EP4355802A1 - Procédé de fabrication additive pour la production d'articles tridimensionnels - Google Patents

Procédé de fabrication additive pour la production d'articles tridimensionnels

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Publication number
EP4355802A1
EP4355802A1 EP22734910.7A EP22734910A EP4355802A1 EP 4355802 A1 EP4355802 A1 EP 4355802A1 EP 22734910 A EP22734910 A EP 22734910A EP 4355802 A1 EP4355802 A1 EP 4355802A1
Authority
EP
European Patent Office
Prior art keywords
composition
weight
novolak
formaldehyde
reaction temperature
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
EP22734910.7A
Other languages
German (de)
English (en)
Inventor
Robert Liska
Raffael Johannes Bodo Andre WOLFF
Patrick KNAACK
Jürgen STAMPFL
Katharina Ehrmann
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.)
Technische Universitaet Wien
Original Assignee
Technische Universitaet Wien
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 Technische Universitaet Wien filed Critical Technische Universitaet Wien
Publication of EP4355802A1 publication Critical patent/EP4355802A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—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
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—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
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2061/00—Use of condensation polymers of aldehydes or ketones or derivatives thereof, as moulding material
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • 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

Definitions

  • the present invention relates to additive manufacturing processes for producing three-dimensional objects using photopolymerizable compositions comprising phenol-formaldehyde resins.
  • the phenolic resins obtained by hardening phenolic resins are among the first industrially produced plastics, with the first phenol-formaldehyde resin, invented back in 1907, still being sold today under the Bakelite brand name. These polycondensates are known for their chemical resistance, excellent flame properties and thermal stability, which is why they are used in space, aviation and the automotive industry, among other things. Due to the relatively large amounts of water formed during polycondensation, molding processing with simultaneous curing of phenolic resins usually takes place not only at elevated temperatures to promote condensation, but also under very high pressures of sometimes even over 150 bar to prevent the water from evaporating and escaping, which can otherwise lead to the formation of bubbles. In addition, processing was mainly limited to injection molding and melt pressing, with chipboard being one of the best-known examples of products based on phenol-formaldehyde resins as binders.
  • These materials are based on reactive components that are cured by heating or exposure to light, where radical (eg for acrylates) or cationic (eg for epoxides) polymerization are usually used.
  • Photoinitiators are added to the resin for light-induced curing in order to initiate the polymerization of the reactive components.
  • WO 2015/074088 A2 discloses photopolymerizable compositions with a dynamic viscosity at room temperature of at least 20 Pa.s, which are heated to at least 30° C. during curing (“hot lithography”). For comparison: 20 Pa.s roughly corresponds to the viscosity of ethylene glycol or viscous honey, while butter with a viscosity of around 30 Pa.s is barely flowable.
  • compositions comprising phenolic resins that are said to be suitable for 3D printing. These each comprise a thermally curable novolak resin, a low molecular weight second resin selected from phenolic resins, polyvinyl alcohols and polyacrylates, diisocyanates as chain extenders, allyl or buteneamine as capping agents, polyunsaturated fatty acids as crosslinkers and toughness and strength modifiers.
  • compositions are prepared in a twin screw extruder by mixing the two resins together, heating the mixture above 150°C to melt them, sequentially adding the chain extender, capping agent, crosslinker and enhancers, and extruding and pelletizing the mixture.
  • the granules are processed into three-dimensional bodies using the 3D printing process known as "melt extrusion accumulation molding", in which layers of the remelted granules are applied one after the other and solidified by cooling. Photopolymerization is thus not mentioned therein.
  • RU 2699556 C1 from 2019 discloses mixtures of a special phenolic resin modified with propargyl halide groups, a photopolymerizable vinyl ester resin based on bisphenol A and a free-radical photoinitiator. To process these mixtures, the vinyl ester resin is first photopolymerized by exposure, after which the modified phenolic resin is thermally cured in the solid product thus obtained.
  • Both resoles and novolaks are disclosed as suitable phenolic resins and the production of polymer films, three-dimensional products and prototypes by means of stereolithography is mentioned as possible applications. In fact, however, the respective mixtures are only introduced between two glass plates and subsequently cured in two stages, ie by initial exposure to light and subsequent heating.
  • JP 2019/203097 A discloses specific Novo Cresol-based lak resins with some 1-ethoxyethyl-protected OH groups for use in photoresists.
