Granted Patent B2

US 12,502,853 · App. 18/686,045 · Granted Dec 23, 2025

Inventors: Sven Meyer (Apensen, DE); Stephan Neffgen (Pinneberg, DE); Sunhild C. Salmen (Hamburg, DE); Jens Träger (Hetlingen, DE)

Assignee: MÜHLBAUER TECHNOLOGY GMBH

B29C71/0009B05D3/002B05D3/0254B29C71/04B29C2071/0027B33Y40/20

Abstract

Claims (65)

1 . A method of aftertreatment of 3-D objects ( 10 ) printed from a light-curing resin formulation, wherein a 3-D object ( 10 ) taken from a 3-D printer is aftertreated by the following steps:

a) exposing a surface ( 11 ) of the 3-D object ( 10 ) to an aftertreatment fluid ( 16 ) comprising a light-curing resin formulation for a given contact time, where the aftertreatment fluid ( 16 ) and contact time are chosen such that the aftertreatment fluid ( 16 ) can penetrate into a fissure ( 12 ) or a pore ( 13 ) on the surface ( 11 ) of the 3-D object ( 10 ) within the contact time owing to capillarity;

b) removing the aftertreatment fluid ( 16 ) remaining on the surface of the 3-D object ( 10 ); and

c) irradiating the 3-D object ( 10 ) with light for post-curing of the light-curing resin formulation used to print the 3-D object ( 10 ) and curing the aftertreatment fluid ( 16 ) that has penetrated into fissures ( 12 ) and/or pores ( 13 ) at the surface ( 11 ) of the 3-D object ( 10 );

wherein the exposing of the surface ( 11 ) of 3-D object ( 10 ) to the aftertreatment fluid ( 16 ) comprises a coating of the surface ( 11 ) of the 3-D object ( 10 ) with aftertreatment fluid ( 16 ) or dipping it into an aftertreatment fluid bath; and

wherein in the case of cleaning of the surface ( 11 ) of the 3-D object ( 10 ) with aftertreatment fluid ( 16 ), the aftertreatment fluid bath is configured as an ultrasound bath or has a stirrer system for washing the 3-D object ( 10 ) with aftertreatment fluid ( 16 ).

2 . The method as claimed in claim 1 ,

characterized in that

the surface ( 11 ) of the 3-D object ( 10 ), before being exposed to the aftertreatment fluid ( 16 ), is cleaned with a detergent ( 15 ) distinct from the aftertreatment fluid ( 16 ) to remove residues ( 14 ) of uncured or incompletely cured resin formulation adhering to the surface of the 3-D object.

3 . The method as claimed in claim 2 ,

characterized in that

the detergent ( 15 ) is a volatile organic solvent.

4 . The method as claimed in claim 3 ,

characterized in that

the detergent ( 15 ) at 23° C. has a volatility index of 1 to 15.

5 . The method as claimed in claim 1 ,

characterized in that

the exposing of the surface ( 11 ) of the 3-D object ( 10 ) to the aftertreatment fluid ( 16 ) includes cleaning of the surface ( 11 ), for which the aftertreatment fluid ( 16 ) has a lower viscosity than a viscosity of residues ( 14 ) of uncured or incompletely cured resin formulation used in the 3-D printing that adhere to the surface of the 3-D object ( 10 ).

6 . The method as claimed in claim 1 ,

characterized in that

a removing of the aftertreatment fluid ( 16 ) remaining on the surface of the 3-D object ( 10 ) and/or a removing of detergent ( 15 ) is effected by blowing away the aftertreatment fluid ( 16 ) and/or the detergent ( 15 ).

7 . The method as claimed in claim 1 ,

characterized in that

the aftertreatment fluid ( 16 ) at 23° C. and a shear rate of 1 s −1 has a viscosity of 2 Pa s to 0.005 Pa s.

8 . The method as claimed in claim 1 ,

characterized in that

the aftertreatment fluid ( 16 ) comprises at least one free-radically photopolymerizable monomer.

