US 2026/0275042 A1 · PHOTOCURABLE RESIN FOR HIGH-RESOLUTION 3-D PRINTING

Abstract

Provided are photocurable resins comprising a poly(siloxane)-based copolymer together with a photoinitiator, and other optional ingredients such as a photocurable diluent, a photoabsorber, a photosensitizer, or a hydrophillic additive. Also provided are methods of stereolithographically printing a 3-D object from a disclosed resin. Also provided is an improved method for stereolithographically printing a 3-D object, the improvement comprising the use of a disclosed photocurable resin. Further provided is a 3-D microfluidic device such as an artificial lung prepared from a disclosed photocurable resin.

Claims21

Dependent claims

1-20. (canceled)

A method for stereolithographically printing a three-dimensional object, comprising:

(a) providing a vessel comprising a photocurable resin, wherein the photocurable resin comprises:
(i) 5-99% by weight of a copolymer having a methacryloxypropyl-methysiloxane repeating unit represented by formula (I)
and
a dimethylsiloxane repeating unit represented by formula (II)
wherein the methacryloxypropyl-methysiloxane repeating unit constitutes 1-10 mol % of the copolymer, and the dimethylsiloxane repeating unit constitutes the balance of the mol % of the copolymer, and
wherein the copolymer has a viscosity average molecular weight (Mv) ranging from about 20 kDa to about 60 kDa;
(ii) 10-95% by weight of a methacryloxypropyl terminated dimethylsiloxane represented by formula (IV)
wherein n is an integer ranging from 1 to 350;
(iii) 0.01-10% by weight of a phosphine oxide photoinitiator selected from phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl-(2,4,6,trimethylbenzoyl) phosphine oxide (TPO), ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), or a combination thereof,
(iv) 0.01-5% by weight of a photoabsorber selected from 1-(Phenyldiazenyl) naphthalen-2-ol (Sudan I) or 1-(2,4-Dimethylphenylazo)-2-naphthol (Sudan II);
and
(v) 0.01-5% by weight of a photosensitizer selected from 2-chloro-thioxanthone, isopropylthioxanthone (ITX), or a combination thereof;
(b) positioning a build surface on which the object is to be printed at a distance on a vertical Z-axis from a bottom of the vessel;
(c) selectively photopolymerizing a first portion of the resin to provide a first photocured layer adjacent to the build surface;
(d) adjusting the distance of the build surface on the vertical Z-axis;
(e) selectively photopolymerizing a second portion of the resin to provide a second photocured layer, wherein the first and second photocured layers form an integral photocured layer;
and
(f) sequentially repeating steps (d) and (e) until the three-dimensional object is printed.

15 more elements

A three-dimensional microfluidic device stereolithographically printed from a photocurable resin, the device comprising:

a first network of channels or conduits for transporting a gas;
and
a second network of channels or conduits for transporting a liquid;
wherein the first network and the second network are separated by one or more membranes that allow for diffusion and gas exchange between the first and second networks;
and wherein the photocurable resin comprises:
(a) 5-99% by weight of a copolymer having a methacryloxypropyl-methysiloxane repeating unit represented by formula (I)
and
a dimethylsiloxane repeating unit represented by formula (II)
wherein the methacryloxypropyl-methysiloxane repeating unit constitutes 1-10 mol % of the copolymer, and the dimethylsiloxane repeating unit constitutes the balance of the mold % of the copolymer, and wherein the copolymer has a viscosity average molecular weight (Mv) ranging from about 20 kDa to about 60 kDa;
(b) 10-95% by weight of a methacryloxypropyl terminated dimethylsiloxane represented by formula (IV)
wherein n is an integer ranging from 1 to 350;
(c) 0.01-10% by weight of a phosphine oxide photoinitiator selected from phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl-(2,4,6, trimethylbenzoyl) phosphine oxide (TPO), ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), or a combination thereof;
(d) 0.01-5% by weight of a photoabsorber selected from 1-(PhenyldiazenyI) naphthalen-2-ol (Sudan I) or 1-(2,4-Dimethylphenylazo)-2-naphthol (Sudan II);
and
(e) 0.01-5% by weight of a photosensitizer selected from 2-chloro-thioxanthone, isopropylthioxanthone (ITX), or a combination thereof.

