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WO2024099798A1 - Compositions durcissables par rayonnement pour la fabrication additive d'articles à ténacité élevée - Google Patents

Compositions durcissables par rayonnement pour la fabrication additive d'articles à ténacité élevée Download PDF

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Publication number
WO2024099798A1
WO2024099798A1 PCT/EP2023/080047 EP2023080047W WO2024099798A1 WO 2024099798 A1 WO2024099798 A1 WO 2024099798A1 EP 2023080047 W EP2023080047 W EP 2023080047W WO 2024099798 A1 WO2024099798 A1 WO 2024099798A1
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Prior art keywords
component
radiation curable
curable composition
liquid radiation
aliphatic
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Ceased
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PCT/EP2023/080047
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English (en)
Inventor
Erwin PENG
Yili WU
Soumya Sarkar
Dinesh Kumar BASKER
Ma Monica Carlos DELA CRUZ
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Evonik Operations GmbH
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Evonik Operations GmbH
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Publication of WO2024099798A1 publication Critical patent/WO2024099798A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7692—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing at least one isocyanate or isothiocyanate group linked to an aromatic ring by means of an aliphatic group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
    • 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
    • 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

Definitions

  • the present invention pertains to liquid radiation curable compositions suitable for additive manufacturing processes to obtain three dimensional objects with high toughness and good heat resistant properties.
  • additive manufacturing (AM) technology through a photopolymerization process in which layer-by-layer solidification of liquid resinous materials by means of radiation curing (e.g. UV) to manufacture three- dimensional solid polymeric objects has tremendous potential for direct manufacturing of end-use parts.
  • radiation curing e.g. UV
  • VAT photopolymerization is a subset of additive manufacturing (AM) processes that builds three- dimensional objects or articles by selectively curing liquid resin through radiation or an actinic light source.
  • AM additive manufacturing
  • Liquid photopolymer resins generally are a class of thermoset material. Through the formulation chemistry, the liquid photopolymer resin is designed to mimic thermoplastic materials behavior after polymerization.
  • VAT photopolymerization relied on highly cross-linked materials that would result in objects or articles that are brittle network and are considered to have low toughness. Such brittleness and low toughness hindered VAT photopolymerization materials to be used for broader applications when compared with the thermoplastic materials.
  • High toughness materials are required to ensure that the printed objects or articles are able to absorb more energy before breaking and have the flexibility to be deformed with higher strain before breaking and are able to withstand moderate to high mechanical stress to deform.
  • WO2019213585A1 discloses a curable composition for use in a VAT photopolymerization process which comprises a toughness modifier that is a reactive or polymerizable oligomer with an average molecular weight greater than 5000 Da and a reactive diluent that is a reactive or polymerizable compound having a molecular weight of 100-1000 Da.
  • a toughness modifier that is a reactive or polymerizable oligomer with an average molecular weight greater than 5000 Da
  • a reactive diluent that is a reactive or polymerizable compound having a molecular weight of 100-1000 Da.
  • Such combination will result in a solid or highly viscous resin formulation (1 K system) with a viscosity of 1 -70 Pa.s at 90°C-110°C.
  • the polymerization process of such a composition can only be carried out in a high temperature lithography-based photopolymerization process (temperature range of 50°C - 120°C) which limits
  • US9453142B2, US9598606B2, US9676963B2 and US10350823B2 disclose the use of multiple cure mechanisms of hardening to obtain a three-dimensional object or articles.
  • the resin composition comprises polyurethane or polyurea copolymer, silicone resin, epoxy resin or cyanate ester resin.
  • These references rely on the use of polymerizable liquid resins that comprise at least one of a blocked or reactive blocked prepolymer or diisocyanate or chain extender.
  • such reactive blocked component will be cured during the article formation, resulting in the first network formation.
  • the solid objects or articles will undergo a secondary re-solidifying or curing step upon second radiation exposure (e.g.
  • US10316213B1 discloses a dual-cure resin technology that includes a photo-curable component configured to cure when subjected to actinic radiation and a secondary component that comprises a plurality of encapsulants containing a first and second secondary precursor species.
  • the encapsulants are designed to degrade upon correct stimuli, releasing the secondary species for secondary curing to produce secondary polymer.
  • the first secondary precursor species comprises of one of the chain extenders for polyurea or polyurethane formation, e.g. polyamine or polyol species while the second secondary precursor species comprises of diisocyanate or polyisocyanate species.
  • the encapsulation technology allows printed articles or objects to possess good toughness and impact resistant properties, the resin formulation and the encapsulants are sensitive to various stimuli such as humidity and elevated temperature which complicates the VAT photopolymerization process.
