Method for producing an at least partially coated object

Patent metadata

Field	Value
Publication number	US-11981095-B2
Application number	US-201716463510-A
Country	US
Kind code	B2
Filing date	Nov 22, 2017
Priority date	Nov 25, 2016
Publication date	May 14, 2024
Grant date	May 14, 2024

Abstract

The invention relates to a method for producing an at least partially coated object, comprising the step of producing the object from a construction material by means of an additive manufacturing method, the construction material comprising a thermoplastic polyurethane material. Following the production of the object, the method comprises the step of at least partially bringing a preparation into contact with the object, the preparation being selected from: an aqueous polyurethane dispersion; an aqueous dispersion of a polymer comprising OH groups, this dispersion also containing a compound comprising NCO groups; an aqueous preparation of a compound containing NCO groups, but not containing any polymers comprising OH groups; or a combination of at least two thereof. The invention also relates to an at least partially coated object that was obtained by a method according to the invention.

First claim

The invention claimed is:

1. A process for producing an at least partially coated article comprising:
producing the article using an additive manufacturing process from a construction material comprising a thermoplastic polyurethane material; and
at least partially contacting the article with a preparation selected from:
aqueous polyurethane dispersion,
aqueous dispersion of an OH-containing polymer, wherein this dispersion further contains an NCO-containing compound,
aqueous preparation of an NCO-containing compound, wherein this preparation contains no OH-containing polymers, or
a combination of at least two of these,

wherein the residual content of organic solvents in the preparation is less than 2% by weight relative to the total preparation; and
wherein regions of the article contacted by the preparation have an elastic modulus at 50% elongation determined according to DIN 53504 that is 5% greater than an elastic modulus at 50% elongation of regions of the article not contacted by the preparation.

2. The process as claimed in claim 1 , wherein the aqueous polyurethane dispersion is obtained when
A) isocyanate-functional prepolymers are produced from
A1) organic polyisocyanates,
A2) polymeric polyols having number-average molecular weights of 400 to 8000 g/mol and OH functionalities of 1.5 to 6 and
A3) optionally hydroxyl-functional compounds having molecular weights of 62 to 399 g/mol and optionally containing olefinically unsaturated compounds and
A4) optionally isocyanate-reactive, anionic or potentially anionic and/or optionally nonionic hydrophilization agents,

and
B) the free NCO groups thereof are then wholly or partially reacted
B1) optionally with amino-functional compounds having molecular weights of 32 to 400 g/mol and
B2) with amino-functional, anionic or potentially anionic hydrophilization agents by chain extension and the prepolymers are dispersed in water before, during or after step B).

3. The process as claimed in claim 1 , wherein the aqueous dispersion of an OH-containing polymer which further contains an NCO-containing compound comprises the components:
A) one or more compounds comprising uncrosslinked polymer-bonded (meth)acrylates having an OH number of 20 to 300 mg KOH/g of substance and/or
B) optionally compounds distinct from A) having at least one isocyanate-reactive group and at least one radiation-curable double bond,
C) optionally one or more compounds having at least one isocyanate-reactive group but no radiation-curable double bonds,
D) one or more compounds having at least one isocyanate-reactive group and additionally groups which are nonionic, anionic or capable of forming anionic groups and have a dispersing effect for the polyurethane acrylates or D′) one or more compounds having at least one isocyanate-reactive group and additionally groups which are cationic or capable of forming cationic groups and have a dispersing effect for the polyurethane acrylates,
E) one or more organic compounds having 2 or more isocyanate groups,
F) optionally neutralizing amines in combination with compounds D) or F′) neutralization acids F′) in combination with compounds D′),
G) optionally urethanization catalysts and optionally further assistant and additive substances.

4. The process as claimed in claim 1 , wherein the NCO-containing compound in the aqueous preparation of the NCO-containing compound without OH-containing polymers in the preparation is a compound based on aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanates having:
a) an average isocyanate functionality of at least 2.0
b) a content of isocyanate groups (calculated as NCO; molecular weight=42) of 5.0% to 25.0% by weight and
c) an anionically and/or nonionically hydrophilizing component.

