Additive manufacturing process using a building material having a high hard segment content
A method for producing an object comprises the step of producing the object by means of an additive manufacturing process from a construction material. The construction material comprises a first polyurethane polymer which has: a weight percentage ratio of O to N of ≥2 to ≤2.5, determined by elementary analysis; a weight percentage ratio of N to C of ≥0.1 to ≤0.25, determined by elementary analysis; a full-width at half maximum of the melting peak of ≤20 K, determined by dynamic differential scanning calorimetry DSC (2 nd heating at heating rate 20 k/min); and a difference between the melting temperature and the recrystallisation temperature of ≥5 K and ≤100 K, determined by dynamic differential scanning calorimetry DSC (2 nd heating) at a heating and cooling rate of 20 K/min.
1. A process for producing an article comprising the step of producing the article by means of an additive manufacturing process from a build material,
wherein the build material comprises a first polyurethane polymer which has a percent by weight ratio of O to N determined by elemental analysis of ≥2 to ≤2.5, a weight ratio of N to C determined by elemental analysis of ≥0.1 to ≤0.25, a full width at half maximum of the melting peak determined by differential scanning calorimetry (DSC; 2nd heating at heating rate of 5 K/min) of ≤20 K and a difference between the melting temperature and the recrystallization temperature determined by differential scanning calorimetry (DSC; 2nd heating) at a heating and cooling rate of 20 K/min of ≥5 K and ≤100 K.
2. The process as claimed in claim 1 , wherein the first polyurethane polymer comprises a proportion of hard segments of ≥80% by weight to ≤100% by weight, expressed as the weight ratio of the sum of constituents derived from Zerewitinoff-active compounds having three or fewer repeating units in the molecule and the isocyanate units joined thereto to the total weight of the polyurethane polymer.
3. The process as claimed in claim 1 , wherein the first polyurethane polymer is obtained from the reaction of an isocyanate component comprising ≥80% by weight of aliphatic isocyanates and an isocyanate-reactive component.
4. The process as claimed in claim 1 , wherein the first polyurethane polymer is obtained from the reaction of an isocyanate component comprising >80% by weight of linear aliphatic isocyanates and an isocyanate-reactive component comprising ≥80% by weight of linear aliphatic polyols.
5. The process as claimed in claim 1 , wherein the first polyurethane polymer is obtained from the reaction of a linear diisocyanate component comprising ≥80% by weight of a linear aliphatic isocyanate component and a linear diol component comprising ≥80% by weight of a linear aliphatic polyol component.
6. The process as claimed in claim 1 , wherein the build material has a melting point determined by differential scanning calorimetry (DSC; 2 nd heating at a heating rate of 20 K/min) of ≥120° C. to ≤189° C. and the full width at half maximum of the melting point peak (differential scanning calorimetry, DSC; 2nd heating at a heating rate of 5 K/min) of the build material is ≥5 K to ≤20 K.
7. The process as claimed in claim 1 , wherein the build material exhibits after 1000 hours of SAE J 1960 CAM 180 weathering a color number increase of ≤50 in the b value.
8. The process as claimed in claim 1 , wherein a complex viscosity of the molten build material determined via a plate/plate rheometer at 1/s and 0.1% amplitude at 200° C., measured after 1 minute in each case, is still ≥50% of the complex viscosity of the molten build material measured at 190° C. and the complex viscosity of the molten build material measured at 240° C. is only ≤15% of the complex viscosity of the molten build material measured at 190° C.
9. The process as claimed in claim 8 , wherein the complex viscosity of the molten build material at 240° C. regains ≥50% of a starting viscosity according to ISO 6721-10:2015-09 at 1/s and 0.1% deformation at 190° C. after 1 minute after cooling to 190° C.
10. The process as claimed in claim 1 , wherein the production of the article by means of the additive manufacturing process comprises the steps of:
applying a layer of particles comprising the build material to a target surface;
optionally printing a radiant energy-absorbing and/or radiant energy-reflecting material onto a selected portion of the layer and energizing the layer, wherein the selected portion of the layer exhibits a higher or lower absorption of the energy, so that the particles in the selected portion or surrounding the selected portion are joined according to a cross section of the article;
energizing a selected portion of the layer corresponding to a cross section of the article to join the particles in the selected portion;
repeating the steps of applying and energizing for a plurality of layers to join the joined portions of the adjacent layers to form the article.
11. The process as claimed in claim 1 , wherein the production of the article by means of the additive manufacturing process comprises the steps of:
applying a filament of an at least partially molten build material to a carrier to obtain a layer of the build material corresponding to a first selected cross section of the article;
optionally applying a filament of the at least partially molten build material to a previously applied layer of the build material to obtain a further layer of the build material which corresponds to a further selected cross section of the article and is joined to the previously applied layer;
optionally repeating the step of applying a filament of the at least partially molten build material to a previously applied layer of the build material until the article has been formed.
12. The process as claimed in claim 1 , wherein the process is performed inside a build space and the temperature of the build space is ≥5° C. lower than the melting temperature T m of the build material (determined by differential scanning calorimetry DSC; according to DIN EN ISO 11357-1:2017-02 at a heating rate of 20° C./min).
13. An article obtained by a process according to claim 1 , wherein the article is produced from a build material comprising a first polyurethane polymer which has a percent by weight ratio of O to N determined by elemental analysis of ≥2 to ≤2.5, a weight ratio of N to C determined by elemental analysis of →0.1 to ≤0.25, a full width at half maximum of the melting peak determined by differential scanning calorimetry (DSC; 2nd heating at heating rate of 20 K/min) of ≤20 K and a difference between the melting temperature and the recrystallization temperature determined by differential scanning calorimetry (DSC; 2nd heating) at a heating and cooling rate of 20 K/min of ≥5 K and ≤100 K and wherein the article has a tensile strength (ISO 527:2012) in the build direction of the additive manufacturing process used in its production which is ≥20% to ≤100% of the tensile strength (ISO 527:2012) of an injection molded test specimen made of the same build material.
14. The article as claimed in claim 13 , wherein the first polyurethane polymer comprises a proportion of hard segments of ≥80% by weight to ≤100% by weight, expressed as the weight ratio of the sum of constituents derived from Zerewitinoff-active compounds having three or fewer repeating units in the molecule and the isocyanate units joined thereto to the total weight of the polyurethane polymer.
15. The article as claimed in claim 13 , wherein the first polyurethane polymer is obtained from the reaction of an isocyanate component comprising ≥80% by weight of linear aliphatic isocyanates and an isocyanate-reactive component comprising ≥80% by weight of linear aliphatic polyols.