WO2024141320A1 - Composition liquide durcissable par rayonnement, procédé de formation d'un objet imprimé en 3d et objet imprimé en 3d - Google Patents

Composition liquide durcissable par rayonnement, procédé de formation d'un objet imprimé en 3d et objet imprimé en 3d Download PDF

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Publication number
WO2024141320A1
WO2024141320A1 PCT/EP2023/086502 EP2023086502W WO2024141320A1 WO 2024141320 A1 WO2024141320 A1 WO 2024141320A1 EP 2023086502 W EP2023086502 W EP 2023086502W WO 2024141320 A1 WO2024141320 A1 WO 2024141320A1
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Prior art keywords
radiation curable
liquid composition
curable liquid
group
composition according
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PCT/EP2023/086502
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English (en)
Inventor
Wei Zheng FAN
Zhi Zhong CAI
Yan Sheng Li
Jian Hua Fang
Xiao Xia GUO
Zi Qiang LIU
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Basf Se
Basf (China) Company Limited
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Publication of WO2024141320A1 publication Critical patent/WO2024141320A1/fr

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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • 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
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C09D179/085—Unsaturated polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • Another object of the present invention is to provide a process of forming 3D-printed object by using the radiation curable liquid composition according to the present invention.
  • the functionality of the reactive component (2) is in the range from 1 to 12, preferably from 1 to 8.
  • a process of forming 3D-printed object comprising using the radiation curable liquid composition according to any of items 1 to 21.
  • Figure 1 shows photograph of the 3D-printed object obtained from example 1 B.
  • the radiation curable hyperbranched polymer containing polyimide moiety as component (1) comprises a radiation curable group, preferably selected from an ethylenically unsaturated functional group, an epoxy group, or the mixture thereof.
  • the radiation curable hyperbranched polymer containing polyimide moiety is a radiation curable hyperbranched polyimide, for example a radiation curable hyperbranched polyimide of A x B y type, where x is at least 1 or at least 2 and y is at least 2 or at least 3.
  • the radiation curable hyperbranched polyimide comprises a radiation curable group, preferably selected from an ethylenically unsaturated functional group, an epoxy group, or the mixture thereof.
  • variables in triamine (b) of formula (II) have the following definitions: wherein X is selected from selected from -O-, -S-, -CO- (carbonyl) and -SO2- (sulfonyl); and each R1 and R2 can be the same or different and independently selected from hydrogen, C1-C4 alkyl and phenyl.
  • triamine (b) can include, for example the following compound (TAMPB):
  • the diamine has the formula of NH2-R N -NH2, wherein the radical R N is a hydrocarbyl having 2 to 40 carbon atoms, more preferably having 2 to 30 carbon atoms, for example 2 to 20, 3 to 20, 4 to 20 or 6 to 12 carbon atoms.
  • R N can be a linear or else cyclic divalent hydrocarbyl, aliphatic or else aromatic divalent hydrocarbyl.
  • R N is a linear divalent hydrocarbyl, a cyclic divalent hydrocarbyl, an aliphatic divalent hydrocarbyl, or an aromatic divalent hydrocarbyl.
  • the molar ratio of triamine (b) to diamine (c) can be at least 1 :10, preferably at least 1 :8, more preferably at least 1 :6, for example 1 :4, 1 :2, 1 : 1 , 2: 1 , 4: 1 , 6: 1 , 8: 1 or 10: 1.
  • the molar ratio of triamine (b) to diamine (c) can be in the range from 1 :10 to 10:1 , from 1 :8 to 8:1 , or from 1 :6 to 8:1.
  • the triamine (b) is primary amine.
  • diamine (c) is primary amine.
  • the compound having one anhydride group and one or more carboxyl group (d) has 7 to 16 carbon atoms, for example 7, 8, 9, 10, 11 , 12, 13, 14, 15 or 16 carbon atoms.
  • the compound having one anhydride group and one or more carboxyl group (d) can be aliphatic, cycloaliphatic or aromatic.
