# US 11,999,103 B2 · Filament materials comprising marking additives for extrusion-based additive manufacturing systems > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,999,103 B2 - Document ID: US11999103B2 - Status: Granted - Kind: B2 - Application number: 17/815,144 - Filed: 2022-07-26 - Published: 2022-11-17 - Granted: 2024-06-04 - Earliest claimed: 2019-12-20 - Assignees: Xerox Corporation - Applicants: Xerox Corporation - Inventors: Nan Xing Hu - Web page: https://patentgrep.com/patent/US11999103B2 ## CPC - B29C 64/188: involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control (surface shaping B29C59/00; after-treatment of articles without altering their shape B29C71/00) - C08K 3/22: of metals - B29C 64/118: using filamentary material being melted, e.g. fused deposition modelling [FDM] - B33Y 10/00: Processes of additive manufacturing - B33Y 40/20: Post-treatment, e.g. curing, coating or polishing - B33Y 70/00: Materials specially adapted for additive manufacturing - B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials - C08K 3/013: Fillers, pigments or reinforcing additives - C08K 3/042: {Graphene or derivatives, e.g. graphene oxides} - C08K 3/2279: {of antimony} - C08K 3/32: Phosphorus-containing compounds - C08K 3/36: Silica - C08L 5/00: Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00 - C08L 55/02: ABS [Acrylonitrile-Butadiene-Styrene] polymers - C08L 61/28: with melamine - D01F 1/10: Other agents for modifying properties - B41M 5/267: {Marking of plastic artifacts, e.g. with laser} - C08K 2003/2231: {of tin} - C08K 2003/2241: {Titanium dioxide} - C08K 2003/321: {Phosphates} - C08K 2201/011: Nanostructured additives - 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 (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - 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 - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS - B41M: PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING, (correction of typographical errors B41J; processes for applying transfer pictures or the like B44C1/16; fluid media for correction of typographical errors by coating C09D10/00; printing textiles D06P) ## Abstract A filament material and a method for producing the same is disclosed. For example, the filament material includes a polymer resin that is compatible with an extrusion based printing process and a marking additive that allows selective portions of the filament material to change color when exposed to a light, wherein the marking additive is added to approximately 0.01 to 25.00 weight percent (wt %). ## Claims ### Claim 1 A method for producing a filament material for an extrusion based printer, comprising: providing a polymer resin that is compatible with the extrusion based printer; mixing into the polymer resin a marking additive that is color changeable in response to certain light wavelengths to form the filament material such that when a surface of the filament material is exposed to the certain light wavelengths, a mark on the surface of the filament material is formed due to a change in color of the marking additive; and mixing into the polymer resin and the marking additive a developer component comprising at least one of: a polyphenol, a melamine resin, or a polysaccharide. ### Claim 2 (depends on 1) The method of claim 1, wherein the polymer resin comprises at least one of: an acrylic resin; a polymer or a copolymer produced from a monomer selected from a group of: acrylonitrile, butadiene, styrene, an acrylate, a methacrylate, and a mixture thereof; a polyolefin; a polyester; a polycarbonate; polylactic acid; a thermoplastic polyurethane; a polyamide; a polyimide; polysulfone; a poly(aryl ether); a poly(aryl ether ketone); a poly(aryl ether sulfone); poly(ether imide); a polyarylenesulfide, poly(vinyl alcohol), or polyvinylidene fluoride. ### Claim 3 (depends on 1) The method of claim 1, wherein the marking additive comprises an infrared absorption component that absorbs light at wavelengths of 780 nanometers (nm) to 11000 nm. ### Claim 4 (depends on 1) The method of claim 1, wherein the marking additive comprises at least one of: a metal oxide, a non-stoichiometric metal oxide, a metal hydroxide, a copper hydroxyphosphate, a copper pyrophosphate, a base copper carbonate, ammonium octamolebdate, a silver halide, a phthalocyanine, a naphthalocyanine, graphitic