FR3124420A1 - Use of multi-block copolymers as a sacrificial material in a 3D printing process - Google Patents

Use of multi-block copolymers as a sacrificial material in a 3D printing process Download PDF

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Publication number
FR3124420A1
FR3124420A1 FR2106675A FR2106675A FR3124420A1 FR 3124420 A1 FR3124420 A1 FR 3124420A1 FR 2106675 A FR2106675 A FR 2106675A FR 2106675 A FR2106675 A FR 2106675A FR 3124420 A1 FR3124420 A1 FR 3124420A1
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Prior art keywords
monomers
block
use according
copolymer
varying
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FR2106675A
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French (fr)
Inventor
Anne-Laure Brocas
Sylvie Cazaumayou
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Arkema France SA
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Arkema France SA
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Priority to FR2106675A priority Critical patent/FR3124420A1/en
Priority to FR2110633A priority patent/FR3124421B1/en
Priority to PCT/FR2022/051148 priority patent/WO2022269167A1/en
Priority to KR1020247002144A priority patent/KR20240024944A/en
Publication of FR3124420A1 publication Critical patent/FR3124420A1/en
Pending legal-status Critical Current

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    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • 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
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D 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 [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Abstract

TITRE : Utilisation de copolymères multi blocs en tant que matériau sacrificiel dans un procédé d’impression 3D La présente invention se rapporte à l’utilisation de copolymères multi blocs en tant que matériaux sacrificiel du modelage en 3D par dépôt de filaments en fusion.TITLE: Use of Multiblock Copolymers as a Sacrificial Material in a 3D Printing Process The present invention relates to the use of multiblock copolymers as sacrificial materials in 3D modeling by melt filament deposition.

Description

Utilisation de copolymères multi blocs en tant que matériau sacrificiel dans un procédé d’impression 3DUse of multi-block copolymers as a sacrificial material in a 3D printing process

DOMAINE DE L'INVENTIONFIELD OF THE INVENTION

La présente invention se rapporte à l’utilisation de copolymères multi blocs en tant que matériaux sacrificiel du modelage en 3D par dépôt de filaments en fusion. Seuls les copolymères à blocs sont utilisés dans cette invention. Ceci exclu tout autre polymère à architecture ne se présentant pas sous forme de copolymères à blocs.The present invention relates to the use of multiblock copolymers as sacrificial materials for 3D modeling by deposition of molten filaments. Only block copolymers are used in this invention. This excludes any other polymer with an architecture not in the form of block copolymers.

De tels matériaux présentent une solubilisation ou une dispersibilité rapide dans une variété de solvant tout en combinant les propriétés thermomécaniques idéales pour en faire des fils ou joncs utilisables en impression 3D (modelage par dépôt de filaments en fusion) pour supporter des polymères constitutifs de la pièce à fabriquer, y compris des polymères de haute température de transition vitreuse (Tg), avant d’être éliminés par dissolution dans un solvant.Such materials exhibit rapid solubilization or dispersibility in a variety of solvents while combining the ideal thermomechanical properties to make wires or rods that can be used in 3D printing (modeling by deposition of molten filaments) to support the constituent polymers of the part. to be manufactured, including polymers with a high glass transition temperature (Tg), before being eliminated by dissolution in a solvent.

L’impression tridimensionnelle (ou impression 3D) permet de fabriquer de manière additive (en anglais : « additive manufacturing » ou AM) un objet réel à partir d’un objet virtuel. Elle est basée sur la découpe de l'objet virtuel 3D en lamelles 2D de très fine épaisseur. Ces fines lamelles sont déposées une à une en les fixant sur les précédentes, ce qui reconstitue l'objet réel. Parmi les matériaux constitutifs de l’objet, on trouve les matériaux plastique (notamment l'acrylonitrile butadiène styrène (ou ABS) et l’acide polylactique (ou PLA)), mais aussi des Polyaryleetheréctones (PAEK), Poletheryimides (PEI), la cire, le métal ou les céramiques. Des exemples de techniques additives sont le dépôt de filaments en fusion (« Fuse filament fabrication » (FFF)) et le frittage par laser (en anglais « laser sintering »).Three-dimensional printing (or 3D printing) makes it possible to manufacture in an additive manner (in English: "additive manufacturing" or AM) a real object from a virtual object. It is based on cutting the 3D virtual object into very thin 2D strips. These thin strips are deposited one by one by fixing them on the previous ones, which reconstitutes the real object. Among the constituent materials of the object, we find plastic materials (in particular acrylonitrile butadiene styrene (or ABS) and polylactic acid (or PLA)), but also Polyaryleetherectones (PAEK), Poletheryimides (PEI), wax, metal or ceramics. Examples of additive techniques are the deposition of molten filaments (“Fuse filament fabrication” (FFF)) and laser sintering (“laser sintering”).