  • Specific example of the compound having one anhydride group and one or more carboxyl group (d) can include, for example, 1 ,2,4-benzenetricarboxylic anhydride (Trimellitic anhydride), 1 ,2,4-naphthalenetricarboxylic anhydride, 1 ,2,4-butanetricar- boxylic anhydride, 1 ,2,5-hexanetricarboxylic anhydride, 1 ,2,4-cyclohexanetricarbox- ylic anhydride, or combination thereof.
  • 1 ,2,4-benzenetricarboxylic anhydride Trimellitic anhydride
  • 1 ,2,4-naphthalenetricarboxylic anhydride 1 ,2,4-butanetricar- boxylic anhydride
  • 1 ,2,5-hexanetricarboxylic anhydride 1 ,2,4-cyclohexanetricarbox- ylic anhydride, or combination thereof.
  • compound (e) has a carbon-carbon unsaturated bond.
  • compound having one anhydride group (e) can include for example maleic anhydride, itaconic anhydride, citraconic anhydride, and methylene malonic anhydride, more preferably maleic anhydride.
  • compound (e) is different from compound (d). In this regard, compound (e) does not contain the carboxyl group.
  • the molar ratio of compound (d) to compound (e) can be at least 1 :5, preferably at least 1 :3, more preferably at least 1 :2, for example 1 :1 , 2:1 , 4:1 , 6:1 , 8:1 or 10:1.
  • the molar ratio of triamine (b) to diamine (c) can be in the range from 1 :5 to 10:1 , from 1 :3 to 8:1 or from 1 :2 to 8:1.
  • the radiation curable hyperbranched polyimide has a radiation curable group.
  • the radiation curable group can be selected from an ethylenically unsaturated functional group, an epoxy group, or the mixture thereof.
  • the ethylenically unsaturated functional group contains a carboncarbon unsaturated bond, such as those found in the following functional groups: allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamido, methacrylamido, acetylenyl, maleimido, and the like; preferably, the ethylenically unsaturated functional group contains a carbon-carbon unsaturated double bond.
  • hydroxy-functional (meth)acrylate can include for example Ci to C10 hydroxyalkyl (meth)acrylate, such as such as C2 to Cs hydroxyalkyl (meth)acry- late can include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hy- droxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, or 3-hydroxy-2-ethylhexyl (meth)acry- late etc.
  • Ci to C10 hydroxyalkyl (meth)acrylate such as such as C2 to Cs hydroxyalkyl (meth)acry- late can include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hy- droxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acryl
  • the radiation curable hyperbranched polyimide is derived from dianhydride (a), triamine (b), diamine (c), a compound having one anhydride group and one or more carboxyl group (d) and compound (e), and has a radiation curable group, wherein dianhydride (a), triamine (b), diamine (c), compound (d), compound (e) and the radiation curable group are as defined above.
  • the radiation curable hyperbranched polyimide is derived from dianhydride (a), triamine (b), optional diamine (c), a compound having one anhydride group and one or more carboxyl group (d), optional compound (e), and compound (f), wherein dianhydride (a), triamine (b), diamine (c), compound (d), compound (e) and compound (f) are as defined above.
  • the radiation curable hyperbranched polyimide is derived from dianhydride (a), triamine (b), a compound having one anhydride group and one or more carboxyl group (d), and compound (f), wherein dianhydride (a), triamine (b), compound (d), and compound (f) are as defined above.
  • the radiation curable hyperbranched polyimide of the present invention has the following building block:
  • A is a 5-7-membered ring comprising the CO-N-CO moiety or 9 to 13-membered fused ring comprising the CO-N-CO moiety; each R 3 is the radiation curable group, preferably each R3 is independently selected from an ethylenically unsaturated functional group, an epoxy group, or the mixture thereof.
  • A is a 5-7-membered ring having the CO-N-CO moiety and the remaining ring members are carbon atoms; or A is a 9-13-membered fused ring comprising the CO-N-CO moiety and the remaining ring members are carbon atoms.
