WO2025256902A1 - Impression d'un objet tridimensionnel - Google Patents

Impression d'un objet tridimensionnel

Info

Publication number
WO2025256902A1
WO2025256902A1 PCT/EP2025/064474 EP2025064474W WO2025256902A1 WO 2025256902 A1 WO2025256902 A1 WO 2025256902A1 EP 2025064474 W EP2025064474 W EP 2025064474W WO 2025256902 A1 WO2025256902 A1 WO 2025256902A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
printing
printing procedure
procedure according
printed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/064474
Other languages
English (en)
Inventor
Max Röttger
Anne ASMACHER
Kerstin ANDERSECK
Stefanie BURGDORF
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Altana New Technologies GmbH
Original Assignee
Altana New Technologies GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Altana New Technologies GmbH filed Critical Altana New Technologies GmbH
Publication of WO2025256902A1 publication Critical patent/WO2025256902A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate

Definitions

  • the present invention relates to a printing procedure, an object and the use of a printable composition.
  • Three dimensional (3D) printing or additive manufacturing is a process in which a 3D digital model is manufactured by the addition of construction material.
  • the 3D printed object is created by utilizing the computer-aided design (CAD) data of an object through sequential construction of two dimensional (2D) layers that correspond to cross-sections of 3D objects. These layers were printed over one another with the proviso that each layer is rapidly cured (e. g. by UV curing) before the next layer is printed accordingly.
  • CAD computer-aided design
  • inkjet printing tiny drops of ink (having a limited viscosity) are projected directly onto a receiver surface without physical contact between the printing device and the ink-receiver.
  • the printing device stores the printing data electronically and controls a mechanism for ejecting the drops image-wise. Printing is accomplished by moving a print head across the ink-receiver or vice versa or both.
  • 3D-printing concern resin printing technologies like stereolithography, digital light processing and liquid crystal display vat polymerizations in either top-down or bottom-up approaches.
  • Three-dimensional printing technologies are relatively speedy and flexible printing methods for the production of prototype parts, tooling and rapid manufacturing of three-dimensional complex structures directly from a CAD file.
  • Radiation curable compositions for use in three-dimensional printing methods of complex structures are e. g. described in WO 2004/096514.
  • an appropriate printing procedure uses a “printing composition” (typically provided as an ink or as a (liquid) resin) that combines (fulfills) at the same time the following conditions: having a sufficient low viscosity, providing a high viscosity stability (e.g. should not polymerize in the printing apparatus prior the printing) and being (radiation) curable to achieve the desired mechanical properties.
  • a “printing composition” typically provided as an ink or as a (liquid) resin
  • having a sufficient low viscosity providing a high viscosity stability (e.g. should not polymerize in the printing apparatus prior the printing) and being (radiation) curable to achieve the desired mechanical properties.
  • Acryl amides are generally highly photo polymerization reactive (free radical polymerization).
  • the printed composition A in general provides the relevant quality requirements:
  • the composition A provides the basis concerning a sufficient viscosity stability which is a basic requirement to maintain a working printing process (e. g. gelling of the ink or the resin would block and possibly even destroy the printer). Furthermore, the composition allows the generation of a print-product with beneficial mechanical properties - especially: high heat deflection temperature (HDT), low curing (polymerization) shrinkage, low brittleness, high rigidity and low material ageing. A sufficient (photopolymerization) curing after its application is possible in order to provide said mechanical properties and to avoid the generation of uncured material.
  • HDT high heat deflection temperature
  • composition A according to the present invention provides a kind of “compromise” that does take all of these relevant different issues into consideration - e. g. curing has to be intensive enough to provide a corresponding durability on the one hand but must be limited on the other hand in order to avoid brittleness.
  • the irradiation is performed by radiation with UV-light (especially depending on the selection of the radical photo initiator (R)): the radical photoinitiator (R) generates reactive species (free radicals) when exposed to radiation (e. g. UV or visible light).
  • the photo initiator might be comprised in the composition in an amount of 0.2 to 2.0 wt.%, based on the total weight of the printable composition.
  • species of the radical photoinitiator (R) are provided by phosphinoxide-based photoinitiators, preferably by diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and/or phenyl bis(2,4,6- trimethylbenzoyl)phosphine oxide.
  • a quantity of the composition A is provided so that it can be irradiated
  • the quantity of the composition A which has been provided in step 1) is cured by photo polymerization to generate a first cured layer
  • a further quantity of the composition A is provided so that it is in direct contact with the cured layer generated in step 2)
  • the further quantity of the composition A which has been provided in step 3) is cured by photo polymerization to generate a second cured layer that lies on top of the first cured layer.
  • the printing procedure is an inkjet printing process, where in step 1) a first layer of the ink composition A is printed, in step 2) the first layer which has been printed in step 1) is cured by photo polymerization, in step 3) a second layer of the ink composition A is printed on the layer which has been cured in step 2) and in step 4) the second layer which has been printed in step 3) is cured by photo polymerization.