  • a liquid radiation curable composition comprising: component a) 30 to 50 weight percent of one or more reactive oligomer(s), said reactive oligomer(s) containing at least two urethane and/or urea linkages in the backbone and two ethylenic unsaturated group(s) which can form polymeric crosslink networks in the presence of radicals, anions, nucleophiles or combinations thereof, with a weight average molecular weight (/ T) of greater than 5000 g/mol; component b) 5 to 40 weight percent of one or more reactive monomer(s), said reactive monomer(s) containing one ethylenic unsaturated group capable of forming polymeric crosslinked networks in the presence of radicals, anions, nucleophiles or combinations thereof, the said reactive monomer(s) having at least one bicyclic non-aromatic hydrocarbon moiety and a glass transition temperature (T g ) of the cured reactive monomer(s) of greater than 80 °C; component c
  • ethylenic unsaturated group as used herein means a vinyl, allyl, itaconate or a (meth)acrylate group.
  • (meth)acrylate group means either a methacrylate group, an acrylate group or a mixture of both.
  • N-substituted (meth)acrylamide group means an acrylamide group, a methacrylamide group or a mixture of both in which either one or both hydrogen atoms attached to the nitrogen atom in the amide group of the (meth)acrylamide is substituted with an alkyl group.
  • oligomer means an intermediate of a polymerization reaction that involves two or more components.
  • the weight average molecular weight (M w ) is determined by gel permeation chromatography (GPC) measurement using tetrahydrofuran (THF) as eluent with PS/DVB (polystyrene divinylbenzene) column (size: 4.6mm I.D. x 15cm, particle size: 3pm) and PS/DVB (polystyrene divinylbenzene) guard column (size: 4.6mm I.D. x 2cm, particle size: 4pm) at a temperature of 40°C and a flow rate of 0.35 mL/min with refractive index detector.
  • the sample concentration is 5 to 6 mg/mL in THF with injection amount of 20 pL.
  • the weight average molecular weights are calculated relative to polystyrene standard.
  • the glass transition temperature (T g ) is determined in accordance with ASTM D3418.
  • the viscosity is measured using a rotational rheometer equipped with a cone plate (2°) at 25°C and reading is obtained at 1 Hz shear rate.
  • thermomechanical properties such as automotive or aerospace demand for 3D printed objects or articles to exhibit excellent thermomechanical properties as close as possible to the thermomechanical properties of commodity and engineering thermoplastic obtained from conventional injection molding.
  • VAT photopolymerization technology which commonly utilizes (meth)acrylate-based and/or (meth)acrylamide-based thermoset resin chemistry often experience auto-acceleration during the early phase of chain growth (free radical) polymerization whereby the termination reactions are mobility restricted.
  • the resultant networks are inhomogeneous, exhibit high brittleness, are high in crosslink density and are less efficient in dissipating stress (Bagheri, A, Jin, J.: Photopolymerization in 3D Printing. ACS Appl. Polym. Mater. 2019, 1 , 4, 593-611).
  • liquid radiation curable composition according to the invention containing (meth)acrylate and (meth)acrylamide photocrosslinkable moieties can attain printed three- dimensional objects with a high tensile toughness of greater or equal than 45 J/m 3 while having high flexibility shown as an elongation at break of greater or equal than 150% and a high heat deflection temperature (HDT) at 0.455MPa of greater or equal than 45°C.
  • HDT heat deflection temperature
  • the liquid radiation curable composition according to the invention allows for the first time to produce three-dimensional objects with high tensile toughness that are not brittle, have high flexibility, good resistance to load at elevated temperatures without the need for multiple curing steps and a viscosity of the composition allowing processing at room temperature. Such properties were not possible to achieve in the prior art.
  • the liquid radiation curable composition according to the invention has a viscosity of 5000 mPa.s at 25°C or less.
  • the weight average molecular weight (M w ) of component a) ranges from 5000 g/mol to 50000 g/mol, more preferably 5000 g/mol to 30000 g/mol and most preferably 5000 g/mol to 25000 g/mol.
  • Component a) of the liquid radiation curable composition according to the invention comprises one or more reactive oligomers containing at least two urethane and/or urea linkages in the backbone.
  • Said urethane and/or urea linkages in the reactive oligomer(s) of component a) are preferably obtained by reacting aliphatic or aromatic diisocyanate with polyesters polyols, polyether polyols or polyamines to form an amine-Zhydroxyl-terminated or isocyanate-terminated polyurethane/urea intermediate.
