WO2012143182A1 - Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer - Google Patents

Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer Download PDF

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Publication number
WO2012143182A1
WO2012143182A1 PCT/EP2012/054306 EP2012054306W WO2012143182A1 WO 2012143182 A1 WO2012143182 A1 WO 2012143182A1 EP 2012054306 W EP2012054306 W EP 2012054306W WO 2012143182 A1 WO2012143182 A1 WO 2012143182A1
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WO
WIPO (PCT)
Prior art keywords
weight
support material
maleic anhydride
styrene
material according
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.)
Ceased
Application number
PCT/EP2012/054306
Other languages
English (en)
French (fr)
Inventor
Florian HERMES
Stefan Bernhardt
Dirk Poppe
Günter Schmitt
Markus PRIDÖHL
Gerd LÖHDEN
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.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm 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
Priority to CA2833752A priority Critical patent/CA2833752C/en
Priority to RU2013151313/04A priority patent/RU2013151313A/ru
Priority to BR112013023429A priority patent/BR112013023429B8/pt
Priority to JP2014505552A priority patent/JP5893128B2/ja
Priority to CN201280009711.4A priority patent/CN103380156B/zh
Priority to EP12708835.9A priority patent/EP2699611B1/en
Priority to KR1020137026041A priority patent/KR20140009442A/ko
Priority to US13/982,431 priority patent/US8822590B2/en
Priority to AU2012244499A priority patent/AU2012244499B2/en
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of WO2012143182A1 publication Critical patent/WO2012143182A1/en
Priority to IL227363A priority patent/IL227363A/en
Anticipated expiration legal-status Critical
Ceased 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Definitions