  • the printing procedure is a resin printing process, preferably stereolithography.
  • resin printing processes are digital light processing and liquid crystal display vat polymerizations in either top-down or bottom-up approaches.
  • the printing procedure according to the present invention is a three- dimensional printing procedure in which at least three layers of the composition A were printed on top of each other.
  • composition A identical compositions A used
  • the composition A is often liquid at 25 °C (at 1 atm). Furthermore, the composition A is normally also printable and often also jettable (printing through a nozzle be possible) - at elevated temperatures up to 65 °C (at 1 atm).
  • the composition is flowable and printable at temperatures of 10 - 65 °C. However, in some cases temperatures of at least 40 °C are necessary.
  • viscosity reducing compounds/ solvents as “co-compounds” are normally necessary to use these compounds in a printing ink or in a printing resin.
  • these viscosity reducing co-compounds/ solvents should react in order to become structural units of the polymer matrix.
  • Such compounds are often called as “reactive diluents” which are substances which reduce the viscosity for processing and become part of the polymer matrix during its subsequent curing via copolymerization. Below a preferred embodiment with such a photo polymerization reactive compound (N) is described which works as such a kind of “reactive diluent”.
  • Such a composition in many cases generally provides the basis for a sufficient low viscosity. This is especially important in case of an ink-jetting application (at nonelevated temperatures), where the generation of tiny (ink-jettable) ink drops is necessary. However, also in case of resin printing a sufficient low viscosity is generally helpful (“processability of immersion of building platform and recoating of liquid surface”).
  • the component (N) should be preferably highly (photo) polymerization reactive.
  • corresponding acrylates and tertiary acrylamides (“having not such a hydrogen atom”) might be used.
  • at least 50 wt.% of the contained (N) is provided by species of the group consisting of tertiary acrylamides and compounds containing acryloyl groups.
  • ACMO acryloyl morpholine
  • VMOX mono-vinyl oxazolidinone
  • IBOA isobornyl acrylate.
  • I BOA ACMO und VMOX each have a low viscosity (and are also good solvents for (M)) and generally contribute as co-polymerized structural units to beneficial mechanical properties (especially for avoiding brittleness).
  • TCCDA tricyclodecane dimethanol diacrylate
  • At least 50 wt.% of the contained (N) is provided by species of the group consisting of tertiary acrylamides and compounds containing acryloyl groups.
  • the wt.% sum of contained (N) and contained (M) is at least 51 wt.%, preferably a least 64 wt.% and more preferably at least 80 wt. %.
  • composition A is flowable and printable at temperatures of 10 - 65 °C.
  • photopolymerization mixtures are typically based on acrylates which represent effective photopolymerization monomers/oligomers.
  • These groups are known as to be very reactive and efficient free radical polymerization groups (and much more reactive like e. g. meth acryl groups).
  • acryl amides in general are effective photopolymerization compounds.
  • This fact might be a decisive factor for the special mechanical properties of such polymers containing structural units of secondary acrylamides: especially high HDT values might be achieved.
  • polyacrylates (work as effective polymerization based crosslinkers) might be alternatively used but with the disadvantage that a non-desired intensive shrinkage (and sometimes also a low final double bond conversion) is caused.
  • PhAAm N-phenyl acrylamide (a solid); Benzyl-AAm, N-benzyl acrylamide (a solid); tBu-AAm, N-tert butyl acrylamide (a solid); tOctyl-AAm, N-tert-Octylacrylamide (a solid);
  • Butoxymethyl-AAm N-(butoxymethyl)acrylamide (viscous liquid); iButoxymethyl- AAm, N-(isobutoxymethyl)acrylamide (viscous liquid); diacetone acrylamide (solid).
  • At least 50 wt.% of the contained (M) comprises an organic residue R1 which contains an aromatic group.
  • At least 50 wt.% of the contained (M) comprises an organic residue R1 which has at least 6 carbon atoms.
  • At least 50 wt.% of the contained (M) comprises an organic residue R1 which contains a substituted or non-substituted phenyl group.
  • at least 50 wt.% of the contained (M) is contributed by N-Phenyl acrylamide.
  • Phenyl acrylamide for example is a solid and should be solved in the component (N) entirely before its application.
  • the invention also concerns an object which has been prepared by a printing procedure as described above.
  • I BOA, SR506D Isobornylacrylate (I BOA, SR506D) - CAS No 5888-33-5 from ARKEMA
  • IBOMA Isobornylmethacrylate
  • ACMO Acryloyl morpholine
  • VMOX 5-Methyl-3-vinyl-2-oxazolidinone
  • TAGVE Triethylene glycol divinyl ether
  • TMPTA Trimethylolpropane triacrylate
  • Tricyclo [5.2.102,6]decanedimethanol dimethacrylate (TCDDMA, SR834) - CAS No 43048-08-4 from ARKEMA
  • Polyethylene glycol 600 diacrylate (PEG600DA, Miramer M286) - CAS No 26570-48-9 from Ml WON
  • Polyethylene glycol 400 diacrylate (PEG400DA, Miramer M280) - CAS No 26570-48-9 from Ml WON
  • Polyethylene glycol 550 di methacrylate (PEG550DMA, SR252) - CAS No 25852-47-5 from ARKEMA
  • Genomer4230 - aliphatic urethane diacrylate from RAHN
  • BDT-4330 mixture of dendritic acrylate, dipentaerythritol penta- /hexaacrylate and dipentaerythritol hexaacrylate from BOMAR BR941 - mixture of aliphatic urethane hexaacrylate and pentaerythritol tetraacrylate from BOMAR
  • Table 1 Viscosity measurements of reactive diluents.
  • Viscosity is measured on a thermally controlled rotational rheometer in cone-plate geometry (Anton Paar Physica MCR 300, cone diameter: 60 mm, zero-gap distance: 0,061 mm, cone angle: 0,5°, shear-rate 600s -1 ) at temperatures from 25 to 55°C with a heating ramp of 2 K/min following the DIN EN ISO 3219.
