# US 10,246,799 B2 · Polylactic acid resin composition for 3D printing > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,246,799 B2 - Document ID: US10246799B2 - Status: Granted - Kind: B2 - Application number: 15/504,286 - Filed: 2015-08-21 - Published: 2017-08-17 - Granted: 2019-04-02 - Earliest claimed: 2014-09-17 - Assignees: SK Chemicals Co., Ltd. - Applicants: SK Chemicals Co., Ltd. - Inventors: Min-young Kim; Jong Ryang Kim; Tae-Young Kim; Sung-wan Jeon - Web page: https://patentgrep.com/patent/US10246799B2 ## CPC - D01F 6/70: from polyurethanes - B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material - B33Y 10/00: Processes of additive manufacturing - B33Y 70/00: Materials specially adapted for additive manufacturing - C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step - C08G 18/246: {containing also tin-carbon bonds} - C08G 18/348: {Hydroxycarboxylic acids} - C08G 18/428: {Lactides} - C08G 18/48: Polyethers - C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)} - C08G 18/73: acyclic - C08G 18/831: {by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides (by aldehydes C08G18/84, by peroxides C08G18/86)} - C08G 63/06: derived from hydroxycarboxylic acids - C08G 63/08: Lactones or lactides - C08G 71/04: Polyurethanes - B29K 2067/046: {PLA, i.e. polylactic acid or polylactide} - D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS - 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) - 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 - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS ## Abstract A polylactic acid resin composition, which comprises: a hard segment containing a polylactic acid repeat unit; and a soft segment containing a polyurethane polyol repeat unit in which polyether-based polyol repeat units are linearly connected to each other via a urethane linkage, can be processed at low temperatures and at high rates, has a high solidification rate, and is eco-friendly, due to a low melting point thereof, and thus is useful for 3D printing. ## Claims ### Claim 1 A polylactic acid resin composition for three-dimensional (3D) printing, comprising: (a) a hard segment comprising a polylactic acid repeat unit represented by Formula 1; and (b) a soft segment comprising a polyurethane polyol repeat unit in which polyether-based polyol repeat units represented by Formula 2 are linearly linked via urethane bonds, wherein the composition has a melting temperature of 170° C. or less, a glass transition temperature of 55° C. or less, a number-average molecular weight of 50,000 or more, and a viscosity of 1,000 Pas or less when measured at a temperature of 200° C. and at a shear rate of 100 s−1: wherein n in Formula 1 is an integer ranging from 700 to 5,000; and, in Formula 2, A is a linear or branched alkylene group having 2 to 5 carbon atoms, and m is an integer ranging from 10 to 100. ### Claim 2 (depends on 1) The composition according to claim 1, wherein the composition comprises (a) the hard segment in an amount of 65 to 95% by weight and (b) the soft segment in an amount of 5 to 35% by weight, relative to the total weight of the composition. ### Claim 3 (depends on 1) The composition according to claim 1, wherein the polyether-based polyol repeat unit is at least one selected from the group consisting of a polyetherglycol (PEG) repeat unit, a poly(1,2-propyleneglycol) repeat unit, a poly(1,3-propanediol) repeat unit, a polytetramethyleneglycol repeat unit, a polybutyleneglycol repeat unit, a repeat unit of a polyol formed by copolymerization of propylene oxide and tetrahydrofurane, a repeat unit of a polyol formed by copolymerization of ethylene oxide and tetrahydrofurane, and a repeat unit of a polyol formed by copolymerization of ethylene oxide and propylene oxide. ### Claim 4 (depends on 1) The composition according to claim 1, wherein the urethane bond is formed by a reaction between a terminal hydroxyl group in the polyether-based polyol repeat unit and a diisocyanate compound. ### Claim 5 (depends on 4) The composition according to claim 4, wherein the diisocyanate compound is at least one selected from the group consisting of 1,6-hexamethylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-bisphenylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. ### Claim 6 (depends on 1) The composition according to claim 1, further comprising at least one additive selected from the group consisting of a hindered phenol antioxidant, an amine antioxidant, a thio antioxidant, a phosphite antioxidant, silica, colloidal silica, alumina, alumina sol, talc, mica, and calcium carbonate. ### Claim 7 (depends on 1) A polylactic acid filament for 3D printing, comprising the polylactic acid resin composition according to claim 1. ### Claim 8 A method of 3D printing using a polylactic acid resin composition, which comprises: (a) a hard segment comprising a polylactic acid repeat unit represented by Formula 1; and (b) a soft segment comprising a polyurethane polyol repeat unit in which polyether-based polyol repeat units represented by Formula 2 are linearly linked via urethane bonds, wherein the composition has a melting temperature of 170° C. or less, a glass transition temperature of 55° C. or less, a number-average molecular weight of 50,000 or more, and a viscosity of 1,000 Pas or less when measured at a temperature of 200° C. and at a shear rate of 100 s−1: wherein n in Formula 1 is an integer ranging from 700 to 5,000; and, in Formula 2, A is a linear or branched alkylene group having 2 to 5 carbon atoms, and m is an integer ranging from 10 to 100.