  • the ring A has the following structure:
  • the ethylenically unsaturated functional group contains a carbon-carbon unsaturated bond, such as those found in the following functional groups: allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamido, methacrylamido, acetylenyl, maleimido, and the like, especially acrylate and methacrylate.
  • the radiation curable hyperbranched polyimide of the present invention can be formed by reacting dianhydride (a), triamine (b) and optional diamine (c), and capping with compound having one anhydride group and one or more carboxyl group (d) and further grafting with the radiation curable group.
  • the radiation curable hyperbranched polyimide of the present invention can be formed by reacting dianhydride (a), triamine (b) and optional diamine (c), and capping with compound having one anhydride group and one or more carboxyl group (d) and optional compound having one anhydride group (e) and further grafting with the radiation curable group.
  • the radiation curable hyperbranched polyimide of the present invention can be formed by reacting dianhydride (a), triamine (b) and optional diamine (c), and capping with compound having one anhydride group and one or more carboxyl group (d) and optional compound having one anhydride group (e) and further reacted with compound (f).
  • the radiation curable hyperbranched polyimide of the present invention can be formed by reacting dianhydride (a) and triamine (b), and capping with compound having one anhydride group and one or more carboxyl group (d) and further reacted with compound (f).
  • the radiation curable hyperbranched polyimide can be prepared by a process comprising (i) reacting dianhydride (a) with triamine (b) and optional diamine (c) to obtain an amine-terminated hyperbranched polyamic acid;
  • step (ii) capping the amine-terminated hyperbranched polyamic acid obtained in step (i) with the compound having one anhydride group and one or more carboxyl group (d);
  • step (iv) grafting the imidization product obtained in step (iii) with the radiation curable group, preferably by reacting the imidization product obtained in step (iii) with compound (f).
  • the amount of component (1) can be in the range from 0.1 to 50 wt.% (for example 0.1 wt.%, 0.2 wt.%, 0.5 wt.%, 0.8 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 3 wt.%, 5 wt.%, 8 wt.%, 10 wt.%, 12 wt.%, 15 wt.%, 18 wt.%, 20 wt.%, 22 wt.%, 25 wt.%, 28 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, or 50 wt.%), preferably from 1 to 40 wt.% or 2 to 35 wt.%, or 3 to 35 wt.%, or 4 to 35 wt.%, or 5 to 35 wt.%, or 1 to 30 wt.%
  • reactive component (2) of the present invention comprises a monomer and /or oligomer containing at least one radiation curable group.
  • the radiation curable group of reactive component (2) of the present invention may be selected from the group consisting of an ethylenically unsaturated functional group, an epoxy group, or the mixture thereof.
  • the at least one radiation curable group of the monomer and /or oligomer containing at least one radiation curable group suitable as reactive component (2) is selected from the group consisting of an ethylenically unsaturated functional group, an epoxy group, or the mixture thereof.
  • the radiation curable group of component (1) and component (2) is an ethylenically unsaturated functional group, or the radiation curable group of component (1) and component (2) is an epoxy group.
  • epoxidized olefins examples include epoxidized C2-C -olefins, such as ethylene oxide, propylene oxide, iso-butylene oxide, 1 -butene oxide, 2-butene oxide, vinyloxirane, styrene oxide or epichlorohydrin, preference being given to ethylene oxide, propylene oxide, isobutylene oxide, vinyloxirane, styrene oxide or epichlorohydrin, particular preference to ethylene oxide, propylene oxide or epichlorohydrin, and very particular preference to ethylene oxide and epichlorohydrin.
  • C2-C -olefins such as ethylene oxide, propylene oxide, iso-butylene oxide, 1 -butene oxide, 2-butene oxide, vinyloxirane, styrene oxide or epichlorohydrin, preference being given to ethylene oxide, propylene oxide, isobutylene oxide, vinyloxirane, styrene oxide
  • the (meth)acrylate monomer can be monofunctional or multifunctional (such as difunctional, trifunctional) (meth)acrylate monomer.