  • US 2002/076651 A1 discloses compositions for thick-film photoresists in which "epoxidized polyfunctional bisphenol-A-formaldehyde novolak resins" are used, i.e. novolak resins modified with several, preferably eight, epoxy groups per molecule, which are decisive for the polyaddition to epoxy resins; and also WO 2017/112653 A1 discloses - in addition to a large number of other resins - also epoxidized phenol-formaldehyde resin for use in photopolymerizable compositions. The latter, however, comprise two different polymerizable precursor compositions, which should preferably result in the flattening of interpenetrating polymer networks (IPN).
  • IPN interpenetrating polymer networks
  • resoles can also be used as precursors of such resins to be epoxidized.
  • more or less strongly crosslinked epoxy resins are obtained in the curing brought about by means of photoacid generators, which comprise the respective phenolic resin components (or according to WO 2017/112653 A1: can comprise).
  • the aim of the present invention was the development of photopolymerizable compositions from which, by means of additive manufacturing processes, i.e. 3D printing, three-dimensional moldings with improved mechanical properties compared to the prior art can be obtained.
  • a photopolymerizable composition comprising a phenol-formaldehyde resin, a hardener and a photoinitiator in an additive manufacturing process for the production of three-dimensional objects by means of layer-by-layer exposure to harden the composition, wherein the method is characterized in that a) the composition is heated to a reaction temperature of at least 70°C before and during the curing; b) the composition b1) comprises a novolak as the phenol-formaldehyde resin, b2) a formaldehyde derivative which is stable at the reaction temperature as the curing agent and b3) a photoacid generator as the photoinitiator; and c) the curing of the composition is carried out at atmospheric pressure;
  • the novolak comprises essentially no other functionalities participating in the photopolymerization apart from the OH groups;
  • the hardener is not an amine-containing formaldehyde derivative.
  • the invention provides an additive manufacturing process for the production of three-dimensional objects by means of layered exposure for curing a photopolymerizable composition comprising a phenol-formaldehyde resin, a hardener and a photoinitiator, which, as mentioned above, is characterized in that a) the composition is heated to a reaction temperature of at least 70°C before and during curing; b) the composition b1) a novolak as phenol-formaldehyde resin which has a viscosity of not more than 20 Pa.s at the reaction temperature, b2) a formaldehyde derivative stable at the reaction temperature as hardener and b3) a photoacid generator as photoinitiator includes; and c) the curing of the composition is carried out at atmospheric pressure; with the proviso that the hardener is not an amine-containing formaldehyde derivative.
  • the inventors have surprisingly found that in the photoacid-initiated polycondensation of novolaks, i.e. phenolic resins with a formaldehyde-phenol ratio of less than 1:1, with simultaneous crosslinking with formaldehyde derivatives, even at reaction temperatures above 100° C., no increased Pressure needs to be applied to prevent the water formed by the condensation reactions from escaping. Without wishing to be bound by any particular theory, the inventors believe that this is due to the high curing rates of the photopolymerizable compositions in the process of the invention.
  • novolaks i.e. phenolic resins with a formaldehyde-phenol ratio of less than 1:1
  • relatively high-molecular novolaks can also be used as starting resins, while the reaction mixtures remain mixable, e.g than 20 Pa.s.
  • the reaction mixtures remain mixable, e.g than 20 Pa.s.
  • a viscosity of 20 Pa.s roughly corresponds to that of ethylene glycol or viscous honey. Nevertheless, novolaks which have a viscosity in the range of this limit value at the reaction temperature can be used without any problems according to the present invention, sometimes by adding a defined (small) amount of low molecular weight novolak or one or more other viscosity-reducing additives, preferably if required however, by using a formaldehyde derivative as a hardener, which is in the liquid state at the reaction temperature.
  • the mold used as a hardener Aldehyde derivative preferably selected from polyoxymethylene, polyoxymethylene diesters, polyoxymethylene diethers and derivatives of 1,3-dioxolane and 1,3-dioxane, more preferably from 4-phenyl-1,3-dioxane and polyoxymethylene diacetate and other polyoxymethylene diesters , which on the one hand are liquid at the respective reaction temperature and, in the case of the diesters, also consume two molecules of water in the case of acid-catalyzed cleavage of the diester molecule.
  • all of these hardeners are thermally stable in that they do not release any formaldehyde at the respective reaction temperature as long as the reaction mixture has not been exposed to light to split the photoacid generator.
  • This is an essential feature of the present invention with regard to the shape accuracy of the three-dimensional objects to be produced additively.
  • amine-containing formaldehyde derivatives such as hexamethylenetetramine
  • ammonia are released, which can neutralize the photoacid in the process according to the invention present invention excluded.
