Method for producing an object from a precursor, and use of a radically crosslinkable resin in an additive production method

Patent metadata

Field	Value
Publication number	US-11590692-B2
Application number	US-201716349470-A
Country	US
Kind code	B2
Filing date	Nov 14, 2017
Priority date	Nov 14, 2016
Publication date	Feb 28, 2023
Grant date	Feb 28, 2023

Abstract

A process for producing an object from a precursor comprises 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;
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;
III) repeating step II) until the precursor is formed;
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.

First claim

The invention claimed is:

1. A process for producing an object from a precursor, comprising:
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 lowerable in the direction of the gravitational force, and wherein 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;
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 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;
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 component the molar ratio of NCO groups to olefinic C═C double bonds is in a range from ≥1:5 to ≤5:1,
and in that, 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 a 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 which comprises NCO groups and olefinic C═C double bonds, 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.

4. The process according to claim 3 , 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 olefinic C═C double bonds is in a range from ≥1:5 to ≤5:1,
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.

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

6. The process according to claim 5 , wherein at least one free-radical starter is selected from the group:
α-hydroxyphenyl ketone, benzyldimethylketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(4-methoxybenzoyl)diethylgermanium and any combination of at least two thereof
and/or
the isocyanurate trimerization catalyst comprises 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, tributyltin oxide, or a combination thereof.

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

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

9. The process according to claim 1 , wherein in step IV) the treating of the precursor comprises a heating of the body to a temperature of ≥60° C.

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

11. The process according to claim 1 , wherein:
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.

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

• C08F120/36

  containing oxygen in addition to the carboxy oxygen {, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate} · CPC title

• C08G18/792

  formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates · CPC title

• C08G18/225

  of alkali or alkaline earth metals · CPC title

• C08G18/48

  Polyethers · CPC title

• C08G18/022

  the polymeric products containing isocyanurate groups · CPC title