Le modelage par dépôt de filaments en fusion est une technique qui consiste à faire fondre un filament à travers une buse d’extrusion. De cette buse en sort un filament en fusion, d'un diamètre de l'ordre du millimètre. Ce fil est déposé en ligne et vient se coller par re-fusion sur ce qui a été déposé au préalable. Cette technique permet de créer des pièces en bonne matière, disposant de caractéristiques mécaniques, thermiques et d’une stabilité identique aux pièces thermoplastiques injectées et souvent plus légères. Dans le cas des polymères, pour des raisons de consolidation mécanique, cette technique nécessite un support à la production des pièces, lui aussi extrudé conjointement. Ce support de construction est constitué dans une autre matière que celle constitutive de l’objet créé, support qui est éliminée dudit objet, lorsque le processus de construction de ce dernier est fini.Modeling by molten filament deposition is a technique that consists of melting a filament through an extrusion nozzle. From this nozzle emerges a molten filament, with a diameter of the order of a millimeter. This wire is deposited in line and comes to stick by re-fusion on what was deposited beforehand. This technique makes it possible to create parts in good material, with mechanical and thermal characteristics and stability identical to injected thermoplastic parts and often lighter. In the case of polymers, for reasons of mechanical consolidation, this technique requires a support for the production of the parts, also extruded together. This construction support is made of a material other than that constituting the created object, a support which is eliminated from said object, when the process of construction of the latter is finished.

Le support de construction est généralement une composition polymérique soluble ou dispersible répondant à un cahier des charges bien précis. Parmi les propriétés recherchées, outre la résistance mécanique, la température de transition vitreuse du copolymère qui doit être proche du matériau à imprimer, sa stabilité thermique ou sa facilité de mise en œuvre, la cinétique de solubilisation ou de dispersion dans une varité de solvant et en particulier de l’eau est de première importance. Le matériau doit en outre présenter une bonne conservation, lorsque le solvant de solubilisation ou de dispersion est l’eau. Cette dernière caractéristique n’est pas toujours facile à établir car les compositions et filaments hydrosoluble ou hydrodispersibles dans l’eau peuvent s’avérer difficile à conserver en atmosphère humide. On observe des prises en masse des granulés ou un collage des filaments sur les bobines dû à la présence d’humidité ambiante lors du stockage.The construction support is generally a soluble or dispersible polymeric composition meeting very specific specifications. Among the properties sought, in addition to the mechanical resistance, the glass transition temperature of the copolymer which must be close to the material to be printed, its thermal stability or its ease of implementation, the kinetics of solubilization or dispersion in a variety of solvent and especially water is of prime importance. The material must also exhibit good preservation, when the solvent for solubilization or dispersion is water. This last characteristic is not always easy to establish because water-soluble or water-dispersible compositions and filaments in water can prove difficult to preserve in a humid atmosphere. Clumping of the granules or sticking of the filaments on the coils is observed due to the presence of ambient humidity during storage.

ARRIERE-PLAN TECHNIQUETECHNICAL BACKGROUND

Cette technique d’impression 3D, nécessite des matériaux supports permettant la construction de pièces complexes, ceci est par exemple décrit dans WO2010/045147. Parmi les autres matériaux supports solubles dans l’eau, on retrouve :This 3D printing technique requires support materials allowing the construction of complex parts, this is for example described in WO2010/045147. Other water-soluble support materials include:

  • Le polyvinyl alcoolpolyvinyl alcohol
  • Le BVOH copolymère butènediol/alcool vinylique.BVOH butenediol/vinyl alcohol copolymer.
  • Les copolymères (méth)acryliques.(Meth)acrylic copolymers.