  • the urethane and/or urea linkages in the reactive oligomer(s) of component a) can also be obtained by reacting aliphatic or aromatic diisocyanate with mixtures of two or more of polyesters polyols, polyether polyols and/or polyamines.
  • the amine-Zhydroxyl-terminated polyurethane/urea intermediate is preferably reacted with an isocyanate-functionalized (meth)acrylate or the isocyanate-terminated polyurethane/urea intermediate is reacted with a hydroxyl-functionalized (meth)acrylate to form component a).
  • Component a) obtained from that reaction preferably has the following structure:
  • R2 is a hydrocarbon residue formed by the reaction of aliphatic or aromatic diisocyanate with a polyester polyol or a polyether polyol
  • R3 is a hydrocarbon residue formed by the reaction of aliphatic or aromatic diisocyanate with polyester polyol, polyether polyol or diamine.
  • X is either H or CH3
  • Y is O and Z is either O or NH and Y can be the same or different than Z
  • n is an integer ranging from 1 to 100 and m is an integer ranging from 0 to 100.
  • component a) of the liquid radiation curable composition according to the invention comprises one or more reactive oligomers containing only urethane linkages and no urea linkages in the backbone.
  • Said urethane linkages in the reactive oligomer(s) of component a) are preferably obtained by reacting polyester polyol with aliphatic or aromatic diisocyanate to form a hydroxyl-terminated or isocyanate-terminated polyurethane intermediate.
  • the hydroxyl-terminated polyurethane intermediate is reacted with an isocyanate-functionalized (meth)acrylate or the isocyanate-terminated polyurethane intermediate is reacted with a hydroxyl-functionalized (meth)acrylate to form component a).
  • Component a) obtained from the reaction of the hydroxyl-terminated or isocyanate-terminated polyurethane intermediate with isocyanate-functionalized or hydroxyl-functionalized (meth)acrylate has the following structure:
  • R4 being a hydrocarbon residue from the reaction of aliphatic or aromatic diisocyanate with polyester polyol.
  • R5 is a hydrocarbon residue formed by the reaction of a polyester polyol with aliphatic or aromatic organic difunctional acids or anhydrides.
  • Re is a hydrocarbon residue formed by aliphatic or aromatic organic difunctional acids or anhydrides after reaction with a polyol.
  • X is either H or CHs, n is an integer ranging from 1 to 100, p is an integer ranging from 1 to 100.
  • the polyester polyol is preferably obtained from the reaction of aliphatic or aromatic organic difunctional acids or anhydrides or mixtures thereof with a polyol.
  • the polyol is preferably a short chain polyol.
  • short chain polyols as used herein means polyols with a molecular weight of less than 2000 g/mol.
  • the short chain polyol preferably carries two primary OH groups.
  • the aliphatic or aromatic difunctional organic acid(s) or anhydrides used to prepare the polyester-polyol may be cycloaliphatic or heterocyclic in nature.
  • the aliphatic or aromatic organic difunctional acid(s) or anhydrides can be optionally substituted with halogen atoms and/or be unsaturated.
  • the preferred aliphatic or aromatic organic difunctional acids or anhydrides are selected from the group consisting of succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, dichlorophthalic acid, glutaric acid, 1 ,4-cyclohexanedicarboxylic acid, and — where obtainable — their anhydrides or esters.
  • the polyols used to prepare the polyester-polyol are preferably selected from the group consisting of monoethylene glycol, 1 ,2- and 1 ,3-propylene glycol, 1 ,4- and 2,3-butylene glycol, di-p- hydroxyethylbutanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,8-octanediol, decanediol, dodecanediol, neopentyl glycol, cyclohexanediol, 3(4),8(9)-bis(hydroxymethyl)tricyclo[5.2.1 .02,6]decane (Dicidol), 1 ,4- bis(hydroxymethyl)cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis[4-(p- hydroxyethoxy)phenyl]propane, 2-
  • the urethane linkages in the reactive oligomer(s) of component a) are obtained by reacting polyether polyol, with aliphatic or aromatic diisocyanate to form a hydroxylterminated or isocyanate-terminated polyurethane intermediate.
  • the polyether polyols are preferably selected from the group consisting of polyethylene glycol, polypropylene glycol, polypropylene glycolethylene glycol copolymer, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol and polydecamethylene glycol.
  • the hydroxyl-terminated polyurethane intermediate is reacted with an isocyanate-functionalized (meth)acrylate or the isocyanate-terminated polyurethane intermediate is reacted with a hydroxylfunctionalized (meth)acrylate to form component a).