5. The process as claimed in claim 1 , sections of the article that are contacted with the preparation have a porosity Φ of ≥0.01 to ≤0.6 and the porosity Φ is expressed as:
Φ=1−(ρ/ρ 0 )

wherein ρ represents the density of the volume assigned to the sections of the article that are contacted with the preparation and ρ 0 represents the true density of the construction material.

6. The process as claimed in claim 1 , wherein the additive manufacturing process comprises:
applying a layer of particles comprising the construction material onto a target surface;
energizing a selected portion of the layer corresponding to a cross section of the article to join the particles in the selected portion;
repeating the steps of applying and energizing for a plurality of layers so that the joined portions of the adjacent layers become joined to form the article.

7. The process as claimed in claim 6 , wherein the energizing of a selected portion of the layer comprises:
irradiating a selected portion of the layer corresponding to a cross section of the article with an energy beam to join the particles in the selected portion.

8. The process as claimed in claim 6 , wherein the energizing of a selected portion of the layer comprises:
applying a liquid to a selected portion of the layer corresponding to a cross section of the article, wherein the liquid increases the absorption of energy in the regions of the layer contacted by it relative to the regions not contacted by it;
irradiating the layer so that the particles in regions of the layer contacted by the liquid are joined to one another and the particles in regions of the layer not contacted by the liquid are not joined to one another.

9. The process as claimed in claim 1 , wherein the additive manufacturing process comprises:
applying a filament of an at least partially molten construction material onto a carrier to obtain a layer of the construction material corresponding to a first selected cross section of the article;
applying a filament of the at least partially molten construction material onto a previously applied layer of the construction material to obtain a further layer of the construction material which corresponds to a further selected cross section of the article and which is joined to the previously applied layer;
repeating the step of applying a filament of the at least partially molten construction material onto a previously applied layer of the construction material until the article has been formed.

10. The process as claimed in claim 1 , wherein the construction material comprises a thermoplastic polyurethane elastomer having a melting range (DSC, differential scanning calorimetry; second heating at a heating rate of 5 K/min) of ≥20° C. to ≤240° C., a Shore hardness according to DIN ISO 7619-1 of ≥40 A to ≤85 D.

11. The process as claimed in claim 1 , wherein the construction material comprises a thermoplastic polyurethane elastomer having a melting range (DSC, differential scanning calorimetry; second heating at a heating rate of 5 K/min) of ≥20° C. to ≤240° C.,
a Shore A hardness according to DIN ISO 7619-1 of ≥40 A to ≤85 D, and
a melt volume rate (MVR) according to ISO 1133 (10 kg) at a temperature T of 5 to 15 cm 3 /10 min and
exhibiting a change in the melt volume rate (10 kg) at an increase of temperature T by 20° C. of ≤90 cm 3 /10 min.

12. The process as claimed in claim 1 , wherein the construction material comprises a thermoplastic polyurethane elastomer obtained from the reaction of the following components:
a) at least one organic diisocyanate
b) at least one compound having isocyanate-reactive groups and having a number-average molecular weight (M n ) of ≥500 g/mol to ≤6000 g/mol and a number-average functionality of the sum total of the components b) of ≥1.8 to ≤2.5
c) at least one chain extender having a molecular weight (Mn) of 60-450 g/mol an

Assignees

• Covestro Deutschland Ag
• Stratasys Inc

Inventors

• Achten Dirk
• Büsgen Thomas
• Michaelis Thomas
• Wagner Roland
• Mettmann Bettina
• Akbas Levent
• Hättig Jürgen
• Guedou Arnaud

Classifications

• B29C71/0009 Primary

  using liquids, e.g. solvents, swelling agents (spectacle cases, e.g. for cleaning contact lenses A45C11/04; disinfecting or sterilising contact lenses A61L12/00, using liquid substances A61L2/20; cleaning involving the use of liquid in general B08B3/00; for hydrating contact lenses B29D11/00067) · CPC title

• B29C64/153

  using layers of powder being selectively joined, e.g. by selective laser sintering or melting · CPC title

• B33Y40/20

  Post-treatment, e.g. curing, coating or polishing · CPC title

• C08G18/3228

  acyclic · CPC title

• C08G18/3234

  cycloaliphatic · CPC title