# US 9,434,838 B2 · Multi-color ink for 3D printing, 3D printer, and method of controlling the 3D printer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,434,838 B2 - Document ID: US9434838B2 - Status: Granted - Kind: B2 - Application number: 14/502,072 - Filed: 2014-09-30 - Published: 2015-04-02 - Granted: 2016-09-06 - Earliest claimed: 2013-10-02 - Assignees: Samsung Electronics Co., Ltd. - Applicants: Samsung Electronics Co., Ltd. - Inventors: Yeon Kyoung Jung; O Hyun Beak; Keon Kuk; Eun Bong Han; Yong Hyun Lim; Jong Youb Ryu - Web page: https://patentgrep.com/patent/US9434838B2 ## CPC - C08L 33/08: Homopolymers or copolymers of acrylic acid esters - B05C 5/00: Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work (B05C7/00 takes precedence; essentially involving spraying or electrostatic projection B05B) - B05D 5/00: Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures - B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor - C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing - C09D 11/38: characterised by non-macromolecular additives other than solvents, pigments or dyes - C09D 11/40: Ink-sets specially adapted for multi-colour inkjet printing - C09D 11/54: Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink - C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - B05C: APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (spraying apparatus, atomising apparatus, nozzles B05B; plant for applying liquids or other fluent materials to objects by electrostatic spraying B05B5/08) - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) - 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 - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) ## Abstract A multi-color ink for 3D printing, a 3D printer, and a method of controlling the 3D printer are provided. The multi-color ink for 3D printing including a first ink composition that includes a photocurable material, a photoinitiator configured to cure the photocurable material, a first colorant, and an anti-intercolor bleed agent configured to prevent intercolor bleeding occurring when the plurality of ink compositions come into contact with each other, and a second ink composition that includes a photocurable material, a photoinitiator configured to cure the photocurable material, and a second colorant having an acid moiety involved in a reaction with the anti-intercolor bleed agent to cause aggregation. The multi-color ink for 3D printing may enable a clear image by inhibiting intercolor bleeding that occurs when ink compositions with different colors are printed to be adjacent to each other before curing during 3D printing. ## Claims ### Claim 1 A multi-color ink for 3D printing comprising: a plurality of ink compositions comprising a first ink composition and a second ink composition, wherein the first ink composition comprises: at least one photocurable material, a photoinitiator configured to cure the photocurable material; a first colorant, and an anti-intercolor bleed agent configured to prevent intercolor bleeding occurring when the plurality of ink compositions come into contact with each other, and the second ink composition comprises: at least one photocurable material, a photoinitiator configured to cure the photocurable material; and a second colorant having an acid moiety involved in a reaction with the anti-intercolor bleed agent to cause aggregation. ### Claim 2 (depends on 1) The multi-color ink for 3D printing according to claim 1, wherein the anti-intercolor bleed agent is an amide compound represented by Formula 1: wherein R1 to R4 are, each independently, hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylsulfoneamide group, a substituted or unsubstituted C6-C20 arylsulfoneamide group, a substituted or unsubstituted C1-C20 acylamino group, a C1-C20 alkylureido group, a C6-C20 arylureido group, a C2-C20 alkoxycarbonyl group, a C2-C20 alkoxycarbonylamino group, a carbamoyl group, a sulfamoyl group, a sulfo group and a salt thereof, a carboxyl group and a salt thereof, a substituted or unsubstituted C1-C20 hydroxyalkyloxyalkyl group, a substituted or unsubstituted C1-C20 dialkylaminoalkyl group, a substituted or unsubstituted C6-C20 pyridylalkyl group, a substituted or unsubstituted C5-C20 pyridyl group, a substituted or unsubstituted C6-C20 imidazolyl group, a hydrazine group, a hydrazone group, a substituted or unsubstituted C1-C20 pyridylalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 arylalkyl group, a substituted or unsubstituted C6-C20 heteroaryl group, a substituted or unsubstituted C6-C20 heteroarylalkyl group, a substituted