  • the invention relates to a novel support material for the fused deposition modelling process for producing three- dimensional objects.
  • the invention relates more
  • the support materials according to the invention are styrene-maleic anhydride copolymers for example.
  • Rapid prototyping or rapid manufacturing processes are processes of fabrication designed to transpose existing three-dimensional CAD data ideally without manual
  • Rapid prototyping processes have come to be differentiated into various forms, which can be subdivided into two groups: laser-based processes and processes without use of a laser.
  • Stereolithography is the best known laser-based and also oldest 3D printing process. It comprises a liquid composition of a radiation-curable polymer being cured with a laser layer by layer. This process is greatly limited in its usefulness.
  • SLS selective laser sintering
  • the UV inkjet process is a well-known versatile 3D printing process. It is a three-stage process wherein a powdery material is applied in thin layers, a UV-curable liquid is printed thereon in the form of the particular layer of the later three-dimensional product, and finally the printed layer is cured with a UV source. These process steps are repeated layer by layer.
  • TDP three dimension printing
  • thermoplast solidifies to form the three- dimensional object. This process is costly, inconvenient and very slow.
  • FDM Fused deposition modelling
  • SDM selective deposition modelling
  • EP 1,105,828 proposes poly ( 2-ethyl-2-oxazoline ) for use as a support material.
  • this material has a low glass transition temperature at just 58°C and hence is scarcely usable for a printing operation. Printing would have to be done accordingly at low temperatures using a similarly sensitive build material.
  • EP 1 773 560 and EP 1 194 274 propose combinations of plasticizers and highly acid-containing, water-soluble polymers.
  • anhydride formation during printing at high temperatures affects adversely the solubility and the melt viscosity of these support materials.
  • WO 2010 045 147 discloses impact-modified terpolymers of styrene, methacrylic acid and butyl acrylate, commercially available from Innocycling GmbH & Co. KG under the name Belland ® 88140. However, these materials likewise exhibit a non-ideal, retarded solubility in combination with merely insufficiently improved thermal stability.
  • Prior art support materials do not at one and the same time meet the stated requirements of a high glass transition temperature, high thermal stability and removability in relatively weakly basic media, for example at pH 8.
  • the support material shall further be distinctly faster to remove than in the prior art under comparable conditions.
  • the problem addressed by the present invention was more particularly that of providing in particular embodiments a dissolution process in a pH range between 6 and 9, which is relatively uncritical for the user of the printer.
  • This support material is a formulation containing at least 60% by weight, preferably at least 80% by weight and more
  • This support material is at least 60% by weight, preferably at least 80% by weight and more preferably at least 90% by weight soluble in aqueous media at a pH between 6 and 14.
  • maleic anhydride is copolymerizable with a multiplicity of vinyl monomers. Particularly high
  • the maleic anhydride-copolymerizable monomers according to the invention are such electron-rich monomers.
  • the Q/e scheme of Alfred and Price with which a person skilled in the art will be familiar, can be used.
  • the monomers copolymerizable with maleic anhydride are exclusively monomers which are copolymerizable with maleic anhydride on their own without further monomers.
  • Examples thereof are styrene, isobutylene or isobutyl vinyl ether. Styrene and isobutylene are particularly preferred. Further examples are given in the "Handbook of Polymer Synthesis - Part A” (edited by H.R. Kricheldorf ) , Marcel Dekker, Inc., New York, Basle, Hong Kong 1992 in the chapter "Maleic acid and related monomers”.
  • An FDM 3D printing process for the purposes of this
  • invention is a process in which at least one build material and at least one support material are each initially present as solid polymers then melted and thereafter printed.
  • a support material for the purposes of this invention is a material which is printed as described above to form, for example, base structures or other auxiliary functions in the printing operation and after printing has taken place, is removed again by dissolving.
  • This invention comprises exclusively support materials of this definition for FDM 3D printing processes of the above- recited definition.
  • the support material is a copolymer of 50% to 60% by weight of styrene and 40% to 50% by weight of maleic anhydride.
  • the temperatures employed therein for the glass transition temperatures of copolymers to differ from the glass transition temperatures of the particular build material used by not more than 25°C, preferably not more than 10°C and more preferably 5°C.
  • the glass transition temperatures for an FDM 3D printing process using an ABS having a glass transition temperature of 108°C as build material for example are between 83 and 133°C, more precisely between 98 and 118°C and especially between 103 and 113°C.
  • the support material is preferably
  • the pH values stated in the context of the invention relate to the solution medium before dissolving the support material. It will be appreciated that this pH will change during the dissolving. To counteract this change to some extent at least, the solution medium may alternatively be in a buffered state.
  • the molecular weight M w of the copolymer used as support material is generally between 25 000 and 500 000,
  • copolymers additionally include between 2% and 20% by weight of (meth) acrylic acid.
  • the copolymer is in this case more particularly preferably made up of 40% to 55% by weight, in particular between 44 and 51% by weight, of styrene, 35% to 50% by weight and more particularly between 39% and 46% by weight of maleic anhydride and 3% to 18% by weight and more particularly 4% to 16% by weight of
  • the copolymers additionally include 2% to 40% by weight of a methoxy polyethylene glycol methacrylate having a molecular weight M w between 250 and 2000 and preferably between 400 and 800.
  • the copolymer in this case is very particularly preferably made up of 35% to 55% by weight and more particularly between 37% and 51% by weight of styrene, 30% to 50% by weight and more particularly between 32% and 46% by weight of maleic anhydride and 3% to 35% by weight and more particularly 4% to 32% by weight of methoxy
  • the copolymers are ethylene glycol dimethyl dimethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminolymers
  • a bulk polymerization process can be a continuous process carried out in a kneader or an extruder.
  • the present invention copolymers for use in or as support material are produced by solution polymerization with subsequent removal of the solvent.
  • the copolymers may contain up to 40% by weight and preferably not more than 20% by weight of further non- functionalized monomers copolymerizable with styrene.
  • materials is more particularly a copolymer of 50% to 60% by weight of styrene or isobutylene and 40% to 50% by weight of maleic anhydride.
  • the copolymer in the support materials is more particularly a copolymer of 40% to 55% by weight of styrene or isobutylene, 35% to 50% by weight of maleic anhydride and 4% to 16% by weight of (meth) acrylic acid .
  • materials is more particularly a copolymer of 35% to 55% by weight of styrene or isobutylene, 30% to 50% by weight of maleic anhydride and 4% to 35% by weight of methoxy
  • the support materials may additionally contain rheological modifiers, stabilizers, precipitated or pyrogenous silicas, plasticizers, pigments and/or impact modifiers. Further additives are conceivable depending on the intended use, and will be apparent from the processing conditions in each case . Pigments can have the advantage that the support material is easier to distinguish from the build material before printing or during printing.
  • Rheological modifiers can be used to adjust the melt viscosity during printing to specific values. Precipitated or pyrogenous silicas likewise serve to adjust the melt viscosity, for example to increase the pseudo- plasticity.
  • Plasticizers are useful to adjust the flexibility and the melt viscosity of the support material to specific values.
  • Typical plasticizers will be known to a person skilled in the art, and include, but are not limited to, esters and/or ethers of citric acid, aliphatic, cycloaliphatic or
  • aromatic phthalates esters of adipic acid, alkyl and/or aryl phosphates, polyethers, esters of glycerol and
  • Plasticizers can be used in amounts of 0% by weight to 20% by weight, preferably 3% by weight to 15% by weight and even more preferably between 5% by weight and 10% by weight, based on the overall mass of the support material.
  • Stabilizers can be used to additionally improve the thermal stability for example.
  • Stabilizers for improving storage stability such as UV stabilizers for example, can also be added .
  • the support materials may contain up to 40% by weight and preferably not more than 30% by weight of components for improving the flexibility.
  • These components may be impact modifiers as well as plasticizers. Components generally used as impact modifiers find
  • Olefin-based impact modifiers are concerned in one possible embodiment.
  • a person skilled in the art will know that styrene-maleic anhydride copolymers which have been
  • modified with olefins have improved impact resistance.
  • Suitable rubbers preferably contain at least 65% by weight of butadiene.
  • Preferred substrates are butadiene homopolymers or block copolymers of the form A-B or A-B-A consisting of styrene and butadiene.
  • WO 2005 016 978 describes the use of -olefin polymers and copolymers, for example ethylene, propylene and butylene polymers and copolymers, as impact modifiers for styrene- maleic anhydride copolymers. These impact modifiers have the advantage of enhanced thermal stability. This trait is also shown by hydrogenated block copolymers of styrene and butadiene.
  • the polymerization of the maleic anhydride copolymers according to the invention preferably takes place in the presence of the rubbers. What is advantageous is a reaction temperature above the softening point of the rubber or the presence of a solvent for the rubber. This can be, for example, styrene in the case of a bulk polymerization.
  • the reaction is started via thermal initiation or via addition of initiators that form free radicals.
  • Suitable impact modifiers further include functional copolymers, such as epoxy- or maleic acid-functionalized polyolefins based on polyethylene or polypropylene for example. Copolymers of ethylene and glycidyl methacrylates or maleic anhydride are concerned specifically. These components may contain further (meth) acrylates .
  • the core of core-shell particles usually contains
  • the core material used typically comprises amorphous copolymers having a glass transition temperature below 0°C such as butyl or ethylhexyl acrylate for example.
  • the shell usually consists of a hard component having a glass transition temperature above 70°C. These polymers are more particularly known for PMMA or PVC as components generally used as impact modifiers. Suitable particle sizes of these emulsion polymers range from 25 nm to 1000 nm, preferably from 50 nm to 600 nm and more preferably from 80 nm to 400 nm.
  • the shell of the core-shell particles consists, for
  • the core and/or the shell of the particle are in a crosslinked state. This leads to a stabilization of the particles and hence to distinctly improved properties of the components generally used as impact modifiers.
  • the core-shell particles are preferably dispersed via mechanical compounding in a single- or twin-screw extruder for example.
  • the core-shell particles are dispersed in a solvent and the maleic anhydride copolymer is polymerized in their presence.
  • Components generally used as impact modifiers can be used in amounts of 3% by weight to 30% by weight, preferably 8% by weight and 22% by weight and even more preferably between 10% by weight and 15% by weight, based on the overall mass of the support material.
  • additives may be additives for preventing the build-up of static or for modifying the surface properties for example. They may further be adhesion promoters to improve the adherence to the build material.
  • the samples were dried 6 hours at 50°C and then overnight at 150°C in a vacuum drying cabinet.
  • Weight average molecular weights were determined by gel permeation chromatography (GPC) using polystyrene standards
  • PL Guard Column 10 ⁇ , 5 cm, 7.5 mm in diameter, PLgel 10 6 A, 10 ⁇ , 30 cm, 7.5 mm in diameter, PLgel 10 5 A, 10 ⁇ , 30 cm, 7.5 mm in diameter, PLgel 10 4 A, 5 ⁇ , 30 cm, 7.5 mm in diameter, PLgel 10 3 A, 5 ⁇ , 30 cm, 7.5 mm in diameter