  • Component a) of that reaction has the following structure:
  • Rz is a hydrocarbon residue after the reaction of aliphatic or aromatic diisocyanate with polyether polyol
  • Rs is a hydrocarbon residue formed by the reaction of aliphatic or aromatic diisocyanate with polyether polyol
  • X is either H or CHs
  • Y is O
  • q is an integer ranging from 1 to 100.
  • the aliphatic and aromatic diisocyanates are selected from the group consisting of 5- lsocyanato-1-(isocyanatomethyl)-1 ,3,3-trimethylcyclohexane (isophorone diisocyanate), 1 ,6- diisocyanatohexane, 1 ,3-Bis(2-isocyanatopropan-2-yl)benzene, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexane diisocyanate, pentane diisocyanate, 4,4’- methylene bis(cyclohexyl isocyanate), 4-Methyl-1 ,3-phenylene diisocyanate, 2,2'-methylenebis(phenyl isocyanate), 2,4'-methylenebis(phenyl isocyanate), 4,4'-methylenebis(phenyl isocyanate) and mixtures thereof.
  • the polyamines used for obtaining component a) preferably have two primary amine groups at the terminus.
  • Said polyamines according to the invention can be of low(er) molecular weight such as aromatic amine (e.g. diethyl-toluenediamine, dimethylthio-toluenediamine, N,N’-di(sec.butyl)- aminobiphenyl methane) or aliphatic amines (e.g. diethylenetriamine, triethylene tetraamine) which usually act as chain extender.
  • the polyamines used for obtaining component a) can also be of high(er) molecular weight such as amine-terminated ethylene or propylene oxide based polyethers (e.g. Jeffamines®).
  • Component b) of the liquid radiation curable composition according to the invention comprises one or more reactive monomer(s) with a glass transition temperature (T g ) of the cured reactive monomer(s) of greater than 80 °C.
  • T g glass transition temperature of the cured reactive monomer(s)
  • the glass transition temperature (T g ) of the cured reactive monomer(s) ranges from 80°C - 250°C, more preferably from 80°C - 220°C and most preferably from 80°C - 190°C.
  • the reactive monomer(s) of component b) are preferably selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, isoborncyclohexyl acrylate, and isoborncyclohexyl methacrylate.
  • Component c) of the liquid radiation curable composition according to the invention comprises one or more reactive monomer(s) with a glass transition temperature (T g ) of the cured reactive monomer(s) of greater than 80°C.
  • T g glass transition temperature of the cured reactive monomer(s)
  • the glass transition temperature (T g ) of the cured reactive monomer(s) ranges from 80°C - 200°C, more preferably from 80°C - 180°C and most preferably from 80°C - 160°C.
  • the reactive monomer(s) of component c) contain at least one A/-substituted (meth)acrylamide group capable of forming polymeric crosslinked networks in the presence of radicals, anions, nucleophiles or combinations thereof.
  • the reactive monomer(s) contain at least one A/-substituted (meth)acrylamide group in which both hydrogen atoms attached to the nitrogen atom in the amide group of the (meth)acrylamide are substituted with alkyl groups forming a ring.
  • component c) of the radiation curable liquid composition is selected from the group consisting of 4-acrylolmorpholine, A/,A/-dimethyl acrylamide, N,N- diethyl acrylamide, A/-isopropyl acrylamide, A/,A/-dimethylaminopropyl acrylamide, A/-hydroxyethyl acrylamide, diacetone acrylamide and mixtures thereof.
  • Component d) of the liquid radiation curable composition is a photoinitiator or a mixture of photoinitiators capable of producing radicals when irradiated with actinic radiation.
  • the amount of photoinitiator added to the liquid radiation curable composition according to the invention ranges from 0.01 % to 10% weight of the total liquid formulation.
  • the actinic radiation source irradiating the said photoinitiator(s) is a mercury lamp or a LED source that has an emission wavelength between 230 nm to 600 nm, more preferably 300nm to 460nm.
  • component d) is a free radical photoinitiator, more preferably the free radical photoinitiator is an aromatic ketone type photoinitiator or a phosphine oxide type photoinitiator.
  • Aromatic ketone type photoinitiators are preferably selected from the group consisting of 1- hydroxycyclohexyl phenyl ketone, 2-hydroxy-l-(4-(4-(2-hydroxy-2- methylpropionyl) benzyl)phenyl-2- methylpropan- 1 -one, 2-hydroxy-2-methyl- 1 - phenylpropanone, 2-hydroxy-2-methyl-l-(4- isopropylphenyl)propanone, oligo (2- hydroxy -2 -methyl- 1 -(4-(l -methylvinyl)phenyl)propanone, 2- hydroxy-2-methyl- 1 -(4- dodecylphenyl)propanone, 2-hydroxy-2-methyl-l-[(2- hydroxyethoxy)phenyl]propanone, benzophenone, substituted benzophenones, 2,2 -Dimethoxy-1 ,2- diphenylethanone or mixtures thereof.
