# US 12,179,423 B2 · Three-dimensional printing with chemical functionalization agents

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- Number: US 12,179,423 B2
- Document ID: US12179423B2
- Status: Granted
- Kind: B2
- Application number: 17/777,776
- Filed: 2019-12-11
- Published: 2023-02-02
- Granted: 2024-12-31
- Earliest claimed: 2019-12-11
- 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
- Web page: https://patentgrep.com/patent/US12179423B2

## 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
- C09D 11/54: Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
- B29K 2077/00: Use of {PA, i.e.} polyamides, e.g. polyesteramides {or derivatives thereof}, as moulding material
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- C08G 73/0206: {Polyalkylene(poly)amines}
- 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
- 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)
- 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 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 a chemical functionalization 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 chemical functionalization agent can include water and an amine-containing polymer. The amine-containing polymer can be a branched or unbranched polymer that includes a polymer backbone and multiple pendant side chains. The individual side chains can include —NH2, —NH—, or a combination thereof.

## 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;
a chemical functionalization agent comprising water and an amine-containing polymer, wherein the amine-containing polymer is a branched or unbranched polymer comprising a polymer backbone and multiple pendant side chains, wherein individual side chains comprise-NH2, —NH—, or a combination thereof; and
a coloring agent comprising an amine-reactive compound to react with the —NH2 or —NH— of the amine-containing polymer.

### Claim 2 (depends on 1)

The multi-fluid kit of claim 1, wherein the amine-containing polymer has a weight average molecular weight from about 100 Mw to about 10,000 Mw.

### Claim 3 (depends on 1)

The multi-fluid kit of claim 1, wherein the amine-containing polymer is polyethyleneimine or poly(2-aminoethyl methacrylate).

### Claim 4 (depends on 1)

The multi-fluid kit of claim 1, wherein the amine-containing polymer is present in an amount ranging from about 5 wt % to about 20 wt %, with respect to a total weight of the chemical functionalization agent.

### Claim 5 (depends on 1)

The multi-fluid kit of claim 1, wherein the chemical functionalization agent further includes from about 2 wt % to about 10 wt % of an organic co-solvent, based on a total weight of the chemical functionalization agent.

### Claim 6 (depends on 1)

The multi-fluid kit of claim 1, wherein the amine-reactive compound is a dye precursor to covalently attach to the —NH2 or —NH— to form a colored dye.

### Claim 7

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;
a chemical functionalization agent to selectively apply to the powder bed material, the chemical functionalization agent comprising water and an amine-containing polymer, wherein the amine-containing polymer is a branched or unbranched polymer comprising a polymer backbone having multiple pendant side chains, wherein individual side chains comprise —NH2, —NH—, or a combination thereof; and
a coloring agent comprising an amine-reactive compound to react with the —NH2 or —NH— of the amine-containing polymer.

### Claim 8 (depends on 7)

The three-dimensional printing kit of claim 7, wherein the amine-containing polymer is polyethyleneimine or poly(2-aminoethyl methacrylate).

### Claim 9 (depends on 7)

The three-dimensional printing kit of claim 7, wherein the chemical functionalization agent comprises from about 5 wt % to about 20 wt % of the amine-containing polymer, and from about 2 wt % to about 10 wt % of an organic co-solvent.

### Claim 10

A method of making a three-dimensional printed object, the method comprising:
iteratively applying individual build material layers of polymer particles to a powder bed;
based on a three-dimensional object model, selectively applying 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 applying a chemical functionalization agent onto the individual build material layers, wherein the chemical functionalization agent comprises water and an amine-containing polymer, wherein the amine-containing polymer is a branched or unbranched polymer comprising a polymer backbone having multiple pendant side chains, wherein individual side chains comprise —NH2, —NH—, or a combination thereof;
exposing the powder bed to energy to selectively fuse the polymer particles in contact with the electromagnetic radiation absorber to form fused polymer matrix layers from individual build material layers to thereby form the three-dimensional printed object, wherein the three-dimensional printed object includes a first surface portion comprising —NH2, —NH—, or a combination thereof and a second surface portion without the —NH2, —NH—, or the combination thereof; and
applying a coloring agent comprising an amine-reactive compound to the three-dimensional printed object such that the amine-reactive compound attaches to the —NH2, —NH—, or the combination thereof in the first surface portion.

### Claim 11 (depends on 10)

The method of claim 10, wherein the amine-reactive compound is a dye precursor that covalently attaches to the —NH2, —NH—, or the combination thereof to form a colored dye, such that the first surface portion becomes colored while the second surface portion remains uncolored.