speed v in method step ii) is in the range from 1 to 15 m/s, preferably in the range from 2 to 12 m/s, more preferably in the range from 3 to 10 m/s and particularly preferably in the range from 4 to 8 m /s.
  • the scanning distance h in method step ii) is in the range from 0.05 to 0.3 mm, preferably in the range from 0.07 to 0.25 mm, more preferably in the range from 0.08 to 0.2 mm and particularly preferably in the range Range from 0.08 to 0.18mm.
  • the scanning distance h is also called the laser distance or the track distance. In selective laser sintering, scanning is usually done in strips. The scanning distance indicates the distance between the centers of the strips, i.e. between the two centers of the laser beam of two strips.
  • the number of laser scans n in method step ii) is in the range from 1 to 3, preferably n is 1 or 2, most preferably n is 2.
  • step ii) the layer of sintering powder (SP) is usually lowered by the layer thickness of the layer of sintering powder (SP) provided in step i) and a further layer of sintering powder (SP) is applied. This is then exposed again according to step ii).
  • the upper layer of the sintering powder (SP) connects to the lower layer of the sintering powder (SP), and the particles of the sintering powder (SP) within the upper layer connect to one another by liquefaction.
  • steps i) and ii) can therefore be repeated.
  • a further object of the present invention is therefore also a shaped body obtainable by the process according to the invention.
  • the subject of the present invention is therefore also the use of a sintering powder (SP) which contains the components
  • a shaped body is obtained by the process according to the invention.
  • the shaped body can be removed from the powder bed directly after the solidification of the sintering powder (SP) liquefied during exposure to light in step ii). It is also possible to first cool the shaped body and only then to remove it from the powder bed. Any adhering particles of the sintering powder that have not been liquefied can be mechanically removed from the surface using known methods. Processes for the surface treatment of the shaped body include, for example, vibratory finishing or vibratory machining, as well as sandblasting, glass bead blasting or microblasting.
  • a further object of the present invention is therefore a shaped body obtainable by the process according to the invention.
  • the moldings obtained usually contain in the range from 50 to 100% by weight of component (A), in the range from 0 to 50% by weight of component (B), in the range from 0 to 50% by weight of component ( C), in each case based on the total weight of the molding.
  • component (A) is component (A) which was contained in the sintering powder (SP).
  • component (B), if any, is the component (B) contained in the sintering powder (SP)
  • component (C), if any, is the component (C) contained in the Sinter powder (SP) was included.
  • Components (A) and optionally (B) and (C) preferably do not enter into any chemical reaction during exposure in step ii), but the sinter powder (SP) merely becomes free-flowing.
  • the amorphous polymer component (component (A)) is Grivory G16 (amorphous polyamide 6I/6T) from EMS, Zytel HTN 301 (amorphous polyamide 6I/6T) from DuPont and Novadyn DT/DI (amorphous polyamide DT/DI) from the company Shakespeare (US) used.
  • Irganox® 1098 N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) from BASF SE is used as component (B).
  • Ultrasint® PA6 polyamide PA6 from BASF 3D Printing Solutions GmbH, Heidelberg and Ultramid® B27E (polyamide PA6) from BASF SE are used as partially crystalline polyamides.
  • the scanning speed (v) of the laser is 5 m/s in all cases.
  • Test specimen width 10 mm, length 80 mm, thickness 4 mm, distance between supports 64 mm.
  • Speeds 0.1 mm/s for the module determination, 0.3 mm/s for the rest of the measurement
  • volume-related energy density during laser sintering is calculated as follows:
  • Test specimens for mechanical tests were produced with the sintering parameters shown in Tab. 5 and tested according to the standard. Results in Table 6.
  • Tab. 6 Characterization of the mechanical properties by means of a tensile test according to ISO 527-2:2012 at room temperature (23 °C) and a Charpy impact strength test according to DIN EN ISO179-2:2012.
  • “Dry” means storage for 336 hours at 80°C under vacuum.
  • “Conditioned” means storage for 336 hours at 70°C and a relative humidity of 72%.
  • Table 6 shows that the amorphous polyamides PA 6I6T (Grivory G16 and Zytel HTN301) achieve good mechanical properties overall under the claimed process parameters of laser sintering and only show slight discoloration of the components.
  • the storage modulus G' was measured using dynamic mechanical analysis (DMTA) in a temperature range from -100 °C to 200 °C.
  • DMTA dynamic mechanical analysis
  • the change in the storage modulus G' was evaluated over the respective temperature range.
  • the storage modulus G' at the highest temperature of the respective temperature range was subtracted from the value of the storage modulus G' at the lowest temperature and this difference was normalized to the temperature interval.
  • the specified temperature ranges cover typical application temperature ranges.
  • Polyamide 6I6T is characterized by the fact that the change in modulus over a given temperature range is small compared to other materials used in SLS processes, such as Ultrasint® PA 6.
  • PA 6 we get in particular in the temperature ranges 20 °C to 80 °C and 20 °C to 120 °C, the changes in the modulus are factors higher than is the case with PA 6I6T.
  • composition of the mixture of PA 6I6T and PA 6 manufactured in a twin-screw extruder with a screw diameter of 25 mm.
  • the screw speed is 200 rpm
  • the throughput is 20 kg/h
  • the barrel temperature set in the discharge zone is 280 °C.
  • the resulting pressure at the extrusion die with diameter 4 mm is 10 bar.
  • PA 6I6T Grivory G16 natural 74.6% by weight
  • the mixture was ground to produce the sinter powder.
  • Tab. 11 Component properties, test in dry condition at 23 °C, in

