Hydrogel three-dimensional printing with self-crosslinking particulate build material

Patent metadata

Field	Value
Publication number	US-12441889-B2
Application number	US-202017912617-A
Country	US
Kind code	B2
Filing date	Apr 10, 2020
Priority date	Apr 10, 2020
Publication date	Oct 14, 2025
Grant date	Oct 14, 2025

Abstract

This disclosure describes hydrogel three-dimensional printing kits, methods of three-dimensional printing hydrogels, and hydrogel three-dimensional printing systems. In one example, a hydrogel three-dimensional printing kit can include a particulate build material and an aqueous agent. The particulate build material can include from about 90 wt % to 100 wt % of a mixture of a powdered polyhydroxylated swellable polymer dry blended with powdered water-soluble crosslinker that is reactive with hydroxyl groups of the polyhydroxylated swellable polymer to crosslink the polyhydroxylated swellable polymer. The aqueous agent can include water and an organic co-solvent, and the aqueous agent may not include the crosslinker.

First claim

What is claimed is:

1. A three-dimensional printing kit, comprising:
particulate build material comprising from about 90 wt % to 100 wt % of a mixture of a powdered polyhydroxylated swellable polymer dry blended with a powdered water-soluble crosslinker that is reactive with hydroxyl groups of the polyhydroxylated swellable polymer to crosslink the polyhydroxylated swellable polymer, wherein;
the polyhydroxylated swellable polymer is selected from the group consisting of polyvinyl alcohol, gelatin, chitosan, hyaluronic acid, poly(2-hydroxyethyl acrylate), poly(2-hydroxyethyl methacrylate), poly(methacrylic acid), poly(N,N-dimethylacrylamide), poly(N,N-diethylacrylamide), poly(N-isopropylacrylamide), and a combination thereof;
the water-soluble crosslinker is selected from the group consisting of sodium tetraborate, boric acid, cationic barium, and a combination thereof; and
the water-soluble crosslinker is present in the particulate build material in an amount ranging from about 1 wt % to about 50 wt %; and

an aqueous agent comprising water and an organic co-solvent, wherein the aqueous agent does not include the water-soluble crosslinker.

2. The three-dimensional printing kit of claim 1 , wherein the polyhydroxylated swellable polymer is polyvinyl alcohol, and wherein the polyvinyl alcohol has a weight average molecular weight ranging from about 500 Mw to about 500,000 Mw.

3. The three-dimensional printing kit of claim 1 , wherein the water-soluble crosslinker is reactive to form hydrogen bonds with the hydroxyl groups of the polyhydroxylated swellable polymer.

4. The three-dimensional printing kit of claim 1 , wherein the aqueous agent consists of water, the organic co-solvent, and optionally a surfactant.

5. The three-dimensional printing kit of claim 1 , wherein the particulate build material consists of the powdered polyhydroxylated swellable polymer and the powdered water-soluble crosslinker, and wherein the water-soluble crosslinker is present in the particulate build material in an amount ranging from about 10 wt % to about 30 wt %.

6. The three-dimensional printing kit of claim 5 , wherein the powdered polyhydroxylated swellable polymer is polyvinyl alcohol powder and the powdered water-soluble crosslinker is sodium tetraborate powder.

7. The three-dimensional printing kit of claim 1 , wherein the water-soluble crosslinker is selected from the group consisting of sodium tetraborate, boric acid, and a combination thereof.

8. The three-dimensional printing kit of claim 1 , wherein the polyhydroxylated swellable polymer is polyvinyl alcohol, and wherein the polyvinyl alcohol has a weight average molecular weight ranging from about 20,000 Mw to about 200,000 Mw.

9. A hydrogel-three-dimensional printing system, comprising:
the three-dimensional printing kit of claim 1 ; and
a fluid applicator fluidly coupled or coupleable to the aqueous agent, wherein the fluid applicator is directable to iteratively apply the aqueous agent to layers of the particulate build material.

10. A method of three-dimensional printing, the method comprising:
iteratively applying individual layers of a particulate build material to a powder bed, wherein the particulate build material comprises from about 90 wt % to 100 wt % of a mixture of a powdered polyhydroxylated swellable polymer dry blended with powdered water-soluble crosslinker that is reactive with hydroxyl groups of the polyhydroxylated swellable polymer to crosslink the polyhydroxylated swellable polymer, wherein:
the polyhydroxylated swellable polymer is selected from the group consisting of polyvinyl alcohol, cellulose, gelatin, chitosan, hyaluronic acid, poly(2-hydroxyethyl acrylate), poly(2-hydroxyethyl methacrylate), poly(acrylic acid), poly(methacrylic acid), poly(N,N-dimethylacrylamide), poly(N,N-diethylacrylamide), poly(N-isopropylacrylamide), and a combination thereof;
the water-soluble crosslinker is selected from the group consisting of sodium tetraborate, boric acid, cationic barium, and a combination thereof; and
the water-soluble crosslinker is present in the particulate build material in an amount ranging from about 1 wt % to about 50 wt %; and

based on a three-dimensional object model, iteratively and selectively applying an aqueous agent onto the individual layers, wherein the aqueous agent comprises water and an organic co-solvent and does not include the water-soluble crosslinker, thereby forming a three-dimensional printed hydrogel.

11. The method of claim 10 , wherein the particulate build material is maintained at a temperature ranging from about 0° C. to about 75° C.

12. The method of claim 10 , wherein the aqueous agent is applied onto the individual layers at an agent density so that the individual layers include from about 50 wt % to about 95 wt % of the water based on a total weight of individual layer and aqueous agent applied.

13. A three-dimensional printing kit, comprising:
a build material powder consisting of:
a polyvinyl alcohol powder; and
from about 20 wt % to about 30 wt % of a powdered, water-soluble crosslinker dry blended with the polyvinyl alcohol powder, wherein the powdered, water-soluble crosslinker is reactive with hydroxyl groups of the polyvinyl alcohol powder and is selected from the group consisting of sodium tetraborate, boric acid, cationic barium, and a combination thereof; and

an aqueous agent comprising water and an organic co-solvent.

Assignees

• Peridot Print Llc

Inventors

• Discekici Emre Hiro
• Woodruff Shannon Reuben
• Wright Jacob
• Fleischmann Carolin
• Negri Jimenez Graciela Emma

Classifications

• B29K2995/0088

  Molecular weight · CPC title

• B29K2105/24

  crosslinked or vulcanised · CPC title

• B29K2105/0061

  Gel or sol · CPC title

• B29K2029/04

  PVOH, i.e. polyvinyl alcohol (B29K2031/04 takes precedence) · CPC title

• B29C64/165

  using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber · CPC title