  • the viscosity at 25 or 50 °C is shown in the following examples.
  • the Shore hardness D was measured following the DIN EN ISO norm 7619 by a OS-2 measuring device from Hildebrand Pruf- und Messtechnik GmbH with cylindrical specimens in diameter of 40 mm and thickness of 6 mm. The results were taken off the scale after 3 seconds of placing the needle on the specimen. The measurement was repeated 5 times.
  • Tensile testing was performed on a Zwick-Roell tensile tester 1445 following the DIN EN ISO norm 527-1 with 5A specimen.
  • E-Modulus was determined from the slope of the stress-strain curve at deformations from 0.05-0.25 % at 1 mm/min. Tensile strength and elongation at break were determined by pulling the specimen at 5 mm/min.
  • the heat deflection temperature B (0.45 MPa) as a three-point-bending test was performed on a HDT-measuring device Compact 3 from Coesfeld on specimens with dimensions of 80 x 10 x 4 mm according to DIN EN ISO 75.
  • the heat rate was set to 2 K/min in a range from 30 °C until reaching the HDT-value.
  • the impact strength was measured using an IZOD set-up following DIN EN ISO norm 180 with notched specimens (notch base radius 0,25 mm and 8 mm remaining width at notch base) of dimensions of 80 x 10 x 4 mm and an impact pendulum of 1 J on a Zwick HIT5.5P Plus.
  • Resin printing was performed on a 405 nm LCD-printer SLS1s from Prusa.
  • Specimens were printed flat or vertically with 50 pm layer thickness. Each layer has a certain time of illumination which can vary from the illumination time of ten bottom layers. The detachment of specimens from bottom film was set in normal mode.
  • Inkjet printing was performed on a DP Polar inkjet printer using Xaar1003 printing heads and a 395 nm LED light source with an intensity of 12 W/cm 2 .
  • the layer thickness, printing speed and intensity of the light source may vary by each experiment.
  • Different devices were used for post-curing.
  • Thermal post-cure was carried out using an LIF55+ from Memmert placing one tray in the pre-heated chamber.
  • UV post-curing was performed using a LC-3DPrint Box (3D Sys) from 3D Systems or the curing station (atum) from atum3D with broad-spectrum UV lamps or a UVAcube 2000 mercury post-cure unit from Hbnle (Hg).
  • Table 3 Printing parameters, post-curing parameters and mechanical and thermomechanical characterization of resin compositions.
  • Table 4 Synthesis, viscosity and formulation ratios of inkjet compositions (I content (M) wt.%; II ratio (N):(M); III content (N)+(M) wt.%).
  • Table 5 Printing parameters, post-curing parameters and mechanical and thermomechanical characterization of inkjet compositions.
  • Comparative examples 27 - 29 stresses the importance of a defined reactive diluent to secondary acrylamide ratio. The higher the content of the secondary acrylamide, the higher the heat deflection temperature, but the lower the solubility in the mixture.
  • Example 25 is not a stable homogenous mixture over several weeks in storage conditions.
  • Table 6 Synthesis, viscosity and formulation ratios of resin compositions, molded (I content (M) wt.%; II ratio (N):(M); III content (N)+(M) wt.%).
  • IBOA ACMO:PEG600DA:TCDDA:iButoxymethylAAm:B 22 2 1.7 64.
  • APO Genorad16 [22.0:19.0:18.0:18.0:23.0:0.3:0.25] 3 8 0
  • Comparative examples 32, 34 and 35 show the influence of secondary acrylamides in potential resins and inks for printing applications in comparison to formulations only containing of acrylate and methacrylate compounds.
  • the content of the monofunctional secondary acrylamide was added onto the amount of a chosen reactive diluent.
  • Synthesis, processing and liquid as well as mechanical characterization was summarized in Table 8 and Table 9.
  • the compounds of said formulation were mixed and thoroughly stirred at elevated temperatures between 40 and 65 °C.
  • the resin was then printed on an open source SLS1s LCD-screen printer from PRLISA with 405 nm (printing parameters are shown in Table 8: 10x bottom layer illumination time/ time of illumination for each layer/ layer thickness). All vertically printed specimens were cleaned using deminerialized water, dried for 1 to 48 hours at standard atmosphere and post-cured with given different post-processings (Table 8).
  • Examples 33 to 35 show the difference of formulating with secondary acrylamide (33) in comparison to using a methacrylate moiety (34, 35).
  • methacrylates are reaching higher HDT B values than their counter acrylate compounds due to an intrinsic higher glass transition temperature. But with reaching high HDT values the brittleness in terms of elongation at break increases and less ductile materials with lower impact resistance follows. This contrasts with the good balance in impact resistance, flexibility, toughness to high HDT B values in resin and ink formulations composed by secondary acrylamides.
  • due to the lower reactivity towards LED light sources formulations containing methacrylates compared to highly reactive secondary acrylamides need a prolonged curing and therefore processing time.
  • Table 8 Synthesis, viscosity and formulation ratios of resin compositions (I content (M) wt.%; II ratio (N):(M); III content (N)+(M) wt.% ).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé d'impression dans lequel on imprime une composition A qui contient un photo-initiateur radicalaire (R) et au moins 18 % en poids de composé réactif de photopolymérisation (M) fourni par un acrylamide secondaire de structure de type H2C = CH-CO-NH-R1, avec R1 représenté par un résidu organique, le % en poids est par rapport au poids total de la composition A, où au moins deux couches de la composition A ont été imprimées les unes sur les autres et où le durcissement de la composition A est effectué par irradiation.
PCT/EP2025/064474 2024-06-14 2025-05-26 Impression d'un objet tridimensionnel Pending WO2025256902A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP24182217 2024-06-14
EP24182217.0 2024-06-14