Ces compositions de polymères supports comprennent toujours plusieurs copolymères, dont le rôle est d’ajuster solubilité, propriétés mécaniques ou d’autres paramètres, en résultant plus de difficultés de mise au point.These support polymer compositions always include several copolymers, whose role is to adjust solubility, mechanical properties or other parameters, resulting in more development difficulties.

Parmi les autres matériaux supports solubles dans d’autres solvants, on peut citer par exemple le polystyrène impact (HIPS), soluble dans le limonène.Other support materials soluble in other solvents include, for example, impact polystyrene (HIPS), soluble in limonene.

Il est connu dans l’art antérieur que le support doit présenter une température de transition vitreuse (Tg) relativement proche de celle du polymère constitutif de l’objet à imprimer dans un ordre de grandeur inférieur de 10°C de la Tg du polymère constitutif de l’objet à imprimer.It is known in the prior art that the support must have a glass transition temperature (Tg) relatively close to that of the constituent polymer of the object to be printed in an order of magnitude less than 10°C of the Tg of the constituent polymer of the object to be printed.

Dans le cas contraire, la construction de la pièce à imprimer ne se fait pas correctement car le matériau support présente trop de fluage. Ceci est expliqué par exemple dans US5866058.Otherwise, the construction of the part to be printed is not done correctly because the support material has too much creep. This is explained for example in US5866058.

De façon surprenante, la demanderesse a constaté que lorsque les copolymères à blocs sont utilisés seuls ou en combinaison comme matériau support sacrificiel, cette condition de proximité des Tg matériaux à imprimer-matériau support n’est plus nécessaire. Cela présente un avantage car la définition des autres caractéristiques du polymère support présente beaucoup plus de possibilités. Il est ainsi plus facile d’ajuster les autres paramètres tels que mécaniques ou de solubilisation en milieu aqueux sans se soucier des Tg du polymère sacrificiel support, à conditions qu’elles restent inférieures à celle du polymère constitutif de l’objet à imprimer. Ainsi avec des copolymères à blocs dont la tg la plus haute d’un des blocs est par exemple de 50°C, on peut utiliser de tels copolymères à blocs comme matériau support pour construire des objets en matériau de Tg allant de 50°C à 200°C.Surprisingly, the Applicant has found that when the block copolymers are used alone or in combination as a sacrificial support material, this condition of proximity of the Tg materials to be printed-support material is no longer necessary. This has an advantage because the definition of the other characteristics of the support polymer presents many more possibilities. It is thus easier to adjust the other parameters such as mechanical or solubilization in an aqueous medium without worrying about the Tg of the sacrificial polymer support, provided that they remain lower than that of the constituent polymer of the object to be printed. Thus with block copolymers of which the highest tg of one of the blocks is for example 50°C, it is possible to use such block copolymers as a support material for constructing objects in material with a Tg ranging from 50°C to 200°C.

Ceci offre de nouvelles possibilités pour imprimer des objets constitués de poly aryle éther cétones (PAEK), de polyéther imides (PEI), de polamide-imide (PAI), Polysulfone (PSU), poly(ethersulfone) (PES), poly(phenylene sulfide) (PPS) pour lesquels le choix de polymères sacrificiels support est très limité et présente d’autres désavantages.This offers new possibilities for printing objects made of poly aryl ether ketones (PAEK), polyether imides (PEI), polamide-imide (PAI), Polysulfone (PSU), poly(ethersulfone) (PES), poly(phenylene sulfide) (PPS) for which the choice of supporting sacrificial polymers is very limited and has other disadvantages.