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  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention se rapporte à un procédé pour la préparation d'un corps moulé dans lequel, à l'étape i), une couche d'une poudre à fritter (SP) amorphe qui comprend au moins 70 % en poids d'au moins un polyamide amorphe, choisi dans le groupe constitué par le polyamide 6I/6T et le polyamide DT/DI, est formée et à l'étape ii), la couche formée à l'étape i) est sélectivement frittée. La présente invention se rapporte également à un procédé pour la préparation d'une poudre à fritter (SP) amorphe et à une poudre à fritter (SP) amorphe qui peut être obtenue par ce procédé. La présente invention se rapporte en outre à l'utilisation de la poudre à fritter (SP) amorphe dans un procédé de frittage et à des corps moulés qui peuvent être obtenus par le procédé selon l'invention.
EP22761153.0A 2021-08-12 2022-08-03 Procédé pour la préparation d'un corps moulé par frittage laser sélectif d'une poudre à fritter (sp) amorphe contenant du polyamide 6i/6t et/ou du polyamide dt/di Pending EP4384577A1 (fr)

Applications Claiming Priority (2)

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EP21191097 2021-08-12
PCT/EP2022/071860 WO2023016898A1 (fr) 2021-08-12 2022-08-03 Procédé pour la préparation d'un corps moulé par frittage laser sélectif d'une poudre à fritter (sp) amorphe contenant du polyamide 6i/6t et/ou du polyamide dt/di

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EP4384577A1 true EP4384577A1 (fr) 2024-06-19

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US (1) US20240359399A1 (fr)
EP (1) EP4384577A1 (fr)
JP (1) JP2024530054A (fr)
KR (1) KR20240042506A (fr)
CN (1) CN118019804A (fr)
WO (1) WO2023016898A1 (fr)

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US5527877A (en) 1992-11-23 1996-06-18 Dtm Corporation Sinterable semi-crystalline powder and near-fully dense article formed therewith
US5648450A (en) 1992-11-23 1997-07-15 Dtm Corporation Sinterable semi-crystalline powder and near-fully dense article formed therein
KR102214236B1 (ko) 2015-06-23 2021-02-10 사빅 글로벌 테크놀러지스 비.브이. 분말 층 용융결합 공정에서의 무정형 중합체의 개선된 제조성
TW201817812A (zh) 2016-07-29 2018-05-16 巴斯夫歐洲公司 用於雷射燒結粉末之聚醯胺摻合物
TW201821534A (zh) 2016-07-29 2018-06-16 巴斯夫歐洲公司 用於雷射燒結粉末之包含聚芳醚的聚醯胺摻合物
TW201821535A (zh) 2016-07-29 2018-06-16 巴斯夫歐洲公司 用於雷射燒結粉末之包含增強劑的聚醯胺摻合物
US11230646B2 (en) 2016-10-11 2022-01-25 Shpp Global Technologies B.V. Crystalline polycarbonate powders for powder bed fusion in additive manufacturing
CN112166024A (zh) 2018-05-25 2021-01-01 Sabic环球技术有限责任公司 使聚合物物体成形的方法

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Publication number Publication date
CN118019804A (zh) 2024-05-10
WO2023016898A1 (fr) 2023-02-16
KR20240042506A (ko) 2024-04-02
JP2024530054A (ja) 2024-08-14
US20240359399A1 (en) 2024-10-31

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