9 . The method as claimed in claim 8 ,

characterized in that

the at least one free-radically photopolymerizable monomer is selected

from the group of the (meth)acrylates, comprising monomers consisting of two of two or more, (meth)acrylate groups and one group which has 2 to 12 carbon atoms and is selected from linear or branched alkyl and alkylene groups, aliphatic cyclic hydrocarbyl groups, polyoxyalkylene groups and a combination of these groups;

from the group of the (meth)acrylates, comprising monomers consisting of a (meth)acrylate group and a radical which has 2 to 12 carbon atoms and is selected from linear or branched alkyl and alkylene groups, aliphatic cyclic hydrocarbyl groups, polyoxyalkylene groups and a combination of these groups; and/or

from the group of the (meth)acrylates comprising monomer(s) consisting of two or more, (meth)acrylate groups and one group comprising at least one group selected from a urethane group, a bisphenol A group, an aliphatic polycyclic group and an oligoester group.

10 . The method as claimed in claim 1 ,

characterized in that

the aftertreatment fluid ( 16 ) comprises at least one additive.

11 . The method as claimed in claim 10 ,

characterized in that

the aftertreatment fluid ( 16 ) comprises one or more additives, selected from the group of (photo)initiators, stabilizers, dyes and nanoscale fillers.

12 . The method as claimed in claim 1 ,

characterized in that

the 3-D object ( 10 ) is composed of a light-curing resin formulation for 3-D printing comprising 5% to 65% by weight of insoluble filler particles.

13 . The method as claimed in claim 1 ,

characterized in that

the aftertreatment fluid is chosen such that it is subject to immediate concomitant curing on irradiation of the 3-D object for post-curing.

14 . A method of printing 3-D objects, in which a 3-D printing of a 3-D object from a light-curing resin formulation is followed by a method as claimed in claim 1 .

15 . The method as claimed in claim 2 , characterized in that the detergent ( 15 ) has completely evaporated or is removed prior to exposure of the 3-D object ( 10 ) to the aftertreatment fluid ( 16 ).

16 . The method as claimed in claim 7 ,

characterized in that

the aftertreatment fluid ( 16 ) at 23° C. and a shear rate of 1 s −1 has a viscosity of 1.5 Pa s to 0.01 Pa s.

17 . The method as claimed in claim 7 ,

characterized in that

the viscosity in a shear rate range of 0.01-10 s −1 is not more than 10 Pa s.

18 . The method as claimed in claim 8 ,

characterized in that aftertreatment fluid ( 16 ) comprises more than one free-radically photopolymerizable monomer.

19 . The method as claimed in claim 9 ,

characterized in that

the at least one free-radically photopolymerizable monomer is selected

from the group consisting of: PRDMA, propane-1,3-diol dimethacrylate; BDMA, butane-1,3-diol dimethacrylate; BDDMA, butane-1,4-diol dimethacrylate; PDDMA, pentane-1,5-diol dimethacrylate; NPGDMA, neopentyl glycol dimethacrylate;