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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)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/EP2012/054306 2011-04-20 2012-03-13 Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer Ceased WO2012143182A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US13/982,431 US8822590B2 (en) 2011-04-20 2012-03-13 Maleic anhydride copolymers as soluble support material for fused deposition modelling (FDM) printer
RU2013151313/04A RU2013151313A (ru) 2011-04-20 2012-03-13 Сополимеры малеинового ангидрида в качестве растворимого вспомогательного материала для принтера, использующего технологию послойного наложения расплавленной полимерной нити (fdm)
BR112013023429A BR112013023429B8 (pt) 2011-04-20 2012-03-13 Material de suporte removível por dissolução e contendo copolímero de anidrido maleico para o processo de impressão em 3d por modelagem por deposição fundida (fdm)
JP2014505552A JP5893128B2 (ja) 2011-04-20 2012-03-13 熱溶解積層方式（ｆｄｍ）プリンターのための可溶性の支持材料としての無水マレイン酸コポリマー
CN201280009711.4A CN103380156B (zh) 2011-04-20 2012-03-13 作为用于熔融沉积成型（fdm）印刷机的可溶性支撑材料的马来酸酐共聚物
CA2833752A CA2833752C (en) 2011-04-20 2012-03-13 Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer
KR1020137026041A KR20140009442A (ko) 2011-04-20 2012-03-13 용융 침착 모델링 (fdm) 인쇄기용 가용성 지지체 물질로서의 말레산 무수물 공중합체
EP12708835.9A EP2699611B1 (en) 2011-04-20 2012-03-13 Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer
AU2012244499A AU2012244499B2 (en) 2011-04-20 2012-03-13 Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer
IL227363A IL227363A (en) 2011-04-20 2013-07-07 Anhydride stock copolymers as soluble support material for fdm printer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11163199A EP2514775A1 (en) 2011-04-20 2011-04-20 Maleic anhydride copolymers as soluble support material for fused deposition modelling (FDM) printer
EP11163199.0 2011-04-20