  • Exemplary (meth)acrylate monomer can include Ci to C20 alkyl (meth)acrylate, Ci to C10 hydroxyalkyl (meth)acrylate, C3 to C10 cycloalkyl (meth)acrylate, urethane acrylate, 2-(2- ethoxy)ethyl acrylate, tetrahydrofurfuryl (meth)acrylate, 2-phenoxyethylacrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, caprolactone (meth)acrylate, morpholine (meth)acrylate, ethoxylated nonyl phenol (meth)acrylate, (5-ethyl-1,3-dioxan-5-yl) methyl acrylate, phenyl (meth
  • C3 to C10 cycloalkyl (meth)acrylate can include isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate or cyclohexyl methacrylate.
  • alcohols examples include, e.g., difunctional alcohols, such as ethylene glycol, propylene glycol, and their counterparts with higher degrees of condensation, for example such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol etc., 1 ,2-, 1 ,3- or 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 3-methyl-1 ,5-pentanediol, neopentyl glycol, alkox- ylated phenolic compounds, such as ethoxylated and/or propoxylated bisphenols, 1 ,2-, 1 ,3- or 1 ,4-cyclohexanedimethanol, alcohols with a functionality of three or higher, such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythrito
  • (meth)acrylamide monomer can include acryloylmorpholine, methacryloylmorpholine, N- (hydroxymethyl)acrylamide, N-hydroxyethyl acrylamide, N-isopropylacrylamide, N- isopropylmethacrylamide, N-tert-butylacrylamide, N,N’-methylenebisacrylamide, N- (isobutoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, N-[3- (dimethylamino)propyl]methacrylamide, N,N-dimethylacrylamide, N,N- diethylacrylamide, N-(hydroxymethyl)methacrylamide, N-hydroxyethyl methacrylamide, N- isopropylmethacrylamide, N-isopropylmethacrylamide, N-tert- butylmethacrylamide, N,N’-methylenebismethacrylamide, N- (isobutoxymethyl)methacrylamide
  • Phosphine oxides are for example monoacyl- or bisacylphosphine oxides, such as lrgacure®819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), as described for example in EP-A 7 508, EP-A 57474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO), ethyl 2,4,6-trimethylbenzoylphenylphosphinate or bis(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentylphosphine oxide.
  • lrgacure®819 bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide
  • a-hydroxyalkyl aryl ketones are for example 1-benzoylcyclohexan-1-ol (1- hydroxycyclohexyl phenyl ketone), 2-hydroxy-2,2-dimethylacetophenone (2-hydroxy- 2-methyl-1-phenylpropan-1-one), 1 -hydroxyacetophenone, 1-[4-(2- hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1 -propan- 1 -one or polymer containing 2- hydroxy-2-methyl-1-(4-isopropen-2-ylphenyl)propan-1-one in copolymerized form (Esacure® KIP 150).
  • Xanthones and thioxanthones are for example 10-thioxanthenone, thioxanthen-9- one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- diisopropylthioxanthone, 2,4-dichlorothioxanthone or chloroxanthenone.
  • Benzoins and benzoin ethers are for example 4-morpholinodeoxybenzoin, benzoin, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether or 7H-benzoin methyl ether.
  • Phenylglyoxylic acids are described for example in DE-A 19826 712, DE-A 199 13 353 or WO 98/33761.
  • Photo-initiators which can be used as well are for example benzaldehyde, methyl ethyl ketone, 1 -naphthaldehyde, triphenylphosphine, tri-o-tolylphosphine or 2,3- butaned-ione.
  • the amount of the photo-initiator (3) can be in the range from 0.1 to 10 wt.%, for example 0.2 wt.%, 0.5 wt.%, 0.8 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 5 wt.%, 8 wt.%, or 10 wt.%, preferably in the range from 0.1 to 8 wt.% or from 0.1 to 5 wt.% or from 0.5 to 5 wt.%, based on the total weight of the radiation curable liquid composition of the present invention.