  • a novolak which at the reac tion temperature has a viscosity of not more than 10 Pa.s, not more than 5 Pa.s or not more than 1 Pa.s in order not to be too severely restricted with regard to the selection of the hardener and/or to be able to add further additives, such as other, e.g. also relatively high molecular weight, resins to the reaction mixture. According to the invention, however, the latter is to be preferred only in certain cases.
  • the novolak used according to the present invention contains essentially no - and preferably none at all - apart from the OH groups, other functionalities participating in the photopolymerization, so that curing takes place almost exclusively through polycondensation between the phenol groups of the novolak and the formaldehyde groups of the harder.
  • "essentially none” is to be understood herein that only in exceptional cases a small proportion of such other functionalities may be contained in order to slightly modify, if necessary, a specific parameter of the polycondensates obtained.
  • a small proportion is to be understood here as a single-digit mole percentage, based on the average number of OH groups in the novolak, such as, for example, 1 to 5 or 1 to 2 mole %.
  • the photoacid generator used as a photoinitiator according to the present invention is not specifically restricted, so that in principle all compounds that are conventionally used and are commercially available are suitable.
  • the photoacid generator is preferably selected from diaryliodonium and triarylsulfonium salts, more preferably from their hexafluoroantimonate, tetrafluoroborate and tetrakis(pentafluorophenyl)borate salts, which have proven themselves in the past as photoacid generators under a wide variety of reaction conditions and also with exposure release extremely strong acids, sometimes even superacids.
  • the wavelength used for exposure also depends on the choice of photoacid generator.
  • the composition is heated to a reaction temperature not higher than 130°C in order not to induce thermal decomposition of individual components and to limit energy consumption.
  • a particularly preferred reaction temperature range according to the invention is 80.degree. C. to 120.degree.
  • composition according to the present invention can also include other monomers and/or prepolymers that are capable of copolymerizing with the novolak and/or the hardener, and optionally, as already mentioned, also include one or more other additives, to optimize the properties of the reac tion mixtures and/or the three-dimensional objects produced.
  • the composition can, for example, contain vinyl ester, epoxy, furan, melamine-formaldehyde or urea-formaldehyde resins or polyol, saturated or unsaturated polyester resins and alkyd resins as prepolymers and/or bis phenol A diglycidyl ether (“BADGE”), 3,4-epoxycyclohexanecarboxylic acid 3 ⁇ 4'-epoxy-cyclohexylmethyl ester (“CE”), or another epoxide as a comonomer.
  • BADGE bis phenol A diglycidyl ether
  • CE 3,4-epoxycyclohexanecarboxylic acid 3 ⁇ 4'-epoxy-cyclohexylmethyl ester
  • another epoxide as a comonomer.
  • one or more carboxylic anhydrides can be added to the polymerizable composition as additives, which are preferably selected from dicarboxylic anhydrides, more preferably from phthalic anhydride, butanedicarboxylic anhydride, maleic anhydride and cyclohexane-1,2-dicarboxylic anhydride. These also act as water scavengers, among other things, by binding the water released during the condensation reactions.
  • Other suitable additives are, for example, the fillers customary in phenolic resins, as well as dyes and pigments, which can each be used in amounts such that the properties of the composition or the three-dimensional object obtained therefrom are not impaired.
  • inorganic and organic fillers can be used as fillers, such as glass fibers, glass beads, clay minerals, silicates (silicic acid, quartz, talc, mica), carbonates, iron powder, silanes, graphite, graphene, cork, carbon fibers, felt flour, felt fibers , cotton fibers, lignin, cellulose (fibers), duromers, thermoplastic fibers, organoborates and organophosphates, just to name a few.
  • the composition comprises 30 to 90% by weight novolak, 10 to 50% by weight hardener and 1 to 10% by weight photoacid generator, in particularly preferred embodiments 50 to 80% by weight novolak, 20 to 40% by weight of hardener and about 5% by weight of photoacid generator, in each case in proportions such that their total is 100% by weight.
  • One or more other monomers and / or prepolymers can be added, for example, in such amounts that they up to 50% of Replace quantity of novolak.
  • carboxylic acid anhydrides serving as water scavengers as additives can be contained, for example, in proportions of 5 to 25% by weight, based on 100% by weight as the sum of all components, preferably in proportions of 10 to 20% by weight. .
  • the generative manufacturing process is preferably a 3D printing process and more preferably a hot lithography (“Hot Lithogra- phy”) process, by means of which three-dimensional objects with excellent mechanical properties can be produced very quickly and extremely accurately, usually by laser exposure , can be produced.
  • Hot Lithogra- phy hot lithography
  • the present invention also provides three-dimensional objects obtained by the new inventive method defined above, having improved mechanical properties compared to the prior art.
