WO2020263480A1 - Dual cure additive manufacturing resins for the production of objects with mixed tensile properties - Google Patents
Dual cure additive manufacturing resins for the production of objects with mixed tensile properties Download PDFInfo
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- WO2020263480A1 WO2020263480A1 PCT/US2020/034521 US2020034521W WO2020263480A1 WO 2020263480 A1 WO2020263480 A1 WO 2020263480A1 US 2020034521 W US2020034521 W US 2020034521W WO 2020263480 A1 WO2020263480 A1 WO 2020263480A1
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- Prior art keywords
- resin
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- weight
- rigid
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- 230000000996 additive effect Effects 0.000 title claims abstract description 25
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- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- MTYUOIVEVPTXFX-UHFFFAOYSA-N bis(2-propylheptyl) benzene-1,2-dicarboxylate Chemical compound CCCCCC(CCC)COC(=O)C1=CC=CC=C1C(=O)OCC(CCC)CCCCC MTYUOIVEVPTXFX-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- DUDCYUDPBRJVLG-UHFFFAOYSA-N ethoxyethane methyl 2-methylprop-2-enoate Chemical compound CCOCC.COC(=O)C(C)=C DUDCYUDPBRJVLG-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019000 fluorine Nutrition 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000163 poly(trimethylene ether) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- BYBCMKKXISPQGR-UHFFFAOYSA-N pyrrole-2,5-dione;styrene Chemical compound O=C1NC(=O)C=C1.C=CC1=CC=CC=C1 BYBCMKKXISPQGR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 235000003499 redwood Nutrition 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/74—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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Definitions
- the present invention concerns additive manufacturing resins, methods of using the same, and products made from such resins.
- a dual cure additive manufacturing resin useful to produce objects with mixed tensile properties
- the resin comprising: (a) light polymerizable component comprised of: (i) a reactive blocked prepolymer, said prepolymer comprised of a rigid or elastic polyurethane, polyurea, or copolymer thereof ( e.g ., in an amount of from 5, 10, or 20 percent by weight to 70, 80, or 90 percent by weight); (ii) a volatile (meth)acrylate monomer, wherein said monomer is rigid when said prepolymer is elastic, or said monomer is elastic when said prepolymer is rigid (e.g., in an amount of from 90, 80, or 70 percent by weight to 20, 10, or 5 percent by weight); (Hi) a photoinitiator (e.g, in an amount of from 0.1 to 4 percent by weight); and (iv) optionally, but preferably, an ultraviolet light absorber and/or pigment (e.g, in an amount when present of from 0.
- the reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, alcohol (meth)acrylate, maleimide, or n-vinyl formamide blocking agent. In some embodiments, the reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, maleimide, or n-vinyl formamide blocking agent.
- the glass transition temperature of a polymer formed only from one of said elastomeric monomers, prepolymers, or crosslinkers is 25 degrees Celsius or less; and the glass transition temperature of a polymer formed from only one of said rigid monomers, prepolymers, or crosslinkers is 50 degrees Celsius or more.
- the volatile monomer is rigid (e.g, is isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), 3,3,5-trimethylcyclohexyl methacrylate; 2- phenoxyethyl methacrylate or a combination thereof); and/or said crosslinker is present and rigid (e.g, is neopentyl glycol dimethacrylate (NPGDMA), ethoxylated bisphenol A dimethacrylate; acrylate ester; 1,4-butanediol dimethacrylate; di ethylene glycol diacrylate; tricyclodecane dimethanol diacrylate; pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, or a combination thereof).
- IBOMA is isobornyl methacrylate
- IBOA isobornyl acrylate
- IBOA isobornyl acrylate
- the volatile monomer is elastomeric (e.g . lauryl methacrylate (LMA), rnethoxy polyethylene glycol (550) monoacrylate; 2(2-ethoxyethoxy) ethyl acrylate; cyclic Trimethylolpropane formal acrylate; caprolactone acrylate; or a combination thereof); and/or said crosslinker is present and is elastomeric (e.g., a polyethylene glycol dimethacrylate crosslinker such as di (ethylene glycol) methyl ether methacrylate (DEGMA); alkoxylated neopentyl glycol diacrylate; polypropylene glycol (400) dimethacrylate; 1,12- dodecanediol dimethacrylate; tetraethylene glycol dimethacrylate, or a combination thereof).