L’invention concerne l’utilisation d’au moins un copolymère multi blocs en tant que matériau sacrificiel dans un procédé d’impression 3D de polymères dont la Tg est comprise entre 50 et 200 °C, au moins un copolymère(s) multi blocs comprenant au moins un bloc constitué de i monomères Mienchaînés de façon statistique, i étant un nombre entier variant de 2 à 5, bornes incluses et d’au moins un bloc constitué de j monomères Mjenchaînés de façon statistique, j étant un nombre entier variant de 2 à 5, bornes incluses , Miétant sélectionné parmi des monomères A dont la Tg de leurs homopolymères est inférieure à 0°C et des monomères B hydrophiles , la proportion massique de A variant de 80 à 95 % et la proportion massique de B variant de 5 à 20 %.The invention relates to the use of at least one multiblock copolymer as sacrificial material in a process for 3D printing of polymers whose Tg is between 50 and 200°C, at least one multiblock copolymer(s) comprising at least one block consisting of i monomers M i linked in a statistical manner, i being an integer varying from 2 to 5, limits included, and of at least one block consisting of j monomers M j linked in a statistical manner, j being a whole number varying from 2 to 5, limits included, M i being selected from A monomers whose Tg of their homopolymers is less than 0°C and hydrophilic B monomers, the mass proportion of A varying from 80 to 95% and the mass proportion of B varying from 5 to 20%.

Mjétant sélectionné parmi des monomères C dont la Tg de leurs homopolymères est inférieure à 0°C, des monomères D dont la Tg de leurs homopolymères est supérieure à 25°C et des monomères E hydrophiles, les proportions massiques des monomères C, D, E étant comprises respectivement entre 25-35 %, 25-35 %, 35-45 %.M j being selected from C monomers whose Tg of their homopolymers is less than 0°C, D monomers whose Tg of their homopolymers is greater than 25°C and hydrophilic E monomers, the mass proportions of the monomers C, D , E being respectively between 25-35%, 25-35%, 35-45%.

Claims (9)

Utilisation d’au moins un copolymère multi blocs en tant que matériau sacrificiel dans un procédé d’impression 3D de polymères dont la Tg est comprise entre 50 et 200 °C, au moins un copolymère(s) multi blocs comprenant au moins un bloc constitué de i monomères Mienchaînés de façon statistique, i étant un nombre entier variant de 2 à 5, bornes incluses et d’au moins un bloc constitué de j monomères Mjenchaînés de façon statistique, j étant un nombre entier variant de 2 à 5, bornes incluses , Miétant sélectionné parmi des monomères A dont la Tg de leurs homopolymères est inférieure à 0°C et des monomères B hydrophiles , la proportion massique de A variant de 80 à 95 % et la proportion massique de B variant de 5 à 20 %.
Mjétant sélectionné parmi des monomères C dont la Tg de leurs homopolymères est inférieure à 0°C, des monomères D dont la Tg de leurs homopolymères est supérieure à 25°C et des monomères E hydrophiles, les proportions massiques des monomères C, D, E étant comprises respectivement entre 25-35 %, 25-35 %, 35-45 %.Use of at least one multiblock copolymer as sacrificial material in a process for 3D printing of polymers whose Tg is between 50 and 200°C, at least one multiblock copolymer(s) comprising at least one block consisting of i monomers M i linked in a statistical manner, i being an integer varying from 2 to 5, limits included, and of at least one block consisting of j monomers M j linked in a statistical manner, j being an integer varying from 2 to 5, limits included, M i being selected from A monomers whose Tg of their homopolymers is less than 0°C and hydrophilic B monomers, the mass proportion of A varying from 80 to 95% and the mass proportion of B varying from 5 to 20%.
M j being selected from C monomers whose Tg of their homopolymers is less than 0°C, D monomers whose Tg of their homopolymers is greater than 25°C and hydrophilic E monomers, the mass proportions of the monomers C, D , E being respectively between 25-35%, 25-35%, 35-45%. Utilisation selon la revendication 1 dans laquelle le au moins copolymère à bloc est un copolymère di blocs ou un copolymère tri blocs.Use according to Claim 1, in which the at least block copolymer is a diblock copolymer or a triblock copolymer. Utilisation selon la revendication 2 dans laquelle le copolymère à blocs est un copolymère di-blocs.Use according to claim 2 wherein the block copolymer is a di-block copolymer. Utilisation selon la revendication 3 dans laquelle le copolymère di-blocs présente une proportion massique des blocs constitués des monomères de la famille A et B variant de 5 à 40% (bloc 1) et une proportion massique des blocs constitués des monomères C, D, et E variant de 50 à 90 % (bloc 2).Use according to claim 3, in which the diblock copolymer has a mass proportion of the blocks made up of monomers of family A and B varying from 5 to 40% (block 1) and a mass proportion of the blocks made up of monomers C, D, and E varying from 50 to 90% (block 2). Utilisation selon la revendication 1 dans laquelle le ou les copolymères à blocs sont préparés par polymérisation radicalaire contrôlée.Use according to Claim 1, in which the block copolymer(s) are prepared by controlled radical polymerization. Utilisation selon la revendication 5 dans laquelle les copolymères à blocs sont préparés par polymérisation radicalaire contrôlée par les nitroxides.Use according to Claim 5, in which the block copolymers are prepared by radical polymerization controlled by nitroxides. Utilisation selon la revendication 6 dans laquelle les copolymères à blocs sont préparés par polymérisation radicalaire contrôlée par le N-tert-Butyl-1-diethylphosphono-2,2- dimethylpropyl Nitroxide.Use according to Claim 6, in which the block copolymers are prepared by controlled radical polymerization with N-tert-Butyl-1-diethylphosphono-2,2-dimethylpropyl Nitroxide. Utilisation selon la revendication 6 dans laquelle au moins un copolymère à blocs est constitué de blocs 1 mettant en œuvre l’acrylate de butyle et l’acide acrylique et de blocs 2 mettant en œuvre l’acrylate de butyle, le styrène et l’acide méthacrylique.Use according to claim 6 in which at least one block copolymer consists of blocks 1 implementing butyl acrylate and acrylic acid and blocks 2 implementing butyl acrylate, styrene and acid methacrylic. utilisation selon la revendication 1 dans laquelle au moins un copolymère à blocs présente une masse moléculaire en poids comprise entre 80000 g/mole et 150000 g/mole.use according to Claim 1, in which at least one block copolymer has a molecular mass by weight of between 80,000 g/mole and 150,000 g/mole.
FR2106675A 2021-06-23 2021-06-23 Use of multi-block copolymers as a sacrificial material in a 3D printing process Pending FR3124420A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
FR2106675A FR3124420A1 (en) 2021-06-23 2021-06-23 Use of multi-block copolymers as a sacrificial material in a 3D printing process
FR2110633A FR3124421B1 (en) 2021-06-23 2021-10-07 Use of a multiblock copolymer composition as a sacrificial material in a 3D printing process
PCT/FR2022/051148 WO2022269167A1 (en) 2021-06-23 2022-06-15 Use of multiblock copolymers as sacrificial material in a 3d printing process
KR1020247002144A KR20240024944A (en) 2021-06-23 2022-06-15 Use of multiblock copolymers as sacrificial materials in 3D printing processes