  • the sole figure 1 is a photograph of three-dimensional objects produced in the examples according to the invention.
  • composition components indicated below were each mixed in a container with stirring and heating up to 80°C until a homogeneously distributed mixture was obtained which, on cooling to room temperature, was used in all cases where a novolak was used as the phenolic resin , a highly viscous, became a substantially solid mass, while the comparative example using resole remained liquid even after cooling.
  • a construction platform is first immersed in the liquefied composition from above up to a defined distance from the bottom of the tub. This distance corresponds to the thickness of a layer to be hardened, which in turn depends on the depth of penetration of the light into the respective composition. In the examples, layer thicknesses of 50-100 ⁇ m were set for this.
  • the UV laser then scans the underside of the composition through the transparent tank floor under computer control at a speed of up to 1000 mm/s in order to harden the first layer, after which the construction platform is raised by the amount corresponding to the layer thickness so that fresh liquid formulation can flow between the hardened layer and the bottom of the tank, which in turn is then exposed and thereby hardened, etc.
  • the phenolic resin used as the novolak was, in most of the examples, Supraplast 3616 ("Novolak 1") from Süd-West-Chemie GmbH in Neu-Ulm, Germany, which has a number-average molecular weight Mn of 341, a weight-average molecular weight Mw of 474 and, according to the manufacturer, has a melting range of 30-50 °C, a melt viscosity at 50 °C of 200-400 Pa.s and a melt viscosity at 80 °C of 2-8 Pa.s.
  • Example 5 used phenolic resin was Supraplast 052 ("Resol”) from Süd-West-Chemie GmbH, a viscous at room temperature (dynamic viscosity at 20 ° C up to 18 Pa.s), self-condensing resol resin, which according to the manufacturer a gel time at 100 °C of 70-90 min and an initial boiling point > 100 °C.
  • Resol Supraplast 052
  • a viscous at room temperature dynamic viscosity at 20 ° C up to 18 Pa.s
  • self-condensing resol resin which according to the manufacturer a gel time at 100 °C of 70-90 min and an initial boiling point > 100 °C.
  • PAG 1 HRcure-9392 by Tianjin Huiren Chemtech Co., Ltd; 4-(Octyloxy)phenyl)-(phenyl)iodonium hexafluoroantimonate
  • PAG 2 SpeedCure 937 from Lambson Limited; Bis(4-dodecylphenyl)iodonium hexafluoroantimonate
  • PAG 3 SpeedCure 976s from Lambson Limited; Sulfandiyldibenzene-4,1-diyl)-bis-(diphenylsulfonium)-bis(hexafluoroantimonate)
  • PAG 4" Irgacure 290 from BASF Corporation; (4-(4-Acetylphenylthio)phenyl)sulfonium tetrakis(pentafluorophenyl)borate
  • the prepolymers capable of copolymerization used in Examples 17 and 18 were Epilok 60-838 ("Prepolymer 1"), an epoxidized novolak resin from Bitrez Ltd. with a dynamic viscosity at 50 °C of around 40 Pa.s and at 70 °C of around 5 Pa.s, in Example 19 Supraplast 680/95 (“prepolymer 2”), a melamine-formaldehyde resin from Süd-West -Chemie GmbH with a melting range of 70-95 °C, and in example 20 Deuteron SF 707 (“prepolymer 3”), a liquid at room temperature Fl arn substance-formaldehyde Flarz Deuteron GmbFI in Achim, Germany, used.
  • Prepolymer 1 Epilok 60-838
  • Prepolymer 2 an epoxidized novolak resin from Bitrez Ltd. with a dynamic viscosity at 50 °C of around 40 Pa.s and at 70 °C of around 5 Pa.s
  • Hardeners The hardeners used in the formulations are listed in Table 1 overleaf together with the other components, ie the phenolic resin (“Flarz”), the photoacid generator (“PAG”) and any comonomers/prepolymers “CoM/Prä") Proportions in the tested formulations (in % by weight of the total composition) and the respective reaction temperatures (in °C) for Examples 1 to 22 according to the invention ("B1" to “B22”) and Comparative Examples 1 to 5 (“V1" to "V5").
  • the desired object could be printed without any problems from the formulations listed above for Examples 1 to 22 according to the invention, which consisted in each case of a hard duromer with the stated composition that was no longer deformable even when heated and was infusible.
  • the inventors attribute this negative result to the fact that the large amounts of ammonia released during the decomposition of hexamethylenetetramine neutralize the photoacid formed by exposure to light, which means that it no longer triggers the Polycondensation of the novolak is able. For this reason, those amine-containing hardeners which liberate ammonia when they decompose are excluded from the scope of the present invention. It was also surprising that no solid object could be printed with the resol resin considered to be self-condensing in comparison example 5 in combination with 10% by weight of photo acid generator - without formaldehyde flair be attributed to low reaction temperatures in the 3D printing process.
  • the additive manufacturing process according to the invention preferably 3D printing processes, can be used for the first time to produce three-dimensional objects based on formaldehyde-crosslinked novolak duromers with excellent mechanical properties, without other binders or co-flares need to be added - although according to the present invention this option also exists.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)