- LMA lauryl methacrylate
- 550 monoacrylate
- the chain extender consists essentially of a polyol, said organometallic catalyst is present, and said blocking agent is n-vinyl formamide (and optionally wherein said resin is packaged with ail constituents mixed together in a single container, i.e., as a IK resin).
- Also provided is a method of making a three-dimensional object having at least two portions with different glass transition temperatures comprising: (a) producing an intermediate object by light polymerization of a resin as taught herein in an additive manufacturing process (e.g, stereolithography), with each of the at least two portions receiving a different dose of light during said producing; (b) optionally cleaning said intermediate object; and then (c) heating said intermediate object to produce said 3D object, with the glass transition temperature of each portion defined by the dose of light received by that portion during said producing step.
- an additive manufacturing process e.g, stereolithography
- one of said portions is rigid, and the other of said portions is flexible or elastomeric.
- the manufacturing process comprises bottom-up stereolithography (e.g, continuous liquid interface production).
- a three-dimensional object produced by additive manufacturing from a single dual cure resin comprising at least two portions having different glass transition temperatures, each of said at least two portions comprising: (a) a light polymerization product of (i) a reactive blocked prepolymer, (ii) a volatile reactive monomer, and (iii) optionally, a crosslinker; and (b) a heat polymerization product of: (i) a polyol and/or a polyamine, and (ii) a deblocked prepolymer produced by the thermal degradation of said light polymerization product; with each of said portions differing from one another in: (i) the degree of incorporation of said volatile reactive monomer and/or said crosslinker into said light polymerization product, and (ii) the amount of said heat polymerization product present, with (Hi) the amount of heat polymerization product present in each portion inversely related to the degree of incorporation of said volatile reactive monomer and/or crosslinker into said light polymerization product in that portion
- the at least two portions meet one another at a non-planar (e.g curved, angled, or combinations thereof) boundary zone.
- the at least two portions meet one another at a boundary zone having an average thickness of at least one, two, or three millimeters, where said different glass transition temperatures change to one another gradually across said boundary zone.
- the at least two portions meet one another at a boundary zone comprised of an open cell lattice.
- one of said at least two portions is contained within another of said at least two portions.
- Figure 1A illustrates a first light exposure script for producing objects as described herein.
- Figure IB illustrates a second light exposure script for producing objects as described herein.
- Figure 2A illustrates an object produced with a script of Figure 1 A following baking thereof.
- Figure 2B illustrates an object produced with a script of Figure 1B following baking thereof.
- Figure 3A is a partial cut-away illustration of an object produced as described herein.
- Figure 3B is a partial cut-away illustration of an object produced as described herein.
- the resin may have: (a) light polymerizable component comprising: (i) a reactive blocked prepolymer, said prepolymer comprised of a rigid or elastic polyurethane, polyurea, or copolymer thereof; and (ii) a volatile (meth)acrylate monomer, wherein said monomer is rigid when said prepolymer is elastic, or said monomer is elastic when said prepolymer is rigid; and (b) a heat polymerizable component comprising: (i) a chain extender selected from the group consisting of polyols, polyamines, and combinations thereof.
- the resin may also include a photoinitiator, an ultraviolet light absorber and/or pigment, and/or a crosslinker.
- An organometallic catalyst may be included in the resin in some embodiments.
- the reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, alcohol (meth)acrylate, maleimide, or n-vinyl formamide blocking agent. In some embodiments, the reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, maleimide, or n-vinyl formamide blocking agent.
- the glass transition temperature of a polymer formed only from one of said elastomeric monomers, prepolymers, or crosslinkers is 25 degrees Celsius or less; and the glass transition temperature of a polymer formed from only one of said rigid monomers, prepolymers, or crosslinkers is 50 degrees Celsius or more.
- ABS Patent Nos. 9,453,142 and 9,598,606 to Rolland et al.
- a particular example of a suitable reactive (or UV-curable) blocking agent is a tertiary amine-containing (meth)acrylate (e.g., /-butyl ami noethyl methacrylate, t-BAEMA).
- Polyisocyanates useful in carrying out the present invention include, but are not limited to, l,l'-methylenebis(4-isocyanatobenzene) (MDI), 2,4- diisocyanato-l-methylbenzene (TDI), methylene-bis(4-cyclohexylisocyanate) (H I2 MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), polymeric MDI, 1,4- phenylene diisocyanate (PPDI), and o-tolidine diisocyanate (TODI).