HDDMA, hexane-1,6-diol dimethacrylate; NDDMA, nonane-1,9-diol dimethacrylate; DDDMA, decane-1,10-diol dimethacrylate; DDDDMA, dodecane-1,12-diol dimethacrylate; PRDA, propane-1,3-diol diacrylate; BDA, butane-1,3-diol diacrylate; BDDA, butane-1,4-diol diacrylate; PDDA, pentane-1,5-diol diacrylate; NPGDA, neopentyl glycol diacrylate; HDDA, hexane-1,6-diol diacrylate; NDDA, nonane-1,9-diol diacrylate; DDDA, decane-1,10-diol diacrylate; DDDDA, dodecane-1,12-diol dimethacrylate; EGDMA, ethylene glycol dimethacrylate; DEGDMA, diethylene glycol dimethacrylate; TEDMA, triethylene glycol dimethacrylate; TEGDMA, tetraethylene glycol dimethacrylate; EGDA, ethylene glycol diacrylate; DEGDA, diethylene glycol diacrylate; TEDA, triethylene glycol diacrylate; TEGDA, tetraethylene glycol diacrylate; PEG200DMA, polyethylene glycol 200 dimethacrylate; PEG300DMA, polyethylene glycol 300 dimethacrylate; PEG400DMA, polyethylene glycol 400 dimethacrylate; PEG600DMA, polyethylene glycol 600 dimethacrylate; PEG200DA, polyethylene glycol 200 diacrylate; PEG300DA, polyethylene glycol 300 diacrylate; PEG400DA, polyethylene glycol 400 diacrylate; PEG600DA, polyethylene glycol 600 diacrylate; PPGDMA, polypropylene glycol dimethacrylate; PPGDA, polypropylene glycol diacrylate; NPG(PO)2DMA, propoxylated (2) neopentyl glycol dimethacrylate; NPG(PO)2DA, propoxylated (2) neopentyl glycol diacrylate;

from the group consisting of: EMA, ethyl methacrylate; allyl methacrylate; allyl acrylate; n-BMA, n-butyl methacrylate; IBMA, isobutyl methacrylate, t-BMA, tert-butyl methacrylate; EHMA, 2-ethylhexyl methacrylate; LMA, lauryl methacrylate; TDMA, tridecyl methacrylate; CHMA, cyclohexyl methacrylate; BZMA, benzyl methacrylate; IBOMA, isobornyl methacrylate; HEMA, 2-hydroxyethyl methacrylate; HPMA, 2-hydroxypropyl methacrylate; DMMA, dimethylaminoethyl methacrylate; DEMA, diethylaminoethyl methacrylate; GMA, glycidyl methacrylate; THFMA, tetrahydrofurfuryl methacrylate; ETMA, ethoxyethyl methacrylate; AIB, isobutyl acrylate; TBA, tert-butyl acrylate; LA, lauryl acrylate; CEA, cetyl acrylate; STA, stearyl acrylate; CHA, cyclohexyl acrylate; BZA, benzyl acrylate; IBOA, isobornyl acrylate; 2-MTA, 2-methoxyethyl acrylate; ETA, 2-ethoxyethyl acrylate; EETA, ethoxyethoxyethyl acrylate; PEA, 2-phenoxyethyl acrylate; THFA, tetrahydrofurfuryl acrylate; HEA, 2-hydroxyethyl acrylate; HPA, 2-hydroxypropyl acrylate; 4HBA, 4-hydroxybutyl acrylate; DMA, dimethylaminoethyl acrylate; 3F, trifluoroethyl acrylate; 17F, heptadecafluorodecyl acrylate; 2-PEA, 2-phenoxyethyl acrylate; TBCH, 4-tert-butylcyclohexyl acrylate; DCPA, dihydrodicyclopentadienyl acrylate; EHA, 2-ethylhexyl acrylate; and 3EGMA, triethylene glycol monomethacrylate; and/or

from the consisting of: bis-MA, bisphenol A dimethacrylate; bis-GMA, bisphenol A glycerol dimethacrylate; BPA(EO)DMA, ethoxylated bisphenol A dimethacrylate (EO=1-30); BPA(PO)DMA, propoxylated bisphenol A dimethacrylate (PO=1-30); BPA(EO)DA, ethoxylated bisphenol A diacrylate (EO=1-30); BPA(PO)DA, propoxylated bisphenol A diacrylate (PO=1-30); BPA(PO)GDA, propoxylated bisphenol A-glycerol diacrylate; UDMA, diurethane dimethacrylate; TCDD(M)A and PEM-665.

20 . The method as claimed in claim 3 ,

characterized in that

the detergent ( 15 ) is a volatile organic solvent comprising isopropanol and/or ethanol.

Assignments (1)

Priority Claims (1)

Continuity (1)

References Cited (12)