12 more elements

A method of manufacturing a three-dimensional microfluidic device for use as an artificial organ or extracorporeal support device, the method comprising:

(a) providing a photocurable resin comprising:
(i) 5-99% by weight of a copolymer having a methacryloxypropyl-methysiloxane repeating unit represented by formula (I)
and
a dimethylsiloxane repeating unit represented by formula (II)
wherein the methacryloxypropyl-methysiloxane repeating unit constitutes 1-10 mol % of the copolymer, and the dimethylsiloxane repeating unit constitutes the balance of the mol % of the copolymer, and wherein the copolymer has a viscosity average molecular weight (Mv) ranging from about 20 kDa to about 60 kDa;
(ii) 10-95% by weight of a methacryloxypropyl terminated dimethylsiloxane represented by formula (IV)
wherein n is an integer ranging from 1 to 350;
(ii) 0.01-10% by weight of a phosphine oxide photoinitiator selected from phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl-(2,4,6,trimethylbenzoyl) phosphine oxide (TPO), ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), or a combination thereof;
(iv) 0.01-5% by weight of a photoabsorber selected from 1-(Phenyldiazenyl) naphthalen-2-ol (Sudan I) or 1-(2,4-Dimethylphenylazo)-2-naphthol (Sudan II);
and
(v) 0.01-5% by weight of a photosensitizer selected from 2-chloro-thioxanthone, isopropylthioxanthone (ITX), or a combination thereof;
(b) stereolithographically printing the three-dimensional microfluidic device from the photocurable resin by selectively photopolymerizing successive portions of the resin to form a plurality of integral photocured layers, thereby forming the microfluidic device comprising a first network of channels for transporting a gas and a second network of channels for transporting a liquid, wherein the first and second networks are separated by one or more membranes;
and
(c) removing uncured resin from the printed microfluidic device.

11 more elements

Dependencies are inferred from the claim text.

Facts

Application

19/181,112Filed 16 Apr 2025

Priority

27 May 2020

Published

17 Sep 2026

Term ends

Not estimatedThe source records don’t support an estimate.

Classification27 codes

C08G 77/18
Containing silicon bound to oxygen-containing groups: to alkoxy or aryloxy groups
G03F 7/029
With photosensitivity-increasing substances, e.g. photoinitiators: inorganic compounds; Onium compounds; Organic compounds having hetero atoms…
A61M 1/1698
With membranes: blood oxygenators with or without heat-exchangers
B33Y 70/00
Materials specially adapted for additive manufacturing

Family

Application63/030,848Us provisional application · filed 27 May 2020

Application63/057,166Us provisional application · filed 27 Jul 2020

Application17/332,655Continuation · filed 27 May 2021

Application19/181,112Continuation

US 12,286,512 B2Related patent

US 2021/0371597 A1Published application

US 2026/0275042 A1This patent

From the US filing history. Foreign family members aren’t listed.

Abstract

Claims21

Dependent claims

1-20. (canceled)

A method for stereolithographically printing a three-dimensional object, comprising:

(a) providing a vessel comprising a photocurable resin, wherein the photocurable resin comprises:
(i) 5-99% by weight of a copolymer having a methacryloxypropyl-methysiloxane repeating unit represented by formula (I)
and
a dimethylsiloxane repeating unit represented by formula (II)
wherein the methacryloxypropyl-methysiloxane repeating unit constitutes 1-10 mol % of the copolymer, and the dimethylsiloxane repeating unit constitutes the balance of the mol % of the copolymer, and
wherein the copolymer has a viscosity average molecular weight (Mv) ranging from about 20 kDa to about 60 kDa;
(ii) 10-95% by weight of a methacryloxypropyl terminated dimethylsiloxane represented by formula (IV)
wherein n is an integer ranging from 1 to 350;
(iii) 0.01-10% by weight of a phosphine oxide photoinitiator selected from phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl-(2,4,6,trimethylbenzoyl) phosphine oxide (TPO), ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), or a combination thereof,
(iv) 0.01-5% by weight of a photoabsorber selected from 1-(Phenyldiazenyl) naphthalen-2-ol (Sudan I) or 1-(2,4-Dimethylphenylazo)-2-naphthol (Sudan II);
and
(v) 0.01-5% by weight of a photosensitizer selected from 2-chloro-thioxanthone, isopropylthioxanthone (ITX), or a combination thereof;
(b) positioning a build surface on which the object is to be printed at a distance on a vertical Z-axis from a bottom of the vessel;
(c) selectively photopolymerizing a first portion of the resin to provide a first photocured layer adjacent to the build surface;
(d) adjusting the distance of the build surface on the vertical Z-axis;
(e) selectively photopolymerizing a second portion of the resin to provide a second photocured layer, wherein the first and second photocured layers form an integral photocured layer;
and
(f) sequentially repeating steps (d) and (e) until the three-dimensional object is printed.