  • Phosphine type photoinitiators are preferably selected from the group consisting of diphenyl(2,4,6- trimethylbenzoyl) phosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide (BAPO) or Ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate (TPO-L) or mixtures thereof.
  • TPO diphenyl(2,4,6- trimethylbenzoyl) phosphine oxide
  • BAPO phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide
  • TPO-L Ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate
  • the liquid, radiation curable composition according to the invention may comprise one or more additive(s) selected from the group consisting of filler(s), pigment(s), thermal stabilizer(s) or antioxidant(s), non-reactive diluent or solvents), UV light stabilizer(s), UV light absorber(s), radical inhibitor(s).
  • Filler(s) may be inorganic or organic particles or mixtures of both.
  • filler(s) are nano-sized to micron-sized inorganic particles selected from the group consisting of silica, alumina, zirconia, titania or mixtures thereof.
  • filler(s) include organic particles, such nano-sized to micron-sized organic particles are selected from the group consisting of poly (methyl methacrylate), poly(vinyl alcohol), poly(vinyl butyrate), polyamide, polyimide or mixtures thereof.
  • Solvents) or non-reactive diluent(s) that may be present are for example n- hexane, n- heptane, n- octane, cyclohexane, cyclopentane, toluene, xylene, ethylbenzene, methanol, ethanol, n- butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl acetate, n- butylacetate, n- amyl acetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n- amyl ketone, cyclohexanone, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, 1 , 2 -dimethoxyethane, tetra
  • Suitable thermal stabilizers) or antioxidants are preferably selected from the group consisting of phenolic primary antioxidant (e.g. Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 3,5- Bis(1 ,1-dimethylethyl)-4-hydroxybenzenepropanoic acid thiodi-2,1 -ethanediyl ester, octadecyl-3-[3,5-di- tert-butyl-4-hydroxyphenyl]propionate], Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate or mixture thereof).
  • phenolic primary antioxidant e.g. Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate
  • Suitable UV light absorbers are preferably selected from the group consisting of 2-isopropylthioxanthone, 1-phenylazo-2-naphtol as well as optical brightener such as 2,5-bis- (5-tert-butyl-2-benzoxazolyl) thiophene, 4, 4'-bis(2-methoxystyryl)-1 ,1 '-biphenyl.
  • Suitable UV light stabilizers are preferably selected from the group consisting of 2,2,6, 6-Tetramethyl-4- piperidinol; bis(2,2,6,6,-tetramethyl-4-piperidyl)sebaceate; bis (1 , 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate and Methyl 1 , 2, 2, 6, 6- pentamethyl-4- piperidyl sebacate; decanedioic acid, bis (2, 2,6,6- tetramethyl-1- (octyloxy)-4-piperidinyl) ester; bis (1 ,2,2,6, 6-pentamethyl-4-piperidinyl)-[[3, 5-bis (1 , 1- dimethylethyl)-4- hydroxyphenyl]methyl] butylmalonate or mixtures thereof.
  • a radical inhibitor can be added to provide additional thermal stability.
  • Suitable radical inhibitors are methoxyhydroquinone (MEHQ) or various aryl compounds like butylated hydroxytoluene (BHT).
  • the liquid radiation curable composition according to the invention is especially suitable to be used in additive manufacturing processes especially in VAT photopolymerization processes.
  • additive manufacturing processes usually comprise the repeated steps of deposition or layering and irradiating the composition to form a three-dimensional object.
  • Irradiation can be provided by an actinic light source that has an emission wavelength between 230 nm to 600 nm.
  • the irradiation during printing can be in the form of laser (e.g. in stereolithography or SLA), projection (e.g. in digital light processing or DLP) or mask-projection/illumination (e.g. when liquid crystal display or LCD is used as a mask).
  • the total actinic irradiation dose required for the curing of the liquid radiation curable composition per layer is greater than 5 mJ/cm 2 per layer 100 pm layer thickness.
  • the total actinic irradiation dose can be up to 100 mJ/cm 2 for a 100 pm layer thickness print setting.
  • the total actinic irradiation is between 5 mJ/cm 2 and 70 mJ/cm 2 at 100 pm layer thickness. More preferably if the total actinic irradiation is between 5 mJ/cm 2 and 40 mJ/cm 2 at 100 pm layer thickness.