  • the radiation curable liquid composition of the present invention comprising following components:
  • Plasticizers can be used to lower the glass transition temperature (Tg) of the polymer. Plasticizers work by being embedded between the chains of polymers, spacing them apart (increasing the “free volume”), and thus lowering the glass transition temperature of the polymer and making it softer. Plasticizers may be selected by a skilled person for the present invention according to practical applications. Exemplary plasticizers include polycarboxylic acids and their esters, epoxidized vegetable oils; sulfonamides, organophosphates, glycols/polyether and their derivatives, polymeric plasticizer, biodegradable plasticizers, and the like.
  • the plasticizers can be selected from the group consisting of cyclohexane dicarboxylic acid and its esters, preferably esters of 1 ,2-cyclohexane dicarboxylic acid, more preferably 1 ,2-cyclohex- ane dicarboxylic acid diisononyl ester (such as Hexamoll® DINCH from BASF SE).
  • the amount of component (4) in the curable composition of the present invention may be in the range from 0 to 60% by weight, for example 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 50% by weight, 60% by weight, preferably from 0 to 50% by weight, or from 0 to 40% by weight, or from 0 to 30% by weight, based on the total weight of the radiation curable liquid composition of the present invention.
  • the process comprises the steps of: (p-i) forming a layer of the radiation curable liquid composition
  • the process further comprises a step of post-curing the 3D object obtained in step (p-v) as a whole to form a final 3D object.
  • the post-curing can be carried out by UV radiation, thermal treatment or combination thereof.
  • the present invention further relates to a 3D-printed object formed from the radiation curable liquid composition of the present invention or obtained by the process of the present invention.
  • Non-limiting examples of the 3D-printed objects comprise sole, outerwear, cloth, footwear, toy, mat, tire, hose, gloves, seals, medical appliances such as hearing aids, dental parts.
  • a further aspect of this disclosure relates to use of the radiation curable liquid composition of the present invention in 3D-printing.
  • the specific techniques are as mentioned above.
  • EDC-HCI (3-dimethylaminopropyl)-ethylcarbodiimide-hydrochloride
  • I BOA Isobornyl acrylate
  • Vmox vinyl methyl oxazolidinone
  • TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • Tg was measured by DSC by ramping at 10 °C/min from room temperature to 200 °C under nitrogen flow in the chamber.
  • the radiation curable hyperbranched polyimide PI-1 was well soluble in DCM, THF, DMAc, NMP, DMF and DMSO.
  • the radiation curable hyperbranched polyimide PI-2 showed good miscibility with vinyl methyl oxazolidinone (Vmox), 4-acryloylmorpholine (ACMO) and Ultracur3D® ST 45.
  • trimellitic anhydride TMAN
  • step (i) 7.02 mmol of trimellitic anhydride (TMAN) was added in one portion to the solution obtained in step (i) and the reaction mixture was stirred at room temperature for additional 10 h.
  • step (i) 7.02 mmol of trimellitic anhydride (TMAN) was added in one portion to the solution obtained in step (i) and the reaction mixture was stirred at room temperature for additional 10 h.
  • the radiation curable hyperbranched polyimide PI-3 showed good miscibility with vinyl methyl oxazolidinone (Vmox), 4-acryloylmorpholine (ACMO) and Ultracur3D® ST 45.
  • the radiation curable hyperbranched polyimide PI-4 was well soluble in DCM, THF, DMAc, NMP, DMF and DMSO.
  • the cured materials exhibited good mechanical properties. Comparing with comparative examples (composition without polyimide component), the tensile strength of the cured materials of the examples 1 B, 2B, 2C, 3B and 4B exhibited obviously increase.
  • the cured material of the examples had higher glass transition temperature and Heat Deflection Temperature (HDT) which indicated better thermal stability of materials.
  • HDT Heat Deflection Temperature

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Abstract

La présente invention concerne une composition liquide durcissable par rayonnement comprenant un polymère hyper-ramifié durcissable par rayonnement contenant une fraction polyimide, un procédé de formation d'un objet imprimé en 3D à l'aide de celle-ci, et un objet imprimé en 3D formé à partir de celle-ci. La composition liquide durcissable par rayonnement de la présente invention présente une faible viscosité et peut former un objet imprimé en 3D ayant d'excellentes propriétés mécaniques et une température d'application élevée.
