# US 11,078,374 B2 · Active-energy-ray-curable liquid composition, three-dimensional object forming material set, method for producing three-dimensional object, and three-dimensional object producing apparatus > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,078,374 B2 - Document ID: US11078374B2 - Status: Granted - Kind: B2 - Application number: 16/308,709 - Filed: 2017-06-05 - Published: 2019-05-16 - Granted: 2021-08-03 - Earliest claimed: 2016-06-13 - Assignees: Ricoh Company, Ltd. - Applicants: Ricoh Company, Ltd. - Inventors: Hiroyuki Naito; Hiroshi Iwata; Yoshihiro Norikane; Yoshihito Shimada; Kenji Sugiura - Web page: https://patentgrep.com/patent/US11078374B2 ## CPC - 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 - B29C 64/112: using individual droplets, e.g. from jetting heads - B29C 64/124: using layers of liquid which are selectively solidified - B33Y 10/00: Processes of additive manufacturing - B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor - B33Y 70/00: Materials specially adapted for additive manufacturing - C08L 71/02: Polyalkylene oxides - C09D 11/033: characterised by the solvent - C09D 11/107: from unsaturated acids or derivatives thereof - C09D 11/30: Inkjet printing inks - C09D 11/36: based on non-aqueous solvents - 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) - 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 - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Provided is an active-energy-ray-curable liquid composition containing a monomer (A) having a hydrogen-bonding capacity and a solvent (B) having a hydrogen-bonding capacity, wherein the active-energy-ray-curable liquid composition satisfies conditions below, a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray is a solid having a compressive stress of 2.0 kPa or greater when compressed by 1% at 25 degrees C., and the cured product has a water decaying property. ## Claims ### Claim 1 An active-energy-ray-curable liquid composition comprising: a monofunctional monomer (A) having a hydrogen-bonding capacity; and a solvent (B) having a hydrogen-bonding capacity, wherein the solvent (B) comprises at least one selected from the group consisting of a diol that comprises 3 or more but 6 or less carbon atoms, a monoalcohol that comprises 6 or more carbon atoms, a cyclic alcohol that comprises 6 or more carbon atoms, a polypropylene glycol monoether that comprises 6 or more carbon atoms, a carboxylic acid compound, an amine compound, an ester compound, a ketone compound, and a urea compound, and wherein the active-energy-ray-curable liquid composition satisfies conditions below, a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray is a solid having a compressive stress of 2.0 kPa or greater when compressed by 1% at 25 degrees C., and the cured product has a water decaying property. ### Claim 2 An active-energy-ray-curable liquid composition comprising: a monofunctional monomer (A) having a hydrogen-bonding capacity; and a solvent (B) having a hydrogen-bonding capacity, wherein a cured product of the active-energy-ray-curable liquid composition has a water decaying property, wherein the solvent (B) comprises at least one selected from the group consisting of a diol that comprises 3 or more but 6 or less carbon atoms, a monoalcohol that comprises 6 or more carbon atoms, a cyclic alcohol that comprises 6 or more carbon atoms, a polypropylene glycol monoether that comprises 6 or more carbon atoms, a carboxylic acid compound, an amine compound, an ester compound, a ketone compound, and a urea compound, and wherein a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray is a solid having a compressive stress of 0.5 kPa or greater when compressed by 1% at 25 degrees C. ### Claim 3 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, wherein the active-energy-ray-curable liquid composition satisfies at least any one of a condition A to a condition C below as the water decaying property, when a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray and having a depth of 20 mm, a width of 20 mm, and a height of 5 mm is immersed in 20 mL of water and subjected to ultrasonic application at a temperature of either 40 degrees C. or 60 degrees C. for 30 minutes, a residual solid has a volume of less than 30% by volume, when a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray and having a depth of 20 mm, a width of 20 mm, and a height of 5 mm is immersed in 20 mL of water and left to stand still at 25 degrees C. for 1 hour, a residual solid has a volume of 90% by volume or less, when a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray and having a depth of 20 mm, a width of 20 mm, and a height of 5 mm is immersed in 20 mL of water and left to stand still at 25 degrees C. for 1 hour, a residual solid has a size of 1 mm or less in at least one direction or the cured product is completely dissolved. ### Claim 4 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, wherein the active-energy-ray-curable liquid composition satisfies a condition below, a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray and having a depth of 20 mm, a width of 20 mm, and a height of 5 mm has a height change rate of 10% or less between a height of the cured product immediately after cured and a height of the cured product after left to stand still at 40 degrees C. for 24 hours. ### Claim 5 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, further comprising a hydrogen-bondable polymer (C). ### Claim 6 (depends on 5) The active-energy-ray-curable liquid composition according to claim 5, wherein the hydrogen-bondable polymer (C) has a number average molecular weight of 