Publications (1)

Publication Number Publication Date
WO2025256902A1 true WO2025256902A1 (fr) 2025-12-18

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PCT/EP2025/064474 Pending WO2025256902A1 (fr) 2024-06-14 2025-05-26 Impression d'un objet tridimensionnel

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Country Link
WO (1) WO2025256902A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004096514A2 (fr) 2003-04-29 2004-11-11 Objet Geometries Ltd. Compositions et procede convenant pour l'impression de maquettes en trois dimensions
US20200157265A1 (en) * 2018-11-19 2020-05-21 Sivapackia Ganapathiappan Low Viscosity UV-Curable Formulation For 3D Printing
US20240059823A1 (en) * 2018-10-22 2024-02-22 Canon Kabushiki Kaisha Curable resin composition and cured product thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004096514A2 (fr) 2003-04-29 2004-11-11 Objet Geometries Ltd. Compositions et procede convenant pour l'impression de maquettes en trois dimensions
US20240059823A1 (en) * 2018-10-22 2024-02-22 Canon Kabushiki Kaisha Curable resin composition and cured product thereof
US20200157265A1 (en) * 2018-11-19 2020-05-21 Sivapackia Ganapathiappan Low Viscosity UV-Curable Formulation For 3D Printing

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
no. 162881-26-7

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