Process for producing an object from a precursor and use of a free-radically crosslinkable resin in an additive manufacturing process

Patent metadata

Field	Value
Publication number	US-10449714-B2
Application number	US-201715812116-A
Country	US
Kind code	B2
Filing date	Nov 14, 2017
Priority date	Nov 14, 2016
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

A process for producing an object from a precursor comprises the steps of: depositing a free-radically crosslinked resin atop a carrier to obtain a ply of a construction material joined to the carrier which corresponds to a first selected cross section of the precursor; depositing a free-radically crosslinked resin atop a previously applied ply of the construction material to obtain a further ply of the construction material which corresponds to a further selected cross section of the precursor and which is joined to the previously applied ply; repeating step II) until the precursor is formed; wherein the depositing of a free-radically crosslinked resin at least in step II) is effected by exposure and/or irradiation of a selected region of a free-radically crosslinkable resin corresponding to the respectively selected cross section of the object and wherein the free-radically crosslinkable resin has a viscosity (23° C., DIN EN ISO 2884-1) of ≥5 mPas to ≤100000 mPas. In the process the free-radically crosslinkable resin comprises a curable component in which NCO groups and olefinic C═C double bonds are present, wherein in the curable component the molar ratio of NCO groups to olefinic C═C double bonds is in a range from ≥1:5 to ≤5:1.

First claim

The invention claimed is:

1. A process for producing an object from a precursor, comprising the steps of:
I) depositing a free-radically crosslinked resin atop a carrier to obtain a ply of a construction material joined to the carrier which corresponds to a first selected cross section of the precursor; wherein the carrier is arranged inside a container and is vertically raisable counter to the direction of the gravitational force, and the container provides the free-radically crosslinkable resin,
II) depositing a free-radically crosslinked resin atop a previously applied ply of the construction material to obtain a further ply of the construction material which corresponds to a further selected cross section of the precursor and which is joined to the previously applied ply;
wherein before each step II) the carrier is raised by a predetermined distance so that below the lowermost ply of the construction material viewed in the vertical direction a layer of the free-radically crosslinkable resin is formed,

III) repeating step II) until the precursor is formed;
wherein the depositing of a free-radically crosslinked resin at least in step II) is effected by exposure and/or irradiation of a selected region of a free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor and
wherein the free-radically crosslinkable resin has a viscosity (23° C., DIN EN ISO 2884-1) of ≥5 mPas to ≤100000 mPas,
wherein
the free-radically crosslinkable resin has a curable component in which NCO groups and olefinic C═C double bonds are present,
wherein in the curable compound the molar ratio of NCO groups to olefinic C═C double bonds is in a range from ≥1:5 to ≤5:1,

and wherein, after step III), step IV) is further performed:
IV) treating the precursor obtained after step III) under conditions sufficient to at least partially trimerize to isocyanurate groups NCO groups present in the free-radically crosslinked resin of the obtained precursor to obtain the object.

2. The process according to claim 1 , wherein isocyanurate groups are further present in the curable component, wherein the molar ratio of NCO groups to isocyanurate groups is in a range from ≤100:1 to ≥1:2 and in the curable component the molar ratio of olefinic C═C double bonds to isocyanurate groups is in a range from ≤100:1 to ≥1:5.

3. The process according to claim 1 wherein the curable component comprises a curable compound comprising isocyanurate groups, NCO groups and olefinic C═C double bonds, wherein
in the curable compound the molar ratio of NCO groups to isocyanurate groups is in a range from ≤100:1 to ≥1:2, and
in the curable compound the molar ratio of olefinic C═C double bonds to isocyanurate groups is in a range from ≤100:1 to ≥1:5.

4. The process according to claim 1 wherein the free-radically crosslinkable resin further comprises a free-radical starter and/or an isocyanate trimerization catalyst.

5. The process according to claim 1 wherein at least one free-radical starter is selected from the group: α-hydroxyphenylketone, benzyldimethylketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(4-methoxybenzoyl)diethylgermanium and any combination of at least two thereof
and/or
the isocyanurate trimerization catalyst is selected from: potassium acetate, potassium acetate in combination with a crown ether, potassium acetate in combination with a polyethylene glycol, potassium acetate in combination with a polypropylene glycol, tin octoate, sodium phenoxide, potassium hydroxide, trioctyl phosphine and/or tributyltin oxide.

6. The process according to claim 1 wherein in the resin the molar ratio of NCO groups to Zerewitinoff-active H atoms is ≥500.

7. The process according to claim 1 wherein the curable component has a number-average molecular weight M n of ≥200 g/mol to ≤5000 g/mol.

8. The process according to claim 1 wherein in step IV) the treating of the precursor obtained after step III) under conditions sufficient to at least partially trimerize to isocyanurate groups NCO groups present in the free-radically crosslinked resin of the obtained precursor comprises a heating of the body to a temperature of ≥60° C.

9. The process according to claim 1 wherein the surface of the precursor obtained after step III) and/or of the object obtained after step IV) is contacted with a compound comprising Zerewitinoff-active H atoms, wherein water occurring as natural atmospheric humidity in the atmosphere surrounding the precursor and/or the object is excluded.

10. The process according to claim 1 wherein:
the carrier is arranged inside a container and is vertically lowerable in the direction of the gravitational force,
the container contains the free-radically crosslinkable resin in an amount sufficient to cover at least the carrier and crosslinked resin deposited atop the carrier,
before each step II) the carrier is lowered by a predetermined distance so that above the uppermost ply of the construction material viewed in the vertical direction a layer of the free-radically crosslinkable resin is formed and
in step II) an energy beam exposes and/or irradiates the selected region of the layer of the free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor.

11. The process according to claim 1 wherein:
in step II) a plurality of energy beams simultaneously expose and/or irradiate the selected region of the layer of the free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor.

12. The process according to claim 1 wherein:
in step II) the free-radically crosslinkable resin is applied from one or more printing heads corresponding to the respectively selected cross section of the precursor and is subsequently exposed and/or irradiated.

Assignees

• Covestro Deutschland Ag

Inventors

• Achten Dirk
• Büsgen Thomas
• Tillack Jörg
• Ludewig Michael
• Tomczyk Christoph
• Wagner Roland

Classifications

• C09J2475/00

  Presence of polyurethane · CPC title

• C09J175/14

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

• C09J5/00

  Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers · CPC title

• C09D175/14

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

• C08J3/244

  Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing · CPC title