# US 10,767,071 B2 · Liquid material for forming three-dimensional object and material set for forming three-dimensional object, three-dimensional object producing method and three-dimensional object producing apparatus

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- Number: US 10,767,071 B2
- Document ID: US10767071B2
- Status: Granted
- Kind: B2
- Application number: 15/041,761
- Filed: 2016-02-11
- Published: 2016-09-22
- Granted: 2020-09-08
- Earliest claimed: 2015-03-19
- Assignees: Ricoh Company, Ltd.
- Applicants: Keiko Osaka; Takeo Yamaguchi
- Inventors: Keiko Osaka; Takeo Yamaguchi
- Web page: https://patentgrep.com/patent/US10767071B2

## CPC

- C09J 139/06: Homopolymers or copolymers of N-vinyl-pyrrolidones
- B22F 1/102: Metallic powder coated with organic material
- B22F 3/003: {Apparatus, e.g. furnaces (in general F27B)}
- B22F 10/14: by jetting of binder onto a bed of metal powder
- B29C 64/00: 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
- B29C 64/165: using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- C04B 35/486: Fine ceramics
- C04B 35/64: Burning or sintering processes (C04B33/32 takes precedence {; powder metallurgy B22F})
- C08K 3/08: Metals
- C08K 5/053: Polyhydroxylic alcohols
- C08K 5/17: Amines; Quaternary ammonium compounds
- C08K 5/51: Phosphorus bound to oxygen
- C08L 29/04: Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
- C08L 39/06: Homopolymers or copolymers of N-vinyl-pyrrolidones
- C08L 71/02: Polyalkylene oxides
- C09D 129/04: Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
- C09D 139/06: Homopolymers or copolymers of N-vinyl-pyrrolidones
- C09D 171/02: Polyalkylene oxides
- C09J 171/02: Polyalkylene oxides
- B22F 2998/10: Processes characterised by the sequence of their steps
- B33Y 10/00: Processes of additive manufacturing
- B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor
- C08K 5/175: {containing COOH-groups; Esters or salts thereof}
- C08K 5/5317: Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08L 2312/00: Crosslinking
- Y02P 10/25: Process efficiency
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Provided is a liquid material for forming a three-dimensional object used for forming a three-dimensional object made of a powder material for forming a three-dimensional object containing an organic material and a base material, wherein the liquid material contains a cross-linking agent cross-linkable with the organic material and a water-soluble resin having a weight average molecular weight of greater than or equal to 50,000.

## Claims

### Claim 1

A liquid consisting of:
a solvent;
a cross-linking agent which comprises a metal salt;
a water-soluble resin having a weight average molecular weight of greater than or equal to 50,000;
optionally, a stabilizing agent which is at least one selected from the group consisting of a compound that comprises an amino group, a compound that comprises a phosphono group, a gluconic acid, and a salt of the gluconic acid; and
optionally, at least one selected from the group consisting of a surfactant, a defoamer, a pH adjustor, an antiseptic/fungicide, a chelate agent, and an anti-rust agent,
wherein the liquid is used for forming a three-dimensional object made of a powder that comprises an organic material and a base material,
wherein the liquid is capable of dissolving the organic material, and
wherein the cross-linking agent is cross-linkable with the organic material.

### Claim 2 (depends on 1)

The liquid according to claim 1,
wherein the water-soluble resin has a weight average molecular weight of greater than or equal to 700,000.

### Claim 3 (depends on 1)

The liquid according to claim 1,
wherein the water-soluble resin comprises polyvinyl pyrrolidone.

### Claim 4 (depends on 1)

The liquid according to claim 1,
wherein the cross-linking agent comprises a zirconium compound.

### Claim 5 (depends on 1)

The liquid according to claim 1, further comprising the stabilizing agent.

### Claim 6 (depends on 5)

The liquid according to claim 5,
wherein the compound that comprises an amino group comprises a polyvalent alcohol that comprises an amino group, an amine compound that comprises a hydroxyl group, or a chelate agent that comprises an amino group.

### Claim 7 (depends on 1)

The liquid according to claim 1,
wherein the solvent comprises a water-soluble organic solvent having a vapor pressure of higher than or equal to 10 mmHg at 100° C.

### Claim 8

A material set for forming a three-dimensional object, comprising:
a powder for forming a three-dimensional object, where the powder comprises an organic material and a base material; and
a liquid for forming a three-dimensional object, where the liquid consists of:
a solvent;
a cross-linking agent cross-linkable with the organic material, the cross-linkable agent comprising a metal salt;
a water-soluble resin having a weight average molecular weight of greater than or equal to 50,000;
optionally, a stabilizing agent which is at least one selected from the group consisting of a compound that comprises an amino group, a compound that comprises a phosphono group, a gluconic acid, and a salt of the gluconic acid; and
optionally, at least one selected from the group consisting of a surfactant, a defoamer, a pH adjustor, an antiseptic/fungicide, a chelate agent, and an anti-rust agent,
wherein the liquid is capable of dissolving the organic material.

### Claim 9 (depends on 8)

The material set for forming a three-dimensional object according to claim 8,
wherein the base material is coated with the organic material.

### Claim 10 (depends on 8)

The material set for forming a three-dimensional object according to claim 8,
wherein the base material is a base material non-reactive with the liquid.

### Claim 11 (depends on 8)

The material set for forming a three-dimensional object according to claim 8,
wherein the base material comprises at least one of a metal and a ceramic.

### Claim 12 (depends on 8)

The material set for forming a three-dimensional object according to claim 8,
wherein the organic material comprises a water-soluble resin.

### Claim 13 (depends on 12)

The material set for forming a three-dimensional object according to claim 12,
wherein the water-soluble resin comprises a modified polyvinyl alcohol resin.

### Claim 14

A three-dimensional object producing method comprising:
forming a layer of a powder for forming a three-dimensional object, where the powder comprises an organic material and a base material; and
delivering a liquid for forming a three-dimensional object to a predetermined region of the layer of the powder,
wherein the three-dimensional object producing method repeats the forming and the delivering to produce a three-dimensional object,
wherein the liquid consists of:
a solvent;
a cross-linking agent cross-linkable with the organic material, the cross-linkable agent comprising a metal salt;
a water-soluble resin having a weight average molecular weight of greater than or equal to 50,000;
optionally, a stabilizing agent which is at least one selected from the group consisting of a compound that comprises an amino group, a compound that comprises a phosphono group, a gluconic acid, and a salt of the gluconic acid; and
optionally, at least one selected from the group consisting of a surfactant, a defoamer, a pH adjustor, an antiseptic/fungicide, a chelate agent, and an anti-rust agent, and
wherein the liquid is capable of dissolving the organic material.

### Claim 15 (depends on 14)

The three-dimensional object producing method according to claim 14, further comprising
sintering the three-dimensional object produced through repetition of the forming and the delivering.