Abstract

L'invention concerne l'utilisation d'une composition photopolymérisable comprenant une résine phénol-formaldéhyde, un agent de durcissement et un photoinitiateur dans un procédé de fabrication additive pour la production d'articles tridimensionnels au moyen d'une exposition couche par couche pour le durcissement de la composition, présentant des caractéristiques de caractérisation telles que a) la composition est chauffée à une température réactionnelle d'au moins 70 °C avant et pendant le durcissement ; b) la composition comprend b1) une novolaque en tant que résine phénol-formaldéhyde, b2) un dérivé du formaldéhyde en tant qu'agent de durcissement qui est stable à la température réactionnelle , et b3) un agent de formation de photoacides en tant que photo-initiateur ; et c) le durcissement de la composition est conduit à une pression standard ; à condition que l'agent de durcissement ne soit pas un dérivé du formaldéhyde contenant une amine.
EP22734910.7A 2021-06-14 2022-06-14 Procédé de fabrication additive pour la production d'articles tridimensionnels Pending EP4355802A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA112/2021A AT525128B1 (de) 2021-06-14 2021-06-14 Generative Fertigungsverfahren zur Herstellung von dreidimensionalen Gegenständen
PCT/EP2022/066196 WO2022263454A1 (fr) 2021-06-14 2022-06-14 Procédé de fabrication additive pour la production d'articles tridimensionnels

Publications (1)

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EP4355802A1 true EP4355802A1 (fr) 2024-04-24

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US (1) US20240287304A1 (fr)
EP (1) EP4355802A1 (fr)
AT (1) AT525128B1 (fr)
WO (1) WO2022263454A1 (fr)

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CN119391170B (zh) * 2025-01-02 2025-03-28 广州简米餐具有限公司 一种环保密胺复合材料及其制备方法

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US6391523B1 (en) * 2000-09-15 2002-05-21 Microchem Corp. Fast drying thick film negative photoresist
AT515138B1 (de) 2013-11-22 2016-05-15 Univ Wien Tech Vorrichtung zum Verarbeiten von photopolymerisierbarem Material zum schichtweisen Aufbau eines Formkörpers
EP2875934B1 (fr) 2013-11-22 2017-04-05 Technische Universität Wien Dispositif de traitement de matériau photopolymérisable pour le montage en couche d'un corps moulé
CN103980657B (zh) 2014-04-30 2015-08-05 中国科学院化学研究所 一种3d打印改性酚醛树脂材料及其制备方法
EP3023226B1 (fr) 2014-11-19 2017-02-08 Ivoclar Vivadent AG Dispositif de stéréo-lithographie et dispositif de chauffage
CN108139665B (zh) * 2015-12-22 2022-07-05 卡本有限公司 用于用双重固化树脂的增材制造的双重前体树脂系统
JP7095405B2 (ja) 2018-05-25 2022-07-05 住友ベークライト株式会社 感光性樹脂組成物用のノボラック型フェノール樹脂
RU2699556C1 (ru) 2019-03-18 2019-09-06 Акционерное общество "Институт новых углеродных материалов и технологий" (АО "ИНУМиТ") Отверждаемая полимерная композиция и способ изготовления из неё отверждённого продукта

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WO2022263454A1 (fr) 2022-12-22
AT525128A1 (de) 2022-12-15
US20240287304A1 (en) 2024-08-29
AT525128B1 (de) 2023-12-15

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