15 more elements

A three-dimensional microfluidic device stereolithographically printed from a photocurable resin, the device comprising:

a first network of channels or conduits for transporting a gas;
and
a second network of channels or conduits for transporting a liquid;
wherein the first network and the second network are separated by one or more membranes that allow for diffusion and gas exchange between the first and second networks;
and wherein the photocurable resin comprises:
(a) 5-99% by weight of a copolymer having a methacryloxypropyl-methysiloxane repeating unit represented by formula (I)
and
a dimethylsiloxane repeating unit represented by formula (II)
wherein the methacryloxypropyl-methysiloxane repeating unit constitutes 1-10 mol % of the copolymer, and the dimethylsiloxane repeating unit constitutes the balance of the mold % of the copolymer, and wherein the copolymer has a viscosity average molecular weight (Mv) ranging from about 20 kDa to about 60 kDa;
(b) 10-95% by weight of a methacryloxypropyl terminated dimethylsiloxane represented by formula (IV)
wherein n is an integer ranging from 1 to 350;
(c) 0.01-10% by weight of a phosphine oxide photoinitiator selected from phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl-(2,4,6, trimethylbenzoyl) phosphine oxide (TPO), ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), or a combination thereof;
(d) 0.01-5% by weight of a photoabsorber selected from 1-(PhenyldiazenyI) naphthalen-2-ol (Sudan I) or 1-(2,4-Dimethylphenylazo)-2-naphthol (Sudan II);
and
(e) 0.01-5% by weight of a photosensitizer selected from 2-chloro-thioxanthone, isopropylthioxanthone (ITX), or a combination thereof.

12 more elements

A method of manufacturing a three-dimensional microfluidic device for use as an artificial organ or extracorporeal support device, the method comprising:

(a) providing a photocurable resin comprising:
(i) 5-99% by weight of a copolymer having a methacryloxypropyl-methysiloxane repeating unit represented by formula (I)
and
a dimethylsiloxane repeating unit represented by formula (II)
wherein the methacryloxypropyl-methysiloxane repeating unit constitutes 1-10 mol % of the copolymer, and the dimethylsiloxane repeating unit constitutes the balance of the mol % of the copolymer, and wherein the copolymer has a viscosity average molecular weight (Mv) ranging from about 20 kDa to about 60 kDa;
(ii) 10-95% by weight of a methacryloxypropyl terminated dimethylsiloxane represented by formula (IV)
wherein n is an integer ranging from 1 to 350;
(ii) 0.01-10% by weight of a phosphine oxide photoinitiator selected from phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl-(2,4,6,trimethylbenzoyl) phosphine oxide (TPO), ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), or a combination thereof;
(iv) 0.01-5% by weight of a photoabsorber selected from 1-(Phenyldiazenyl) naphthalen-2-ol (Sudan I) or 1-(2,4-Dimethylphenylazo)-2-naphthol (Sudan II);
and
(v) 0.01-5% by weight of a photosensitizer selected from 2-chloro-thioxanthone, isopropylthioxanthone (ITX), or a combination thereof;
(b) stereolithographically printing the three-dimensional microfluidic device from the photocurable resin by selectively photopolymerizing successive portions of the resin to form a plurality of integral photocured layers, thereby forming the microfluidic device comprising a first network of channels for transporting a gas and a second network of channels for transporting a liquid, wherein the first and second networks are separated by one or more membranes;
and
(c) removing uncured resin from the printed microfluidic device.

11 more elements

Dependencies are inferred from the claim text.

Photocurable resin for high-resolution 3-d printing

Life of this patent

Abstract

Claims21

Photocurable resin for high-resolution 3-d printing

Life of this patent

Abstract

Claims21