Composition for liquid-based additive manufacturing

Patent metadata

Field	Value
Publication number	US-12473434-B2
Application number	US-202117795725-A
Country	US
Kind code	B2
Filing date	Feb 3, 2021
Priority date	Feb 4, 2020
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

Surface treated silica containing particles are combined with a resin to form a liquid prepolymer composition for use in additive manufacturing. A surface treatment on the silica containing particles may participate in polymerization of the composition. The silica containing particles may be colloidal silica or a silica polymer composite particle.

First claim

What is claimed is:

1 . A method of forming a three-dimensional object, comprising:
a) contacting a substrate with a reservoir of prepolymer composition, the prepolymer composition comprising a resin comprising monomers and oligomers of polymers selected from acrylates, methacrylates, vinyl polymers, olefins, silicones, and epoxies and silica-containing particles selected from i) 0.1-50 wt % colloidal silica particles having a particle size of 5 nm-600 nm treated with at least one surface treatment agent, and ii) 0.1-50 wt % silica-polymer composite particles having a particle size of 10 nm-3 microns and comprising colloidal silica particles treated with at least one surface treatment agent, wherein the surface treatment agent comprises an organopolysiloxane, an organosiloxane, an organosilane, a haloorganosilane, or an organosilazane, and wherein the prepolymer composition has a viscosity no more than 500 cP greater than the neat resin at a temperature of 25° C. and a shear rate of 100 s −1 ; b) selectively exposing the prepolymer composition imagewise to actinic radiation to form solid polymer at the substrate and having a build surface parallel to the substrate, the solid polymer being a sequential portion of the three-dimensional object; c) contacting the build surface with the prepolymer composition; d) selectively exposing the prepolymer composition to actinic radiation to increase the mass of the solid polymer, the additional polymer being a subsequent sequential portion of the three-dimensional object and e) repeating steps c) and d) until the three dimensional object is formed.

2 . The method of claim 1 , wherein the surface treatment agent comprises a hydroxy-substituted or terminated siloxane oligomer having 7 to 14 mers or a cyclic siloxane having 4-14 silicon atoms in the ring.

3 . The method of claim 1 , wherein the surface treatment agent comprises R 1 Si[(OR 2 ) x R 3 3-x ] wherein R 1 is selected from the group consisting of C 1 -C 30 branched and straight chain alkyl, alkenyl, and C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, and R 4 Q, where R 4 is an alkyl linker with the general formula C n H 2n , where n=0-10, and Q is an epoxy, thiol, or a substituted or unsubstituted vinyl, allyl, acrylate ester, or methacrylate ester group, R 2 and R 3 are independently methyl or ethyl, and x is 1, 2, or 3, hexamethyldisilazane, or dimethyldichlorosilane.

4 . The method of claim 1 , wherein the surface treatment agent comprises a polysiloxane oligomer or co-oligomer of at least one group [R 3 3-x (OR 2 ) x ]SiR 4 Q having a viscosity of 4-3500 cSt, wherein R 4 is an alkyl linker with the general formula C n H 2n , where n=0-10, and Q is an epoxy, thiol, or a substituted or unsubstituted vinyl, allyl, acrylate ester, or methacrylate ester group, R 2 and R 3 are independently methyl or ethyl, and x is 1, 2, or 3.

5 . The method of claim 4 , wherein the polysiloxane oligomer or co-oligomer has a viscosity of 500-3500 cSt.

6 . The method of claim 1 , wherein the silica-containing particles are silica-polymer composite particles.

7 . The method of claim 6 , wherein the silica-polymer composite particles comprise a plurality of silica particles and a polymer matrix, wherein the silica particles are surface-modified with a first hydrophobizing agent comprising [R 3 3-x (OR 2 ) x ]SiR 4 Q, wherein R 4 Q, where R 4 is an alkyl linker with the general formula C n H 2n , where n=0-10, and Q is an epoxy, thiol, or a substituted or unsubstituted vinyl, allyl, acrylate ester, or methacrylate ester group, R 2 and R 3 are independently methyl or ethyl, and x is 1, 2, or 3.

Assignees

• Cabot Corp

Inventors

• Fomitchev Dmitry
• Palumbo Paul S
• Bates Jodi A
• Zhang Xiaofeng
• Lewis Russell H
• Step Eugene N
• Korchev Andriy
• Wimble Joshua M
• Sargent Patrick
• Schimmoeller Bjoern

Classifications

• C08K9/08

  Ingredients agglomerated by treatment with a binding agent · CPC title

• C08K9/06 Primary

  with silicon-containing compounds · CPC title

• C08K3/36

  Silica · CPC title

• C01P2006/22

  Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability · CPC title

• B33Y70/10

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title