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FR2106675A FR3124420A1 (en) 2021-06-23 2021-06-23 Use of multi-block copolymers as a sacrificial material in a 3D printing process

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5866058A (en) 1997-05-29 1999-02-02 Stratasys Inc. Method for rapid prototyping of solid models
WO2010045147A2 (en) 2008-10-17 2010-04-22 Stratasys, Inc. Support material for digital manufacturing systems
WO2012143182A1 (en) * 2011-04-20 2012-10-26 Evonik Röhm Gmbh Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer
WO2016102802A1 (en) * 2014-12-23 2016-06-30 Arkema France Water-soluble block copolymer and use thereof as a support material for 3d printing
US20170369623A1 (en) * 2014-12-23 2017-12-28 Arkema France Water-soluble diblock copolymer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017112687A1 (en) * 2015-12-24 2017-06-29 Stratasys, Inc. Water soluble support material for high temperature additive manufacturing applications

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5866058A (en) 1997-05-29 1999-02-02 Stratasys Inc. Method for rapid prototyping of solid models
WO2010045147A2 (en) 2008-10-17 2010-04-22 Stratasys, Inc. Support material for digital manufacturing systems
WO2012143182A1 (en) * 2011-04-20 2012-10-26 Evonik Röhm Gmbh Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer
WO2016102802A1 (en) * 2014-12-23 2016-06-30 Arkema France Water-soluble block copolymer and use thereof as a support material for 3d printing
US20170369623A1 (en) * 2014-12-23 2017-12-28 Arkema France Water-soluble diblock copolymer

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FR3124421B1 (en) 2023-07-14
FR3124421A1 (en) 2022-12-30

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