or unsubstituted C6-C20 heteroarylalkenyl group, or a substituted or unsubstituted C3-C20 heterocycloalkyl group, and R3 and R4 are connected to each other to form a substituted or unsubstituted C1-C20 alkylene group, wherein at least one of the R1 to R4 comprises an acrylate group or methacrylate group at one end thereof. ### Claim 3 (depends on 2) The multi-color ink for 3D printing according to claim 2, wherein the anti-intercolor bleed agent is an amide compound represented by Formula 2: wherein R1 and R2 are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylsulfoneamide group, a substituted or unsubstituted C6-C20 arylsulfoneamide group, a substituted or unsubstituted C1-C20 acylamino group, a C1-C20 alkylureido group, a C6-C20 arylureido group, a C2-C20 alkoxycarbonyl group, a C2-C20 alkoxycarbonylamino group, a carbamoyl group, a sulfamoyl group, a sulfo group and a salt thereof, a carboxyl group and a salt thereof, a substituted or unsubstituted C1-C20 hydroxyalkyloxyalkyl group, a substituted or unsubstituted C1-C20 dialkylaminoalkyl group, a substituted or unsubstituted C6-C20 pyridylalkyl group, a substituted or unsubstituted C5-C20 pyridyl group, a substituted or unsubstituted C6-C20 imidazolyl group, a hydrazine group, a hydrazone group, a substituted or unsubstituted C1-C20 pyridylalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 arylalkyl group, a substituted or unsubstituted C6-C20 heteroaryl group, a substituted or unsubstituted C6-C20 heteroarylalkyl group, a substituted or unsubstituted C6-C20 heteroarylalkenyl group, or a substituted or unsubstituted C3-C20 heterocycloalkyl group, wherein at least one of R1 and R2 comprises an acrylate group or methacrylate group at one end thereof, n is an integer of 2 to 6, m is an integer of 0 to 6, X is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylsulfoneamide group, a substituted or unsubstituted C6-C20 arylsulfoneamide group, a substituted or unsubstituted C1-C20 acrylamino group, a C1-C20 alkylureido group, a C6-C20 arylureido group, a C2-C20 alkoxycarbonyl group, a C2-C20 alkoxycarbonylamino group, a carbamoyl group, a sulfamoyl group, a sulfo group and a salt thereof, a carboxyl group and a salt thereof, a substituted or unsubstituted C1-C20 hydroxyalkyloxyalkyl group, a substituted or unsubstituted C1-C20 dialkylaminoalkyl group, a substituted or unsubstituted C6-C20 pyridylalkyl group, a substituted or unsubstituted C5-C20 pyridyl group, a substituted or unsubstituted C6-C20 imidazolyl group, a hydrazine group, a hydrazone group, a substituted or unsubstituted C1-C20 pyridylalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 arylalkyl group, a substituted or unsubstituted C6-C20 heteroaryl group, a substituted or unsubstituted C6-C20 heteroarylalkyl group, a substituted or unsubstituted C6-C20 heteroarylalkenyl group, or a substituted or unsubstituted C3-C20 heterocycloalkyl group. ### Claim 4 (depends on 1) The multi-color ink for 3D printing according to claim 1, wherein the anti-intercolor bleed agent is a cycloamine compound. ### Claim 5 (depends on 4) The multi-color ink for 3D printing according to claim 4, wherein the cycloamine compound is a pyrrole derivative, a pyridine derivative, a quinoline derivative, an isoquinoline derivative, a pyrrolidine derivative, or a piperidine derivative. ### Claim 6 (depends on 1) The multi-color ink for 3D printing according to claim 1, wherein the acid moiety of the second colorant is a carboxylate group, a sulfonate group, a phosphate group, or a salt thereof. ### Claim 7 (depends on 1) The multi-color ink for 3D printing according to claim 1, wherein a content of at least one of the first colorant and the second colorant is in the range of about 0.01 to about 1% by weight based on a weight of the first ink composition or the second ink composition. ### Claim 8 (depends on 1) The multi-color ink for 3D printing according to claim 1, wherein the anti-intercolor bleed agent is contained in an amount about 0.5 to about 10 times molar ratio of the acid moiety of the second colorant. ### Claim 9 (depends on 1) The multi-color ink for 3D printing according to claim 1, wherein the photocurable material is an acrylate-based or methacrylate-based compound having at least one unsaturated functional group. ### Claim 10 (depends on 9) The multi-color ink for 3D printing according to claim 9, wherein the photocurable material comprises at least one compound selected from the group consisting of a hydroxyl group-containing acrylate-based compound, a water-soluble acrylate-based compound, a polyester acrylate-based compound, a