PCT/EP2023/086502 2022-12-29 2023-12-19 Composition liquide durcissable par rayonnement, procédé de formation d'un objet imprimé en 3d et objet imprimé en 3d WO2024141320A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007508A2 (fr) 1978-07-14 1980-02-06 BASF Aktiengesellschaft Acylphosphinoxydes, leur préparation et leur utilisation
EP0057474A2 (fr) 1979-03-14 1982-08-11 BASF Aktiengesellschaft Composés d'oxydes d'acylphosphines, leur préparation et utilisation
EP0495751A1 (fr) 1991-01-14 1992-07-22 Ciba-Geigy Ag Bisacylphosphines
EP0615980A2 (fr) 1993-03-18 1994-09-21 Ciba-Geigy Ag Durcissement de compositions contenant des initiateurs Bisacylphosphinoxide
DE19618720A1 (de) 1995-05-12 1996-11-14 Ciba Geigy Ag Bisacyl-bisphosphine, -oxide und -sulfide
WO1998033761A1 (fr) 1997-01-30 1998-08-06 Ciba Specialty Chemicals Holding Inc. Esters phenylglyoxaliques non volatils
DE19826712A1 (de) 1998-06-16 1999-12-23 Basf Ag Strahlungshärtbare Massen, enthaltend Phenylglyoxylate
DE19913353A1 (de) 1999-03-24 2000-09-28 Basf Ag Verwendung von Phenylglyoxalsäureestern als Photoinitiatoren
JP2008231170A (ja) * 2007-03-19 2008-10-02 Nagoya Industrial Science Research Inst 感光性多分岐ポリイミド系ハイブリッド前駆体
WO2019065562A1 (fr) * 2017-09-28 2019-04-04 東レ株式会社 Composition de résine photosensible, feuille photosensible, film durci de celle-ci, procédé de fabrication associé, et construction creuse et composant électronique l'utilisant

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007508A2 (fr) 1978-07-14 1980-02-06 BASF Aktiengesellschaft Acylphosphinoxydes, leur préparation et leur utilisation
EP0057474A2 (fr) 1979-03-14 1982-08-11 BASF Aktiengesellschaft Composés d'oxydes d'acylphosphines, leur préparation et utilisation
EP0495751A1 (fr) 1991-01-14 1992-07-22 Ciba-Geigy Ag Bisacylphosphines
EP0615980A2 (fr) 1993-03-18 1994-09-21 Ciba-Geigy Ag Durcissement de compositions contenant des initiateurs Bisacylphosphinoxide
DE19618720A1 (de) 1995-05-12 1996-11-14 Ciba Geigy Ag Bisacyl-bisphosphine, -oxide und -sulfide
WO1998033761A1 (fr) 1997-01-30 1998-08-06 Ciba Specialty Chemicals Holding Inc. Esters phenylglyoxaliques non volatils
DE19826712A1 (de) 1998-06-16 1999-12-23 Basf Ag Strahlungshärtbare Massen, enthaltend Phenylglyoxylate
DE19913353A1 (de) 1999-03-24 2000-09-28 Basf Ag Verwendung von Phenylglyoxalsäureestern als Photoinitiatoren
JP2008231170A (ja) * 2007-03-19 2008-10-02 Nagoya Industrial Science Research Inst 感光性多分岐ポリイミド系ハイブリッド前駆体
WO2019065562A1 (fr) * 2017-09-28 2019-04-04 東レ株式会社 Composition de résine photosensible, feuille photosensible, film durci de celle-ci, procédé de fabrication associé, et construction creuse et composant électronique l'utilisant

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* Cited by examiner, † Cited by third party
Title
"Advances in Polymer Science", vol. 14, 1974, SPRINGER
"Plastics Additive Handbook", 2001, HANSER PUBLISHERS, pages: 116 - 122
K. K. DIETLIKER: "Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints", vol. 1, 2008, SITA TECHNOLOGY LTD

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