# US 12,179,424 B2 · Three-dimensional printing with secondary antioxidants

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- Number: US 12,179,424 B2
- Document ID: US12179424B2
- Status: Granted
- Kind: B2
- Application number: 17/788,350
- Filed: 2020-01-09
- Published: 2023-02-16
- Granted: 2024-12-31
- Earliest claimed: 2020-01-09
- Assignees: Hewlett-Packard Development Company, L.P.
- Applicants: Hewlett-Packard Development Company, L.P.
- Inventors: Emre Hiro Discekici; Graciela Emma Negri Jimenez; Shannon Reuben Woodruff; Jason Christopher Butler
- Web page: https://patentgrep.com/patent/US12179424B2

## CPC

- 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 10/00: Processes of additive manufacturing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- 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

## Abstract

The present disclosure describes multi-fluid kits for three-dimensional printing, three-dimensional printing kits, and methods of making three-dimensional printed objects. In one example, a multi-fluid kit for three-dimensional printing can include a fusing agent and an antioxidant agent. The fusing agent can include water and an electromagnetic radiation absorber. The electromagnetic radiation absorber can absorb radiation energy and convert the radiation energy to heat. The antioxidant agent can include water and a dispersion of a secondary antioxidant.

## Claims

### Claim 1

A multi-fluid kit for three-dimensional printing comprising:
a fusing agent comprising water and an electromagnetic radiation absorber, wherein the electromagnetic radiation absorber absorbs radiation energy and converts the radiation energy to heat; and
an antioxidant agent comprising water and a dispersion of particles of a secondary antioxidant having an average particle size ranging from about 10 nm to about 800 nm.

### Claim 2 (depends on 1)

The multi-fluid kit of claim 1, wherein the secondary antioxidant comprises a thioether, a thioester, a phosphite, or a combination thereof.

### Claim 3 (depends on 1)

The multi-fluid kit of claim 1, wherein the secondary antioxidant comprises a dilauryl ester of 3,3′-thiodipropionic acid; pentaerythritol tetrakis (beta-laurylthiopropionate); thiobis [2-(1,1-dimethylethyl)-5-methyl-4,1-phenylene]bis[3-(dodecylthio)propionate; tris (2,4-di-tert-butylphenyl) phosphite; 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] undecane, or a combination thereof.

### Claim 4 (depends on 1)

The multi-fluid kit of claim 1, wherein the secondary antioxidant has a melting point ranging from about 30° C. to about 150° C.

### Claim 5 (depends on 1)

The multi-fluid kit of claim 1, wherein the secondary antioxidant is present in the antioxidant agent in an amount ranging from about 0.5 wt % to about 15 wt % with respect to a total weight of the antioxidant agent.

### Claim 6 (depends on 1)

The multi-fluid kit of claim 1, wherein the fusing agent is a colorless fusing agent or a low tint fusing agent.

### Claim 7 (depends on 3)

The multi-fluid kit of claim 3, wherein the secondary antioxidant consists of one of the dilauryl ester of 3,3′-thiodipropionic acid, the pentaerythritol tetrakis(beta-laurylthiopropionate), the thiobis[2-(1,1-dimethylethyl)-5-methyl-4,1-phenylene]bis[3-(dodecylthio) propionate, the tris(2,4-di-tert-butylphenyl) phosphite, or the 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] undecane.

### Claim 8

A three-dimensional printing kit comprising:
a powder bed material comprising polymer particles;
a fusing agent to selectively apply to the powder bed material, the fusing agent comprising water and an electromagnetic radiation absorber, wherein the electromagnetic radiation absorber absorbs radiation energy and converts the radiation energy to heat; and
an antioxidant agent to selectively apply to the powder bed material, the antioxidant agent comprising water and a dispersion of particles of a secondary antioxidant having an average particle size ranging from about 10 nm to about 800 nm.

### Claim 9 (depends on 8)

The three-dimensional printing kit of claim 8, wherein the polymer particles comprise polyamide 6, polyamide 9, polyamide 11, polyamide 12, polyamide 66, polyamide 612, thermoplastic polyamide, polyamide copolymer, polyethylene, thermoplastic polyurethane, polypropylene, polyester, polycarbonate, polyether ketone, polyacrylate, polystyrene, polyvinylidene fluoride, polyvinylidene fluoride copolymer, poly (vinylidene fluoride-trifluoroethylene), poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene), wax, or a combination thereof.

### Claim 10 (depends on 8)

The three-dimensional printing kit of claim 8, wherein the secondary antioxidant comprises a thioether, a thioester, a phosphite, or a combination thereof, and wherein the secondary antioxidant is present in the antioxidant agent in an amount ranging from about 0.5 wt % to about 15 wt % with respect to a total weight of the antioxidant agent.

### Claim 11 (depends on 8)

The three-dimensional printing kit of claim 8, wherein the secondary antioxidant has a melting point ranging from about 30° C. to about 150° C.

### Claim 12 (depends on 8)

The three-dimensional printing kit of claim 8, wherein the secondary antioxidant consists of one of a dilauryl ester of 3,3′-thiodipropionic acid, pentaerythritol tetrakis(beta-laurylthiopropionate), thiobis[2-(1,1-dimethylethyl)-5-methyl-4,1-phenylene]bis[3-(dodecylthio) propionate, tris(2,4-di-tert-butylphenyl) phosphite, or 3,9-bis (octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] undecane.

### Claim 13

A method of making a three-dimensional printed object comprising:
iteratively applying individual build material layers of polymer particles to a powder bed;
based on a three-dimensional object model, selectively jetting a fusing agent onto the individual build material layers, wherein the fusing agent comprises water and an electromagnetic radiation absorber;
based on the three-dimensional object model, selectively jetting an antioxidant agent onto the individual build material layers, wherein the antioxidant agent comprises water and a dispersion of particles of a secondary antioxidant having an average particle size ranging from about 10 nm to about 800 nm; and
exposing the powder bed to energy to selectively fuse the polymer particles in contact with the electromagnetic radiation absorber to form a fused polymer matrix at individual build material layers.

### Claim 14 (depends on 13)

The method of claim 13, further comprising forming the dispersion of the secondary antioxidant by:
melting the secondary antioxidant;
emulsifying the melted secondary antioxidant with water;
cooling the emulsification below a melting point of the secondary antioxidant to form dispersed secondary antioxidant particles; and
milling the dispersed secondary antioxidant particles to reduce an average particle size of the secondary antioxidant particles.

### Claim 15 (depends on 13)

The method of claim 13, wherein the secondary antioxidant comprises a thioether, a thioester, a phosphite, or a combination thereof, and wherein the secondary antioxidant is present in the antioxidant agent in an amount ranging from about 0.5 wt % to about 15 wt % with respect to a total weight of the antioxidant agent.

### Claim 16 (depends on 13)

The method of claim 13, wherein the secondary antioxidant consists of one of a dilauryl ester of 3,3′-thiodipropionic acid, pentaerythritol tetrakis(beta-laurylthiopropionate), thiobis[2-(1,1-dimethylethyl)-5-methyl-4,1-phenylene]bis[3-(dodecylthio) propionate, tris(2,4-di-tert-butylphenyl) phosphite, or 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] undecane.