Publications (1)

Publication Number Publication Date
WO2012143182A1 true WO2012143182A1 (en) 2012-10-26

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Application Number Title Priority Date Filing Date
PCT/EP2012/054306 Ceased WO2012143182A1 (en) 2011-04-20 2012-03-13 Maleic anhydride copolymers as soluble support material for fused deposition modelling (fdm) printer

Country Status (11)

Country Link
US (1) US8822590B2 (enExample)
EP (2) EP2514775A1 (enExample)
JP (1) JP5893128B2 (enExample)
KR (1) KR20140009442A (enExample)
CN (1) CN103380156B (enExample)
AU (1) AU2012244499B2 (enExample)
BR (1) BR112013023429B8 (enExample)
CA (1) CA2833752C (enExample)
IL (1) IL227363A (enExample)
RU (1) RU2013151313A (enExample)
WO (1) WO2012143182A1 (enExample)

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WO2015065826A1 (en) * 2013-11-01 2015-05-07 Kraton Polymers U.S. Llc A fuse molded three dimensional article and a method for making the same
WO2015124557A1 (en) * 2014-02-19 2015-08-27 Basf Se Polymers as support material for use in fused filament fabrication
FR3030529A1 (fr) * 2014-12-23 2016-06-24 Arkema France Copolymere a blocs hydrosoluble et son utilisation comme materiau support pour impression 3d
JP2016531019A (ja) * 2013-07-17 2016-10-06 ストラタシス，インコーポレイテッド 電子写真方式の付加製造用の可溶性支持材料
WO2020077127A1 (en) * 2018-10-10 2020-04-16 Stratasys, Inc. Water dispersible sulfonated thermoplastic copolymer for use in additive manufacturing
US10738142B2 (en) 2014-10-14 2020-08-11 Kao Corporation Soluble material for three-dimensional molding
US10954378B2 (en) 2014-10-14 2021-03-23 Kao Corporation Soluble material for three-dimensional molding
US10982043B2 (en) 2015-06-19 2021-04-20 Stratasys, Inc. Recycling and reuse of sulfonated polymer material in additive manufacturing
US11065601B2 (en) 2015-12-18 2021-07-20 University Of Canterbury Separation medium
US11220062B2 (en) 2017-10-10 2022-01-11 Stratasys, Inc. Water-dispersible thermoplastic material comprising sulfonated copolymer for use in additive manufacturing
FR3124420A1 (fr) * 2021-06-23 2022-12-30 Arkema France Utilisation de copolymères multi blocs en tant que matériau sacrificiel dans un procédé d’impression 3D
US12157800B2 (en) 2021-04-12 2024-12-03 Stratasys, Inc. Method for underwater processing of water-dispersible materials

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EP3024881B1 (en) 2013-07-26 2018-09-05 Hewlett-Packard Development Company L.P. Composite support material for three-dimensional printing
WO2015091815A1 (de) * 2013-12-18 2015-06-25 Styrolution Group Gmbh Formmassen basierend auf vinylaromat-polymeren für den 3d druck
US10815367B2 (en) * 2013-12-18 2020-10-27 Ineos Styrolution Group Gmbh Moulding compositions based on vinylaromatic copolymers for 3D printing
KR20160101998A (ko) * 2013-12-18 2016-08-26 이네오스 스티롤루션 그룹 게엠베하 3-d 프린팅용의 비닐방향족/디엔 블록 공중합체에 기초한 몰딩 재료들의 용도
JP6574187B2 (ja) 2014-01-16 2019-09-11 ダウ グローバル テクノロジーズ エルエルシー 付加製造支持材料の回収
KR102303883B1 (ko) 2014-01-16 2021-09-24 뉴트리션 ＆ 바이오사이언시즈 유에스에이 1, 엘엘씨 3d 인쇄용 지지재료
US9102099B1 (en) 2014-02-05 2015-08-11 MetaMason, Inc. Methods for additive manufacturing processes incorporating active deposition
US9676159B2 (en) 2014-05-09 2017-06-13 Nike, Inc. Method for forming three-dimensional structures with different material portions
KR20170017928A (ko) * 2014-06-16 2017-02-15 사빅 글로벌 테크놀러지스 비.브이. 적층 가공 방법
CN105936130B (zh) * 2014-09-10 2017-08-15 珠海天威飞马打印耗材有限公司 3d物体的成型方法、3d打印机的工作台以及3d打印机
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