# US 11,993,010 B2 · Three-dimensional printing

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- Number: US 11,993,010 B2
- Document ID: US11993010B2
- Status: Granted
- Kind: B2
- Application number: 17/298,642
- Filed: 2019-09-19
- Published: 2022-05-19
- Granted: 2024-05-28
- Earliest claimed: 2019-08-08
- Assignees: Hewlett-Packard Development Company, L.P.
- Applicants: Hewlett-Packard Development Company, L.P.
- Inventors: Graciela E. Negri Jimenez; Emre Hiro Discekici; Shannon Reuben Woodruff
- Web page: https://patentgrep.com/patent/US11993010B2

## CPC

- B29C 64/188: involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control (surface shaping B29C59/00; after-treatment of articles without altering their shape B29C71/00)
- B29C 64/30: Auxiliary operations or equipment
- 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 40/20: Post-treatment, e.g. curing, coating or polishing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08L 83/04: Polysiloxanes
- C09D 7/61: inorganic
- C09D 7/63: organic
- C09D 11/033: characterised by the solvent
- C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
- C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D 11/322: Pigment inks
- C09D 11/324: containing carbon black
- C09D 11/328: characterised by dyes
- B29K 2083/00: Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
- B29K 2995/0093: hydrophobic
- C08G 77/18: to alkoxy or aryloxy groups
- 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)
- 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

In an example of a method for three-dimensional (3D) printing, a polymeric build material is applied to form a build material layer. A fusing agent is selectively applied, based on a 3D object model, onto the build material layer to form a patterned portion. A hydrophobic agent is selectively applied, based on the 3D object model, onto at least a portion of the patterned portion. The hydrophobic agent includes a lipophilic phase discontinuously dispersed within an aqueous phase by a surfactant, wherein the lipophilic phase includes an organosilane having a central silicon atom coupled to a C6 to C24 aliphatic or alicyclic hydrocarbon and multiple hydrolyzable groups, wherein the organosilane is present in the hydrophobic agent at from about 1 wt % to about 20 wt %. The build material layer is exposed to energy to selectively coalesce the patterned portion and form a 3D object layer having a hydrophobic portion.

## Claims

### Claim 1

A method for three-dimensional (3D) printing, comprising:
applying a polymeric build material to form a build material layer;
based on a 3D object model, selectively applying a fusing agent onto the build material layer, thereby forming a patterned portion;
based on the 3D object model, selectively applying a hydrophobic agent onto at least a portion of the patterned portion, wherein the hydrophobic agent comprises a lipophilic phase discontinuously dispersed within an aqueous phase by a surfactant, wherein the lipophilic phase includes an organosilane having a central silicon atom coupled to a C6 to C24 aliphatic or alicyclic hydrocarbon and multiple hydrolyzable groups, wherein the organosilane is present in the hydrophobic agent at from about 1 wt % to about 20 wt %; and
exposing the build material layer to energy to selectively coalesce the patterned portion and form a 3D object layer having a hydrophobic portion.

### Claim 2 (depends on 1)

The method as defined in claim 1 wherein a weight ratio of the selectively applied organosilane in the hydrophobic agent to an energy absorber in the selectively applied fusing agent ranges from about 0.1 to about 5.

### Claim 3 (depends on 1)

The method as defined in claim 1 wherein:
the 3D object layer having the hydrophobic portion is an outer layer of a 3D printed object;
the fusing agent is a primer fusing agent; and
prior to forming the outer layer, the method further comprises forming a core of the 3D printed object by:
iteratively applying the polymeric build material to form respective build material layers;
selectively applying a core fusing agent on the respective build material layers to form respective patterned portions; and
exposing the respective build material layers to energy.

### Claim 4 (depends on 3)

The method as defined in claim 3 wherein prior to exposing the respective build material layers to energy, the method further comprises patterning hydrophobic edges by:
selectively applying the primer fusing agent on the respective build material layers to form individual patterned portions adjacent to the respective patterned portions; and
selectively applying the hydrophobic agent onto at least a portion of the individual patterned portions.