  • 10 mJ/cm 2 per layer is equivalent to 2.5 seconds of total irradiation process per layer curing.
  • other layer thickness print setting e.g. 10 pm, 20 pm and 50 pm
  • the total actinic irradiation dose required for the curing of the liquid radiation curable composition per layer must be scaled accordingly.
  • the additive manufacturing process that uses the liquid radiation curable composition according to the invention may comprise additional process steps like cleaning, washing, sonication, additional dosage of radiation, heating, polishing, coating or combinations thereof.
  • liquid radiation curable composition can attain printed three-dimensional objects with unique properties having high tensile toughness and at the same time high elongation at break and a high heat deflection temperature.
  • the invention also encompasses a three-dimensional object formed by an additive manufacturing process using the liquid radiation curable composition according to the invention.
  • a three-dimensional object printed using the liquid radiation curable composition according to the invention exhibits an elongation at break of 150% to 400% according to ASTM D638, a tensile toughness of 45 J/m 3 to 100 J/m 3 according to ASTM D638, a heat deflection temperature (HDT) at 0.455MPa of 45°C to 100°C according to ASTM D648.
  • the elongation at break of the three-dimensional object formed by an additive manufacturing process using the liquid radiation curable composition according to the invention in XY direction differs no more than 30% from the elongation at break and tensile toughness in Z direction.
  • the liquid radiation curable resin composition was prepared by mixing the ingredients as mentioned in the tables below in a mixing equipment.
  • the thus prepared resin composition was used to generate three-dimensional test specimens through a DLP 3D printing process (Asiga Max 62 with light source of either 385 nm or 405 nm wavelength) with an actinic irradiation between 5 and 40 mJ/cm 2 ) per 100 micron layer thickness.
  • 3D printing was carried out at temperatures between 25°C to 45°C. Where applicable, lowest possible processing temperature is preferred. Elongation at break, heat deflection temperature and tensile toughness are determined using said printed, washed and UV post-cured three-dimensional test specimen with dimension and shape in accordance with the respective ASTM standards.
  • Table A Abbreviations of the ingredients used for liquid radiation curable compositions
  • Table B list the components a) used for the liquid radiation curable compositions in the following examples.
  • Functionality means the number of ethylenic unsaturated groups in component a).
  • Component a) designated as EP01 is an aliphatic urethane diacrylate synthesized in accordance with the procedure described in WO 2021/122058 A1 .
  • EP02 to EP08 are commercially available oligomers used as component a) in the liquid radiation curable compositions as described in the following examples.
  • the molecular weight Mw was not determined as oligomers with four acrylates are already out of scope for component a) of a composition according to the invention.
  • the tensile toughness was determined from the area under the stress-strain curve of the specimen measured according to ASTM D638 (Type V specimen). A tensile testing machine from Instron, 3300 series with automatic extensometer was used to record the stress-strain curve of the specimen.
  • Heat deflection temperature (HDT) of the printed, washed and UV post-cured specimen is measured at an applied stress of 0.45 MPa (66 psi) according to ASTM D648 Method B.
  • the viscosity of the final liquid radiation curable composition is measured using rotational rheometer equipped with cone plate (2°) and reading is obtained at 1 Hz shear rate. Unless otherwise indicated viscosity is measured at a temperature of 25°C.
  • Example 1 encompasses liquid radiation curable composition 1A, 1 B, 1C, 1 D, 1 E, 1 F and 1 G. All liquid radiation curable compositions comprise TPO (Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide) as component d).
  • TPO Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
  • Composition 1A comprises as component a) an aliphatic urethane diacrylate (EP01) with a weight average molecular weight of 18700 g/mol, component b) IBoA and component c) ACMO.
  • EP01 aliphatic urethane diacrylate
  • component b) IBoA component c) ACMO.
  • Composition 1 B comprises as component a) an aliphatic urethane diacrylate (EP01) with a weight average molecular weight of 18700 g/mol, component b) IBoMA and component c) ACMO.
  • EP01 aliphatic urethane diacrylate
  • Composition 1 C comprises as component a) a commercially available aliphatic urethane diacrylate (EP02) with a weight average molecular weight of 5020 g/mol, component b) IBoA and component c) ACMO.
  • EP02 commercially available aliphatic urethane diacrylate
  • Composition 1 D comprises as component a) an aliphatic urethane diacrylate (EP03) with a weight average molecular weight of 9993 g/mol, component b) IBoMA and component c) ACMO.
