Modeling material for forming photofabrication model in ink-jet three dimensional printing, supporting material for supporting the shape of photofabrication model on photofabrication and production method of photofabrication model

Patent metadata

Field	Value
Publication number	US-9790382-B2
Application number	US-201615164905-A
Country	US
Kind code	B2
Filing date	May 26, 2016
Priority date	Nov 1, 2010
Publication date	Oct 17, 2017
Grant date	Oct 17, 2017

Abstract

The present invention aims to provide a supporting material for supporting the shape of a photofabrication model on photofabrication in ink-jet three dimensional printing method in which the photocured product is excellent in solubility in water and is easy to remove after photofabrication, and the like. A modeling material for forming a photofabrication model in ink-jet three dimensional printing method containing a curable resin component with a weighted average of SP value of 9.0 to 10.3; and a supporting material for supporting the shape of a photofabrication model on photofabrication in ink-jet three dimensional printing method containing a water-soluble monofunctional ethylenically unsaturated monomer (F), polyoxypropylene glycol with a number average molecular weight of 100 to 5,000 and/or water (G), and a photopolymerization initiator (D).

First claim

The invention claimed is:

1. A three-dimensional modeling method for forming a three-dimensional fabrication product using an ink-jet three dimensional printing apparatus having a printer head for modeling material for discharging a modeling material onto a modeling table, a printer head for supporting material for discharging a supporting material onto the modeling table, and a light source for curing the modeling material and the supporting material discharged onto the modeling table, the method comprising the steps of:
discharging a modeling material from the printer head for modeling material and discharging a supporting material from the printer head for supporting material for the formation of respective layers on the modeling table;
curing the modeling material and the supporting material discharged onto the modeling table by light from the light source to form the layers; and
repeating the steps of the discharging and the curing to shape a three-dimensional fabrication product formed of the modeling material and the supporting material, and
separating a photocured product of the supporting material from a photocured product of the modeling material to extract the photocured product of the modeling material by immersing the three-dimensional fabrication product formed of the modeling material and the supporting material in water, wherein
the modeling material discharged from the printer head for modeling material comprises curable resin ingredients (A) to (C) with a weighted average of SP value of 9.0 to 10.3 and a photopolymerization initiator (D),
wherein curable resin ingredient (A) is a monofunctional ethylenically unsaturated monomer (A), curable resin ingredient (B) is a polyfunctional ethylenically unsaturated monomer containing no urethane group (B), curable resin ingredient (C) is a urethane group-containing ethylenically unsaturated monomer (C), and
the content of (A) is 50% to 90%, the content of (B) is 3% to 25% and the content of (C) is 5% to 35%, on the basis of the weight of the modeling material, and water-swelling ratio of a photocured product of the modeling material is not more than 1% by weight;
the supporting material discharged from the printer head for supporting material comprises a water-soluble monofunctional ethylenically unsaturated monomer (F), an alkylene oxide adduct (G) being a water-soluble compound which is compatible with the water-soluble monofunctional ethylenically unsaturated monomer (F) and is incompatible with a photocured product of (F) and/or water, and a photopolymerization initiator (D), and
the content of (F) is 3% to 45% and the content of (G) is 50% to 95%, on the basis of the weight of the supporting material.

2. The three-dimensional modeling method according to claim 1 , further comprising the step of removing the excess modeling material and supporting material from surfaces of the layers formed on the modeling table by means of a roller after the step of discharging the modeling material from the printer head for modeling material and discharging the supporting material from the printer head for supporting material, wherein the ink-jet three dimensional printing apparatus has the roller for removing the excess modeling material and supporting material from the surfaces of the modeling material and the supporting material discharged onto the modeling table.

3. The three-dimensional modeling method according to claim 1 , wherein swelling deformation due to water of the photocured product of the modeling material is not more than 2 mm.

4. The three-dimensional modeling method according to claim 1 , wherein the photocured product of the supporting material has a durometer hardness of 17 to 35 HDA as supporting strength.

5. The three-dimensional modeling method according to claim 1 , wherein the monofunctional ethylenically unsaturated monomer (A) contained in the modeling material discharged from the printer head for modeling material has a weighted average of SP value of not more than 10.

6. The three-dimensional modeling method according to claim 1 , wherein (D) is a water-soluble photopolymerization initiator.

7. The three-dimensional modeling method according to claim 2 , wherein the printer head for modeling material, the printer head for supporting material, the roller, and the light source are mounted on a common printer head module.

8. The three-dimensional modeling method according to claim 1 , wherein the polyfunctional ethylenically unsaturated monomer containing no urethane group (B) contained in the modeling material discharged from the printer head for modeling material has a weighted average of SP value of not more than 10.

9. The three-dimensional modeling method according to claim 1 , wherein the urethane group-containing ethylenically unsaturated monomer (C) contained in the modeling material discharged from the printer head for modeling material has a weighted average of SP value of not more than 10.9.

10. A three-dimensional fabrication product comprising the modeling material and the supporting material produced by the three-dimensional modeling method according to claim 1 .

11. A photocured product of the modeling material produced by immersing the three-dimensional fabrication product according to claim 10 in water and removing a photocured product of the supporting material.

12. The three-dimensional modeling method according to claim 1 , wherein (G) is an alkylene oxide adduct having a number average molecular weight of from 100 to 5,000.

13. A three-dimensional modeling method for forming a three-dimensional fabrication product using an ink jet three dimensional printing apparatus having a printer head for modeling material for discharging a modeling material onto a modeling table, a printer head for supporting material for discharging a supporting material onto the modeling table, and a light source for curing the modeling material and the supporting material discharged onto the modeling table, the method comprising the steps of:
discharging a modeling material from the printer head for modeling material and discharging a supporting material from the printer head for supporting material for the formation of respective layers on the modeling table;
curing the modeling material and the supporting material discharged onto the modeling table by light from the light source to form the layers; and
repeating the steps of the discharging and the curing to shape a three-dimensional fabrication product formed of the modeling material and the supporting material, and
separating a photocured product of the supporting material from a photocured product of the modeling material to extract the photocured product of the modeling material by immersing the three-dimensional fabrication product formed of the modeling material and the supporting material in water, wherein
the modeling material discharged from the printer head for modeling material comprises curable resin ingredients (A) to (C) with a weighted average of SP value of 9.0 to 10.3 and a photopolymerization initiator (D),
wherein curable resin ingredient (A) is a monofunctional ethylenically unsaturated monomer (A), curable resin ingredient (B) is a polyfunctional ethylenically unsaturated monomer containing no urethane group (B), curable resin ingredient (C) is a urethane group-containing ethylenically unsaturated monomer (C), and
the content of (A) is 50% to 90%, the content of (B) is 3% to 25% and the content of (C) is 5% to 35%, on the basis of the weight of the modeling material;
the supporting material discharged from the printer head for supporting material comprises a water-soluble monofunctional ethylenically unsaturated

Assignees

• Keyence Co Ltd

Inventors

• Suzuki Hideyuki
• Nakayama Masatoshi

Classifications

• B33Y80/00

  Products made by additive manufacturing · CPC title

• B29K2105/005

  Heat sensitisers or absorbers · CPC title

• C08L75/16

  having terminal carbon-to-carbon unsaturated bonds · CPC title

• C08F290/067

  Polyurethanes; Polyureas · CPC title

• C09D11/30

  Inkjet printing inks · CPC title