polyurethane acrylate-based compound, an epoxy acrylate-based compound, and a caprolactone-modified acrylate-based compound. ### Claim 11 (depends on 1) The multi-color ink for 3D printing according to claim 1, wherein at least one of the first ink composition and the second ink composition further comprises a co-solvent. ### Claim 12 (depends on 1) The multi-color ink for 3D printing according to claim 1, wherein at least one of the first colorant and the second colorant comprises a dye, a pigment, a self-dispersing pigment, or a mixture thereof. ### Claim 13 A multi-color ink for 3D printing comprising a plurality of ink compositions, wherein at least a first of the plurality of ink compositions include: at least one photocurable material having an acrylate or methacrylate functional group, a photoinitiator configured to cure the photocurable material, a first colorant, and an anti-intercolor bleed agent that prevents an intercolor bleeding occurring when at least two of the plurality of ink compositions come into contact with each other in the 3D printing; and at least a second of the plurality of ink compositions include a second colorant having an acid moiety reactable with the anti-intercolor bleed agent in the 3D printing. ### Claim 14 (depends on 13) The multi-color ink for 3D printing according to claim 13, wherein the anti-intercolor bleed agent is an amide compound represented by Formula 1: wherein R1 to R4 are, each independently, hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C1-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylsulfoneamide group, a substituted or unsubstituted C6-C20 arylsulfoneamide group, a substituted or unsubstituted C1-C20 acylamino group, a C1-C20 alkylureido group, a C6-C20 arylureido group, a C2-C20 alkoxycarbonyl group, a C2-C20 alkoxycarbonylarnino group, a carbamoyl group, a sulfamoyl group, a sulfo group and a salt thereof, a carboxyl group and a salt thereof, a substituted or unsubstituted C1-C20 hydroxyalkyloxyalkyl group, a substituted or unsubstituted C1-C20 dialkylaminoalkyl group, a substituted or unsubstituted C6-C20 pyridylalkyl group, a substituted or unsubstituted C5-C20 pyridyl group, a substituted or unsubstituted C6-C20 imidazolyl group, a hydrazine group, a hydrazone group, a substituted or unsubstituted C1-C20 pyridylalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 arylalkyl group, a substituted or unsubstituted C6-C20 heteroaryl group, a substituted or unsubstituted C6-C20 heteroarylalkyl group, a substituted or unsubstituted C6-C20 heteroarylalkenyl group, or a substituted or unsubstituted C6-C20 heterocycloalkyl group, and R3 and R4 are connected to each other to form a substituted or unsubstituted C1-C20 alkylene group, wherein at least one of the R1 to R4 comprises an acrylate group or methacrylate group at one end thereof. ### Claim 15 (depends on 13) The multi-color ink for 3D printing according to claim 13, wherein the anti-intercolor bleed agent is a cycloamine compound. ### Claim 16 (depends on 15) The multi-color ink for 3D printing according to claim 15, wherein the cycloamine compound is a pyrrole derivative, a pyridine derivative, a quinoline derivative, an isoquinoline derivative, a pyrrolidine derivative, or a piperidine derivative. ### Claim 17 (depends on 13) The multi-color ink for 3D printing according to claim 13, wherein the photocurable material is a copolymer formed via polymerization of at least two types of acrylate or methacrylate monomers. ### Claim 18 (depends on 13) The multi-color ink for 3D printing according to claim 13, wherein the one or more ink compositions further comprise a solvent. ### Claim 19 (depends on 13) The multi-color ink for 3D printing according to claim 13, wherein the first colorant is a dye, a pigment, a self-dispersing pigment, or a mixture thereof. ### Claim 20 (depends on 13) The multi-color ink for 3D printing according to claim 13, wherein the second colorant is reactable with the anti-intercolor bleed agent to generate aggregates. ### Claim 21 (depends on 20) The multi-color ink for 3D printing according to claim 20, wherein the acid moiety of the second colorant is a carboxylate group, a sulfonate group, a phosphate group, or a salt thereof. ### Claim 22 (depends on 20) The multi-color ink for 3D printing according to claim 20, wherein a content of the second colorant is in the range of about 0.01 to about 1% by weight based on the at least the second of the plurality of ink compositions, and a molar ratio of the anti-intercolor bleed agent to the acid moiety of the second colorant is about 0.5:1 to about 10:1.