oxide, graphene oxide, or carbon black. ### Claim 5 (depends on 4) The method of claim 4, wherein the metal oxide or the non-stoichiometric metal oxide comprises at least one of: tin, antimony, bismuth, boron, titanium, indium, iron, copper, molybdenum, tungsten, or vanadium. ### Claim 6 (depends on 4) The method of claim 4, wherein the metal hydroxide comprises at least one of: aluminum hydroxide, magnesium hydroxide, or copper hydroxide. ### Claim 7 (depends on 1) The method of claim 1, further comprising: mixing into the polymer resin and the marking additive a support material comprising at least one of: silica, alumina, titanium oxide, mica, kaolin, zinc oxide, calcium carbonate, talc, or ceramic. ### Claim 8 (depends on 1) The method of claim 1, further comprising: mixing into the polymer resin and the marking additive a pigment or a colorant. ### Claim 9 (depends on 1) The method of claim 1, wherein the certain light wavelengths are emitted from a pulsed laser light source or a continuous laser light source. ### Claim 10 (depends on 1) The method of claim 1, wherein the marking additive is present in an amount of 0.01 to 25.00 weight percent (wt %). ### Claim 11 (depends on 1) The method of claim 1, wherein the mark comprises information related to processing parameters of the filament material with the marking additive in the extrusion based printer to automatically set the processing parameters in the extrusion based printer. ### Claim 12 A method for marking a three-dimensional (3D) printed object that is printed with a filament material with a marking additive, comprising: receiving, by a processor, instructions to print the 3D printed object; controlling, by the processor, an extrusion based printer to print the 3D printed object in accordance with the instructions, wherein the 3D printed object is printed with the filament material with the marking additive, wherein the filament material with the marking additive comprises a polymer resin and 0.01 to 25.00 weight percent (wt %) of the marking additive that is color changeable in response to certain light wavelengths, wherein the filament material further comprises a support material comprising at least one of: silica, alumina, titanium oxide, mica, kaolin, zinc oxide, calcium carbonate, talc, or ceramic; receiving, by the processor, marking instructions associated with a marking for the 3D printed object; and controlling, by the processor, a laser to expose portions of a surface of the 3D printed object in accordance with the marking instructions to change a color of the portions of the surface of 3D printed object to write the marking on the surface of the 3D printed object. ### Claim 13 (depends on 12) The method of claim 12, wherein the laser comprises at least one of: a fiber laser, a diode laser, a diode array laser, a yttrium aluminum garnet (YAG) laser, or a carbon dioxide laser that emits light at approximately 780 nanometers (nm) to approximately 11,000 nm. ### Claim 14 (depends on 12) The method of claim 12, wherein the marking comprises alphanumeric text, a graphic, or an image. ### Claim 15 (depends on 12) The method of claim 12, wherein the polymer resin comprises at least one of: an acrylic resin; a polymer or a copolymer produced from a monomer selected from a group of: acrylonitrile, butadiene, styrene, an acrylate, a methacrylate, and a mixture thereof; a polyolefin; a polyester; a polycarbonate; polylactic acid; a thermoplastic polyurethane; a polyamide; a polyimide; polysulfone; a poly(aryl ether); a poly(aryl ether ketone); a poly(aryl ether sulfone); poly(ether imide); a polyarylenesulfide, poly(vinyl alcohol), or polyvinylidene fluoride. ### Claim 16 (depends on 12) The method of claim 12, wherein the marking additive comprises at least one of: a metal oxide, a non-stoichiometric metal oxide, a metal hydroxide, a copper hydroxyphosphate, a copper pyrophosphate, a base copper carbonate, ammonium octamolebdate, a silver halide, a phthalocyanine, a naphthalocyanine, graphitic oxide, graphene oxide, or carbon black. ### Claim 17 (depends on 12) The method of claim 12, wherein the filament material further comprises a developer component comprising at least one of: a polyphenol, a melamine resin, or a polysaccharide. ### Claim 18 (depends on 12) The method of claim 12, wherein the filament material further comprises a pigment or a colorant.