# US 11,298,871 B2 · Soluble material for three-dimensional molding

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,298,871 B2
- Document ID: US11298871B2
- Status: Granted
- Kind: B2
- Application number: 16/482,169
- Filed: 2018-01-25
- Published: 2020-02-20
- Granted: 2022-04-12
- Earliest claimed: 2017-01-30
- Assignees: Kao Corporation
- Applicants: Kao Corporation
- Inventors: Jouji Hirai; Tadanori Yoshimura; Tomoya Tsuboi; Hiroki Sawada
- Web page: https://patentgrep.com/patent/US11298871B2

## CPC

- B29C 64/118: using filamentary material being melted, e.g. fused deposition modelling [FDM]
- B33Y 40/00: Auxiliary operations or equipment, e.g. for material handling
- B29C 64/35: Cleaning
- B29C 64/40: Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08L 77/06: Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence)
- C08L 101/00: Compositions of unspecified macromolecular compounds
- B29K 2829/04: PVOH, i.e. polyvinyl alcohol (B29K2831/04 takes precedence)
- B29K 2995/0098: Peel strength; Peelability
- B33Y 10/00: Processes of additive manufacturing
- C08G 63/672: Dicarboxylic acids and dihydroxy compounds
- C08G 63/6856: {Dicarboxylic acids and dihydroxy compounds}
- C08G 63/6886: {Dicarboxylic acids and dihydroxy compounds}
- C08G 69/265: {from at least two different diamines or at least two different dicarboxylic acids}
- C08G 69/42: Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen (C08G69/12, C08G69/32 take precedence)
- 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)
- 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
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

The present invention is a soluble material for three-dimensional modeling that is used as a material of a support material for supporting a three-dimensional object when the three-dimensional object is manufactured by a 3D printer of a fused deposition modeling system and that contains a thermoplastic resin having a hydrophilic group and an organic salt compound represented by a general formula (I) below: (R1—SO3−)nXn+ (I). According to the present invention, it is possible to provide a soluble material for three-dimensional modeling that is used for a support material and that is capable of suppressing the degradation of the modeling accuracy of a three-dimensional object when the three-dimensional object is manufactured by a 3D printer of a fused deposition modeling system, and has a high rate of dissolution to neutral water to be removable speedily from a precursor of the three-dimensional object without use of a strong alkaline aqueous solution.

## Claims

### Claim 1

A soluble material for three-dimensional modeling used as a material of a support material for supporting a three-dimensional object when the three-dimensional object is manufactured by a 3D printer of a fused deposition modeling system, the soluble material comprising
a thermoplastic resin having a hydrophilic group and
an organic salt compound represented by formula (I) below:
(R1—SO3−)nXn+ (I)
where R1 represents a hydrocarbon group that optionally has a substituent group and that has 1 to 30 carbon atoms; n represents a number of 1 or 2; when n is 1, Xn+ represents a sodium ion, a potassium ion, a lithium ion, an ammonium ion, or a phosphonium ion; and when n is 2, Xn+ represents a magnesium ion, a calcium ion, a barium ion, or a zinc ion,
wherein a content of the hydrophilic group in the thermoplastic resin is 0.5 mmol/g or more and 3.0 mmol/g or less.

### Claim 2 (depends on 1)

The soluble material for three-dimensional modeling according to claim 1, wherein the thermoplastic resin is at least one type selected from the group consisting of a polyester resin, a polyamide resin, an acrylic resin, a polyvinyl alcohol resin, a polyvinyl pyrrolidone resin, a polyester amide resin, and a polyurethane resin.

### Claim 3 (depends on 1)

The soluble material for three-dimensional modeling according to claim 1, wherein the hydrophilic group is a sulfonate group.

### Claim 4 (depends on 1)

The soluble material for three-dimensional modeling according to claim 1, having a filament shape.

### Claim 5 (depends on 2)

The soluble material for three-dimensional modeling according to claim 2, wherein the thermoplastic resin is a polyester resin, which has a hydrophilic monomer unit A1 having the hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B1, and a diol monomer unit, and a proportion of the hydrophilic monomer unit A1 to a total of the hydrophilic monomer unit A1 and the hydrophobic dicarboxylic acid monomer unit B1 in the polyester resin is 10 mol % or more and 70 mol % or less.

### Claim 6 (depends on 1)

The soluble material for three-dimensional modeling according to claim 1, wherein a content of the thermoplastic resin in the soluble material for three-dimensional modeling is 70% by mass or more.

### Claim 7 (depends on 6)

The soluble material for three-dimensional modeling according to claim 6, wherein the content of the thermoplastic resin in the soluble material for three-dimensional modeling is 95% by mass or less.

### Claim 8 (depends on 2)

The soluble material for three-dimensional modeling according to claim 2, wherein the thermoplastic resin has a weight-average molecular weight of 3000 or more and 70000 or less.

### Claim 9 (depends on 1)

The soluble material for three-dimensional modeling according to claim 1, wherein n is 1 and Xn+ is the phosphonium ion, which is a tetraalkylphosphonium ion.

### Claim 10 (depends on 1)

The soluble material for three-dimensional modeling according to claim 1, wherein a mass ratio of the organic salt compound to the thermoplastic resin is 0.5 or more and 30 or less.

### Claim 11 (depends on 1)

The soluble material for three-dimensional modeling according to claim 1, wherein a molar ratio of an alkyl sulfonic acid ion (R1—SO3−) in the organic salt compound to the hydrophilic group in the thermoplastic resin is 0.005 or more and 1.0 or less.

### Claim 12 (depends on 1)

A method for manufacturing a three-dimensional object by a fused deposition modeling system, the method comprising:
bringing a precursor of the three-dimensional object that contains the three-dimensional object and a support material into contact with neutral water to remove the support material,
wherein a material of the support material is the soluble material for three-dimensional modeling according to claim 1.

### Claim 13 (depends on 12)

The method according to claim 12, wherein a modeling material that is a material of the three-dimensional object is at least one type selected from the group consisting of an ABS resin, a PP resin, an ASA resin, a PS resin, an HIPS resin, a PVC resin, a polylactic acid resin, a polycarbonate resin, a polyamide resin, a polyetherimide resin, a polyether ether ketone resin, and a polyphenylsulfone resin.

### Claim 14 (depends on 12)

The method according to claim 12, wherein the support material is removed by soaking the precursor of the three-dimensional object in the neutral water and dissolving the support material.