### Claim 5 (depends on 4)

The method as defined in claim 4, further comprising selectively applying the hydrophobic agent on the hydrophobic portion and the hydrophobic edges.

### Claim 6 (depends on 3)

The method as defined in claim 3 wherein:
prior to forming the core of the 3D printed object, the method further comprises building a hydrophobic base by:
iteratively applying the polymeric build material to form individual build material layers;
selectively applying the primer fusing agent on the individual build material layers to form individual patterned portions;
selectively applying the hydrophobic agent onto at least a portion of the individual patterned portions; and
exposing the individual build material layers to energy; and
the core of the 3D printed object is built on the hydrophobic base.

### Claim 7 (depends on 6)

The method as defined in claim 6, further comprising selectively applying the hydrophobic agent on the hydrophobic base and the hydrophobic portion.

### Claim 8 (depends on 1)

The method as defined in claim 1, further comprising repeating the applying of the polymeric build material, the selectively applying of the fusing agent, the selectively applying of the hydrophobic agent, and the exposing to form a predetermined number of 3D object layers and a 3D printed object, wherein the hydrophobic portion extends around an exterior of the 3D printed object.

### Claim 9 (depends on 8)

The method as defined in claim 8, further comprising selectively applying the hydrophobic agent on the hydrophobic portion of the 3D printed object.

### Claim 10

A method of modifying surface hydrophobicity of a three-dimensional (3D) printed object, comprising:
iteratively applying individual build material layers of a polymeric build material;
based on a 3D object model, selectively applying a core fusing agent onto some of the individual build material layers, thereby forming patterned inner portions;
selectively applying a primer fusing agent and a hydrophobic agent onto some of the individual build material layers at areas that are positioned at a 3D object perimeter according to the 3D object model, wherein the hydrophobic agent includes a lipophilic phase discontinuously dispersed within an aqueous phase by a surfactant, wherein the lipophilic phase includes an organosilane having a central silicon atom coupled to a C6 to C24 aliphatic or alicyclic hydrocarbon and multiple hydrolyzable groups, wherein the organosilane is present in the hydrophobic agent at from about 1 wt % to about 20 wt %;
exposing the individual build material layers to energy to selectively coalesce the patterned portions and form the 3D printed object having at least one hydrophobic portion at its perimeter;
removing non-coalesced polymeric build material from the 3D printed object; and
selectively applying the hydrophobic agent on the at least one hydrophobic portion of the 3D printed object.

### Claim 11 (depends on 10)

The method as defined in claim 10 wherein:
i) the primer fusing agent and the hydrophobic agent are selectively applied at edges of the patterned inner portions, and wherein the edges are adjacent to non-patterned polymeric build material; or
ii) the primer fusing agent and the hydrophobic agent are applied to an outermost plurality of the individual build material layers; or
iii) both i and ii.

### Claim 12

A multi-fluid kit, comprising:
a hydrophobic agent including a lipophilic phase discontinuously dispersed within an aqueous phase by a surfactant, wherein the lipophilic phase includes an organosilane having a central silicon atom coupled to a C6 to C24 aliphatic or alicyclic hydrocarbon and multiple hydrolyzable groups, wherein the organosilane is present in the hydrophobic agent at from about 1 wt % to about 20 wt %;
a core fusing agent including an energy absorber having absorption at wavelengths ranging from 400 nm to 4000 nm; and
a primer fusing agent including a plasmonic resonance absorber having absorption at wavelengths ranging from 800 nm to 4000 nm and having transparency at wavelengths ranging from 400 nm to 780 nm.

### Claim 13 (depends on 12)

The multi-fluid kit as defined in claim 12, further comprising a detailing agent.

### Claim 14 (depends on 12)

The multi-fluid kit as defined in claim 12, further comprising a coloring agent.

### Claim 15 (depends on 12)

The multi-fluid kit as defined in claim 12 wherein the organosilane is a trialkoxyorganosilane compound including a C6 to C14 aliphatic or alicyclic hydrocarbon.

### Claim 16 (depends on 12)

The multi-fluid kit as defined in claim 12 wherein the C6 to C24 aliphatic or alicyclic hydrocarbon is free of aromatic hydrocarbons.