  • Composition 1 E comprises as component a) an aliphatic urethane diacrylate (EP04) with a weight average molecular weight of 10820 g/mol, component b) IBoA and component c) ACMO.
  • Composition 1 F comprises as component a) an aliphatic urethane diacrylate (EP05) with a weight average molecular weight of 14832 g/mol, component b) IBoA and component c) ACMO.
  • Composition 1 G comprises as component a) an aliphatic urethane diacrylate (EP06) with a weight average molecular weight of 30524 g/mol, component b) IBoA and component c) ACMO.
  • Table 1 Liquid radiation curable compositions 1A - 1 G and properties of printed specimens
  • the viscosity of the compositions 1A, 1 B, 1C, 1 D, 1 E, 1 F and 1G were 1550 mPa.s, 1490 mPa.s, 788 mPa.s, 322 mPa.s, 602 mPa.s, 1310 mPa.s, 4660 mPa.s at 25°C and therefore within the required range of less than 5000 mPa.s at 25°C.
  • Printed specimens of Composition 1A, 1 B, 1C, 1 D, 1 E, 1 F and 1G according to the invention show an elongation at break between 150% to 400% measured according to ASTM D638, a heat deflection temperature (HDT) at 0.455MPa between 45°C to 100°C according to ASTM D648 and a tensile toughness of greater than 45 J/m 3 measured according to ASTM D638.
  • HDT heat deflection temperature
  • Example 2 is a comparative example encompassing liquid radiation curable compositions 2A and 2B. All liquid radiation curable compositions of Example 2 comprise TPO (Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide) as component d).
  • TPO Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
  • Composition 2A comprises component a) an aliphatic urethane tetraacrylate (EP07), component b) IBoA and component c) ACMO.
  • Composition 2B comprises component a) an aliphatic urethane tetraacrylate (EP07), component b) IBoMA and component c) ACMO.
  • Table 2 Liquid radiation curable compositions 2A and 2B and properties of printed specimens
  • the viscosity of the composition 2A was 1150mPa.s and 2B 1120 mPa.s at 25°C and therefore within the required range of less than 5000 mPa.s at 25°C.
  • composition 2A and 2B are in the required range of heat deflection temperature of between 45°C to 100°C but neither specimen reaches the required elongation at break of 150% to 400% nor the tensile toughness of 45 J/m 3 to 100 J/m 3 .
  • Comparative examples 2A and 2B show the criticality of having a component a) with two ethylenic unsaturated groups.
  • EP07 used as component a) has four acrylate groups and it is therefore out of the inventive range of two ethylenic unsaturated groups.
  • Example 3 encompasses liquid radiation curable composition 3A.
  • Composition 3A comprises as component a) an aliphatic urethane diacrylate (EP08) with a weight average molecular weight of 3060 g/mol, component b) IBoMA and component c) ACMO.
  • EP08 aliphatic urethane diacrylate
  • component b) IBoMA component c) ACMO.
  • Table 3 Composition 3A for liquid radiation curable resin for 3D printing
  • the viscosity of the composition 3A was 1100 mPa.s at 25°C and therefore within the required range of less than 5000 mPa.s at 25°C.
  • a printed specimen of composition 3A lies in the required range of heat deflection temperature of between 45°C to 100°C but does neither reach the required elongation at break of 150% to 400% nor the tensile toughness of 45 J/m 3 to 100 J/m 3 .
  • Comparative Example 3 shows the criticality of the weight average molecular weight Mw of component a. While EP08 has two acrylate groups the weight average molecular weight Mw lies below the required 5000 g/mol according to the invention.
  • Example 4 encompasses liquid radiation curable compositions 4A to 4E.
  • Composition 4A and 4B comprises as component a) an aliphatic urethane diacrylate (EP06) with a weight average molecular weight of 30524 g/mol, component b) IBoA and either CTFA orTMCHA as component c). Neither CTFA nor TMCHA are N-substituted.
  • EP06 aliphatic urethane diacrylate
  • CTFA orTMCHA CTFA or TMCHA
  • Composition 4C comprises as component a) an aliphatic urethane diacrylate (EP06) with a weight average molecular weight of 30524 g/mol, component b) IBoA and component c) ACMO. Component c) which is below the claimed range of 20 wt% - 50 wt %.
  • Composition 4D and 4E comprise as component a) an aliphatic urethane diacrylate (EP06) with a weight average molecular weight of 30524 g/mol, component b) IBoA and component c) ACMO.
  • component a) below the claimed range of 30 wt% - 50 wt % and component c) is above the claimed range of 20 wt % - 50 wt%.
