# US 11,111,404 B2 · Printing method and printing apparatus > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,111,404 B2 - Document ID: US11111404B2 - Status: Granted - Kind: B2 - Application number: 16/574,428 - Filed: 2019-09-18 - Published: 2020-03-19 - Granted: 2021-09-07 - Earliest claimed: 2018-09-19 - Assignees: Seiko Epson Corporation - Applicants: Seiko Epson Corporation - Inventors: Ippei Okuda - Web page: https://patentgrep.com/patent/US11111404B2 ## CPC - C09D 11/322: Pigment inks - B41J 2/2107: {characterised by the ink properties (supplying ink in a solid state B41J2/17593)} - B41J 2/2114: {Ejecting specialized liquids, e.g. transparent or processing liquids (B41J2/211 takes precedence)} - B41J 2/2117: {Ejecting white liquids} - 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 - B41M 5/0017: {Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying} - B41M 5/0047: {by ink-jet printing} - B41M 5/0064: {on plastics, horn, rubber, or other organic polymers} - B41M 7/0018: {using ink-fixing material, e.g. mordant, precipitating agent, after printing, e.g. by ink-jet printing, coating or spraying} - C08L 91/00: Compositions of oils, fats or waxes; Compositions of derivatives thereof - C08L 91/06: Waxes - 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) - B41J: TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS - 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) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract A printing method includes a white ink application step of ejecting a white ink from a printing head to apply the white ink onto a printing medium, a non-white ink application step of ejecting a non-white ink containing a non-white coloring material from a printing head to apply the non-white ink onto the printing medium, and a treatment liquid application step of applying a treatment liquid containing a flocculant onto the printing medium. The white ink contains a white pigment and inorganic fine particles having a smaller volume average particle size than the white pigment. ## Claims ### Claim 1 A printing method comprising: a white ink application step of ejecting a white ink from a printing head to apply the white ink onto a printing medium; a non-white ink application step of ejecting a non-white ink containing a non-white coloring material from a printing head to apply the non-white ink onto the printing medium; and a treatment liquid application step of applying a treatment liquid containing a flocculant onto the printing medium, wherein the white ink contains a titanium oxide white pigment and inorganic fine particles having a smaller volume average particle size than the white pigment, the inorganic fine particles being selected from the group consisting of silica, alumina, zirconia, and zinc oxide. ### Claim 2 (depends on 1) The printing method according to claim 1, wherein the inorganic fine particles are transparent. ### Claim 3 (depends on 1) The printing method according to claim 1, wherein the white pigment has a volume average particle size of from 150.0 nm to 400.0 nm, and the inorganic particles have a volume average particle size of from 10.0 nm to 100.0 nm. ### Claim 4 (depends on 1) The printing method according to claim 1, wherein the white ink containing 1.0 parts by mass to 20.0 parts by mass of the inorganic fine particles relative to 100 parts by mass of the white pigment. ### Claim 5 (depends on 1) The printing method according to claim 1, wherein the treatment liquid contains a cationic polymer as the flocculant. ### Claim 6 (depends on 1) The printing method according to claim 1, wherein the white ink, the non-white ink, a mixture of the white ink and the treatment liquid, and a mixture of the non-white ink and the treatment liquid have respective viscosities, and the ratio of the viscosity of the mixture of the white ink and the treatment liquid to the viscosity of the white ink has a difference of 5.0 or less from the ratio of the viscosity of the mixture of the non-white ink and the treatment liquid to the viscosity of the non-white ink. ### Claim 7 (depends on 1) The printing method according to claim 1, wherein at least one of the white ink and the non-white ink contains a wax. ### Claim 8 (depends on 1) The printing method according to claim 1, wherein the printing medium includes a printing region having an area onto which treatment liquid is applied in a proportion of from 5.0% by mass to 50.0% by mass relative to the total mass of the white ink and the non-white ink applied onto the area. ### Claim 9 (depends on 1) The printing method according to claim 1, wherein the treatment application step is performed before the white ink application step and the non-white ink application step. ### Claim 10 (depends on 1) The printing method according to claim 1, wherein the white ink application step is performed before the non-white ink application step. ### Claim 11 (depends on 1) The printing method according to claim 1, further comprising a post-application heating step of heating the printing medium after the treatment liquid application step, the white ink application step, and the non-white ink application step. ### Claim 12 (depends on 1) The printing method according to claim 1, wherein one of the white ink application step and the non-white ink application step is a subsequent ink application step performed after the other, and a percentage of evaporable constituents in the treatment liquid and ink that are applied before the subsequent ink application step are evaporated, the percentage being from 50.0% by mass to 90.0% by mass at the time when the subsequent ink application step is started. ### Claim 13 (depends on 1) A printing apparatus configured to perform the printing method as set forth in claim 1.