400 or greater. ### Claim 7 (depends on 2) The active-energy-ray-curable liquid composition according to claim 2, wherein the solvent (B) comprises at least one selected from the group consisting of the diol that comprises 3 or more but 6 or less carbon atoms and the monoalcohol that comprises 6 or more carbon atoms. ### Claim 8 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, wherein the solvent (B) comprises at least one selected from the group consisting of the diol that comprises 3 or more but 6 or less carbon atoms and the monoalcohol that comprises 6 or more carbon atoms. ### Claim 9 (depends on 8) The active-energy-ray-curable liquid composition according to claim 8, wherein the diol that comprises 3 or more but 6 or less carbon atoms or the monoalcohol that comprises 6 or more carbon atoms comprises an alcohol having a SP value of 22 MPa1/2 or less, and wherein the active-energy-ray-curable liquid composition further comprises a polyvalent alcohol (D) having a SP value of 30 MPa1/2 or greater. ### Claim 10 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, wherein the monofunctional monomer (A) has a molecular weight of 100 or greater but 500 or less. ### Claim 11 (depends on 10) The active-energy-ray-curable liquid composition according to claim 10, wherein the monofunctional monomer (A) comprises at least any one of acryloylmorpholine and N-hydroxyethylacrylamide. ### Claim 12 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, wherein a ratio by mass (A/B) of a content (% by mass) of the monofunctional monomer (A) to a content (% by mass) of the solvent (B) is 0.20 or greater but 2.5 or less. ### Claim 13 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, wherein a content of the monofunctional monomer (A) is 30% by mass or greater but 60% by mass or less, and wherein a content of the solvent (B) is 10% by mass or greater but 50% by mass or less. ### Claim 14 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, wherein the active-energy-ray-curable liquid composition has a viscosity of 100 mPa·s or less at 25 degrees C. ### Claim 15 A three-dimensional object forming material set comprising: an active-energy-ray-curable liquid composition that comprises a monofunctional monomer (A) having a hydrogen-bonding capacity, and a solvent (B) having a hydrogen-bonding capacity and comprising at least one selected from the group consisting of a diol that comprises 3 or more but 6 or less carbon atoms, a monoalcohol that comprises 6 or more carbon atoms, a cyclic alcohol that comprises 6 or more carbon atoms, a polypropylene glycol monoether that comprises 6 or more carbon atoms, a carboxylic acid compound, an amine compound, an ester compound, a ketone compound, and a urea compound, wherein the active-energy-ray-curable liquid composition satisfies conditions below; and an active-energy-ray-curable liquid composition that does not have a water decaying property, a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray is a solid having a compressive stress of 2.0 kPa or greater when compressed by 1% at 25 degrees C., and the cured product has a water decaying property. ### Claim 16 (depends on 1) A method for producing a three-dimensional object, the method comprising producing a three-dimensional object with the active-energy-ray-curable liquid composition according to claim 1. ### Claim 17 A method for producing a three-dimensional object, the method comprising forming a liquid film with a model material and an active-energy-ray-curable liquid composition that comprises a monofunctional monomer (A) having a hydrogen-bonding capacity and a solvent (B) having a hydrogen-bonding capacity and satisfies conditions below; and curing the liquid film, wherein the method repeats the forming and the curing to form a model part, which is a cured product of the model material, and a support part, which is a cured product of the active-energy-ray-curable liquid composition, wherein after forming the model part and the support part, the method removes the support part by water or water vapor, and wherein the solvent (B) comprises at least one selected from the group consisting of a diol that comprises 3 or more but 6 or less carbon atoms, a monoalcohol that comprises 6 or more carbon atoms, a cyclic alcohol that comprises 6 or more carbon atoms, a polypropylene glycol monoether that comprises 6 or more carbon atoms, a carboxylic acid compound, an amine compound, an ester compound, a ketone compound, and a urea compound, a cured product obtained by irradiating the active-energy-ray-curable liquid composition with 500 mJ/cm2 of an active energy ray is a solid having a compressive stress of 2.0 kPa or greater when compressed by 1% at 25 degrees C., and the cured product has a water decaying property. ### Claim 18 (depends on 1) A three-dimensional object producing apparatus comprising: a container storing the active-energy-ray-curable liquid composition according to claim 1; a liquid film forming unit configured to form a liquid film with the active-energy-ray-curable liquid composition; and a curing unit configured to cure the liquid film. ### Claim 19 (depends on 1) The active-energy-ray-curable liquid composition according to claim 1, wherein a ratio by mass (A/B) of a content (% by mass) of the monofunctional monomer (A) to a content (% by mass) of the solvent (B) is 0.30 or greater but 2.5 or less. ### Claim 20 (depends on 2) The active-energy-ray-curable liquid composition according to claim 2, wherein a ratio by mass (A/B) of a content (% by mass) of the monofunctional monomer (A) to a content (% by mass) of the solvent (B) is 0.30 or greater but 2.5 or less.