Additive manufacturing process using a building material that contains metal-oxide coated mica

Patent metadata

Field	Value
Publication number	US-12454094-B2
Application number	US-201917288347-A
Country	US
Kind code	B2
Filing date	Oct 21, 2019
Priority date	Oct 26, 2018
Publication date	Oct 28, 2025
Grant date	Oct 28, 2025

Abstract

The present invention relates to a method of producing an article, comprising the step of producing the article by means of an additive manufacturing method from a build material comprising an aromatic polycarbonate and interference pigments and/or pearlescent pigments from the group of the metal oxide-coated micas. The invention likewise relates to an article obtainable by the method. The build material further comprises ≥0.05% by weight to ≤3% by weight of anhydride-modified α-olefin polymer.

First claim

The invention claimed is:

1. A method of producing an article, comprising producing the article by means of an additive manufacturing method from a build material,
wherein
the build material, based on the total weight of the build material, comprises
A) ≥50% by weight to ≤98.5% by weight of aromatic polycarbonate,
B) ≥0.8% by weight to ≤3.0% by weight of interference pigment and/or pearlescent pigment from a group of metal oxide-coated micas and
C) ≥0.05% by weight to ≤3% by weight of anhydride-modified α-olefin polymer,
where the sum total of the percentages by weight of A), B) and C) is ≤100% by weight,
wherein the build material A) comprises a polycarbonate having a weight-average molecular weight M w of ≥10 000 to ≤40 000 g/mol, determined by gel permeation chromatography in methylene chloride at 25° C. against polycarbonate standards.

2. The method as claimed in claim 1 , wherein the pearlescent pigment and/or interference pigment B) from the group of the metal oxide-coated micas present is anatase- or rutile-coated mica.

3. The method as claimed in claim 1 , wherein the anhydride-modified α-olefin polymer C) has been modified with maleic anhydride and is based on ethene, propene and/or 1-octene.

4. The method as claimed in claim 1 , wherein the anhydride-modified α-olefin polymer C) has an average molecular weight M w , determined by means of gel permeation chromatography in ortho-dichlorobenzene at 150° C. with polystyrene calibration, of ≥1000 to ≤15 000 g/mol and an acid number of ≥45 to ≤170 mg KOH/g, determined to DIN ISO 17025:2018-03 by means of potentiometric titration.

5. The method as claimed in claim 1 , wherein the build material further comprises D) ≥0.001% by weight to ≤0.500% by weight, based on the total weight of the build material, of one or more phosphorus-containing thermal stabilizers, and the sum total of the percentages by weight of A), B), C) and D) is ≤100% by weight.

6. The method as claimed in claim 5 , wherein the build material further comprises E) >0% by weight to ≤7% by weight, based on the total weight of the build material, of further additives selected from the group consisting of flame retardants, anti-dripping agents, thermal stabilizers other than component D), impact modifiers, fillers, antistats, colorants, pigments other than component B, also including carbon black, lubricants, demolding agents, hydrolysis stabilizers, compatibilizers, UV absorbers and/or IR absorbers,
and the sum total of the percentages by weight of A), B), C), D) and E) is ≤100% by weight.

7. A method of producing an article, comprising producing the article by means of an additive manufacturing method from a build material,
wherein
the build material, based on the total weight of the build material, comprises
A) ≥50% by weight to ≤98.5% by weight of aromatic polycarbonate,
B) ≥0.8% by weight to ≤3.0% by weight of interference pigment and/or pearlescent pigment from a group of metal oxide-coated micas and
C) ≥0.05% by weight to ≤3% by weight of anhydride-modified α-olefin polymer,
where the sum total of the percentages by weight of A), B) and C) is ≤100% by weight,
wherein the production of the article by the additive manufacturing method comprises the steps of:
-applying a layer of particles including the build material to a target surface;
-introducing energy into a selected portion of the layer of particles corresponding to a cross section of the article such that the particles in the selected portion are bonded, thereby producing a bonded portion;
-repeating the steps of applying the layer of particles and introducing energy for a multitude of layers, such that the bonded portion of adjacent layers become bonded in order to form the article.

8. The method as claimed in claim 1 , wherein a layer of the build material applied last in the additive manufacturing method has a surface temperature that is not less than a temperature which, in a dynamic-mechanical analysis of the build material (to ISO 6721-10:2015-09 at an angular frequency of 1/s), corresponds to a point of intersection of a theoretical straight line in the section of a curve of a storage modulus E′ corresponding to a vitreous state of the build material and a theoretical straight line in the section of the curve of the storage modulus E′ in which the storage modulus E′ declines and indicates a glass transition.

9. The method as claimed in claim 1 , wherein a multitude of build materials are used, and at least one of the multitude of build materials is the build material.

10. A method of producing an article, comprising producing the article by means of an additive manufacturing method from a build material,
wherein
the build material, based on the total weight of the build material, comprises
A) ≥50% by weight to ≤98.5% by weight of aromatic polycarbonate,
B) ≥0.8% by weight to ≤3.0% by weight of interference pigment and/or pearlescent pigment from a group of metal oxide-coated micas and
C) ≥0.05% by weight to ≤3% by weight of anhydride-modified a-olefin polymer,
where the sum total of the percentages by weight of A), B) and C) is ≤100% by weight,
wherein the production of the article by the additive manufacturing method comprises the steps of:
-applying a filament of an at least partly molten build material to a carrier, such that a layer of the build material is obtained, corresponding to a first selected cross section of the article;
-applying a filament of the at least partly molten build material to a previously applied layer of the build material, such that a further layer of the build material is obtained, which corresponds to a further selected cross section of the article and which is bonded to the layer applied beforehand;
-repeating the step of applying a filament of the at least partly molten build material to a previously applied layer of the build material until the article has been formed.

11. The method as claimed in claim 1 , wherein the method is conducted within a build chamber, and the build chamber has a temperature that is ≥10° C. lower than the glass transition temperature T g of the build material (determined by DSC to ISO 11357-2:2013-05 at a heating rate of 10° C./min).

Assignees

• Stratasys Inc

Inventors

• Wandner Derk
• Liu Ting
• Kuenzel Jonas

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08L69/00 Primary

  Compositions of polycarbonates; Compositions of derivatives of polycarbonates · CPC title

• C08L23/26

  modified by chemical after-treatment (saponified copolymers C08L23/0861; unsaturated acid salts C08L23/0876) · CPC title

• C08K5/5313

  Phosphinic compounds, e.g. R2=P(:O)OR' · CPC title

• C08K3/34

  Silicon-containing compounds · CPC title