  • Table 4 Liquid radiation curable compositions 4A to 4E and properties of printed specimens
  • the viscosity of the composition 4A was 5530 mPa.s at 25°C and did not meet the required range of less than 5000 mPa.s at 25°C.
  • the viscosity of the composition 4B, 4C, 4D and 4E were 3960 mPa.s, 4930 mPa.s, 1310 mPa.s and 499 mPa.s at 25°C and therefore within the required range of less than 5000 mPa.s at 25°C.
  • a printed specimen of composition 4A neither reaches the required range of heat deflection temperature of between 45°C to 100°C, nor the required elongation at break of 150% to 400% and also not the tensile toughness of 45 J/m 3 to 100 J/m 3 .
  • a printed specimen of composition 4B lies in the required range of elongation at break of 150% to 400% and the required heat deflection temperature of between 45°C to 100°C but does not reach the required tensile toughness of 45 J/m 3 to 100 J/m 3 .
  • composition 4C, 4D and 4E are in the claimed range of heat deflection temperature of between 45°C to 100°C but neither reach the required elongation at break of 150% to 400% and nor the required tensile toughness of 45 J/m 3 to 100 J/m 3 .
  • composition 1 F was used which was printed in XY direction (parallel to the printer platform direction) and another specimen was printed in Z direction (perpendicular to the printer platform direction).
  • Table 5 Properties of printed specimens printed in XY and in Z direction).
  • Printed specimens of composition 1 F printed in XY direction and printed in Z direction are in the required range of elongation at break of 150% to 400%, tensile toughness of 45 J/m 3 to 100 J/m 3 and heat deflection temperature of 45°C to 100°C. Neither elongation at break nor tensile toughness or heat deflection temperature differ more than 30% between printing in XY direction and printing in Z direction.

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Abstract

Une composition liquide durcissable par rayonnement comprenant : composant a) (30) à (50) pour cent en poids d'un ou de plusieurs oligomères réactifs, ledit ou lesdits oligomères réactifs contenant au moins deux liaisons uréthane et/ou urée dans le squelette et deux groupes éthyléniquement insaturés qui peuvent former des réseaux de réticulation polymères en présence de radicaux, d'anions, de nucléophiles ou de combinaisons de ceux-ci, avec un poids moléculaire moyen en poids (Mw) supérieur à 5000 g/mol ; composant b) (5) à (40) pour cent en poids d'un ou de plusieurs monomères réactifs, ledit ou lesdits monomères réactifs contenant un groupe insaturé éthylénique apte à former des réseaux réticulés polymères en présence de radicaux, d'anions, de nucléophiles ou de combinaisons de ceux-ci, ledit ou lesdits monomères réactifs ayant au moins une fraction hydrocarbonée non aromatique bicyclique et une température de transition vitreuse (Tg) du ou des monomères réactifs durcis supérieure à (80) °C ; composant c) (20) à (50) pour cent en poids d'un ou de plusieurs monomères réactifs, ledit ou lesdits monomères réactifs contenant au moins un groupe (méth)acrylamide N-substitué apte à former des réseaux réticulés polymères en présence de radicaux, d'anions, de nucléophiles ou de combinaisons de ceux-ci et ledit monomère présentant une température de transition vitreuse (Tg) du ou des monomères durcis supérieure à (80) °C ; composant d) 0,01 à 10 pour cent en poids d'un ou de plusieurs photo-initiateurs aptes à produire des radicaux lorsqu'ils sont irradiés avec un rayonnement actinique, composant e) 0 à 30 pour cent en poids d'un ou de plusieurs additifs choisis dans le groupe constitué par une ou plusieurs charges, un ou plusieurs pigments, un ou plusieurs stabilisants thermiques ou un ou plusieurs antioxydants, un ou plusieurs diluants ou solvants non réactifs, un ou plusieurs stabilisateurs de lumière UV, un ou plusieurs absorbeurs de lumière UV, un ou plusieurs inhibiteurs de radicaux ; à condition que la composition présente une viscosité de 8000 mPa.s à 25 °C ou moins et que le composant c) de la composition durcissable par rayonnement liquide soit différent du composant b).
PCT/EP2023/080047 2022-11-08 2023-10-27 Compositions durcissables par rayonnement pour la fabrication additive d'articles à ténacité élevée Ceased WO2024099798A1 (fr)

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Title
BAGHERI, AJIN, J.: "Photopolymerization in 3D Printing", ACS APPL. POLYM. MATER, vol. 1, no. 4, 2019, pages 593 - 611, XP055919166, DOI: 10.1021/acsapm.8b00165

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