- a preferred diisocyanate is H I2 MDI, such as Desmodur W, supplied by Covestro AG. Additional examples include but are not limited to those given in US Patent No. 3,694,389 to Levy.
- Reactive blocking agents useful in the present invention include amine (meth)acrylate monomer blocking agents (e.g., tertiary -butylaminoethyl methacrylate (TBAEMA), tertiary pentylaminoethyl methacrylate (TPAEMA), tertiary hexylaminoethyl methacrylate (THAEMA), tertiary-butylaminopropyl methacrylate (TBAPMA), acrylate analogs thereof, and mixtures thereof (see, e.g, US Patent Application Publication No. 20130202392).
- TSAEMA tertiary -butylaminoethyl methacrylate
- TPAEMA tertiary pentylaminoethyl methacrylate
- TPAEMA tertiary hexylaminoethyl methacrylate
- TBAPMA tertiary-butylaminopropyl methacrylate
- blocking agents for isocyanate there are, however, many blocking agents for isocyanate, and those skilled in the art can couple (meth)acrylate groups to other blocking agents to create additional blocking agents that can be used to carry out the present invention, such as an alcohol (meth)acrylate, maleimide or substituted maleimide, or n-vinyl formamide blocking agent. See, e.g., U.S. Pat. No. 3,947,426 to Lander.
- “Diluents” as used herein includes both UV-curable diluents (for example monoacrylates, mono-methacrylates, poly acrylates, polymethacrylates, acrylamides, methacrylamides, etc.), and non-UV-curable diluents (for example, plasticizers such as bis(2- ethylhexyl) phthalate, bis(2-propylheptyl) phthalate, diisononyl phthalate, tri-(2-ethylhexyl) trimellitate, bis(2-ethylhexyl) adipate, diisononyl adipate, dibutyl sebacate, diisobutyl maleate, etc.).
- plasticizers such as bis(2- ethylhexyl) phthalate, bis(2-propylheptyl) phthalate, diisononyl phthalate, tri-(2-ethylhexyl) trim
- Dual cure additive manufacturing resins containing ABPUs are described in, for example, US Patent Nos. 9,453,142 and 9,598,606 to Rolland et al., the contents of which are incorporated by reference herein.
- Part A Light-polymerizable monomers and/or prepolymers. Sometimes also referred to as "Part A" of a dual cure resin, these are monomers and/or prepolymers that can be polymerized by exposure to actinic radiation or light. This resin can comprise difunctional or polyfunctional monomers, but can also include monofunctional monomers (to act as "chain stoppers" to control molecular weight).
- reactive end groups suitable for Part A constituents, monomers, or prepolymers include, but are not limited to: acrylates, methacrylates, a-olefms, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
- Part A includes monomers that are volatile (i.e., they will volatize, especially upon heating).
- the volatile monomer is rigid (e.g ., is isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), 3,3,5-trimethylcyclohexyl methacrylate; 2- phenoxyethyl methacrylate or combinations thereof); and/or a crosslinker is present and rigid (e.g., is neopentyl glycol dimethacrylate (NPGDMA), ethoxylated bisphenol A dimethacrylate; acrylate ester; 1,4-butanediol dimethacrylate; di ethylene glycol diacrylate; tricyclodecane dimethanol diacrylate; pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, or combinations thereof).
- IBOMA is isobornyl methacrylate
- IBOA isobornyl acrylate
- IBOA isobornyl acrylate
- the volatile monomer is elastomeric (e.g. lauryl methacrylate (LMA), methoxy polyethylene glycol (550) monoacrylate; 2(2-ethoxyethoxy) ethyl acrylate; cyclic Trimethylolpropane formal acrylate; caprolactone acrylate; or a combination thereof); and/or a crosslinker is present and is elastomeric (e.g, a polyethylene glycol dimethacrylate crosslinker such as diiethylene glycol) methyl ether methacrylate (DEGMA); alkoxylated neopentyl glycol diacrylate; polypropylene glycol (400) dimethacrylate; 1,12-dodecanediol dimethacrylate; tetraethylene glycol dimethacrylate, or a combination thereof).
- LMA lauryl methacrylate
- 550 methoxy polyethylene glycol
- 550 methoxy polyethylene glycol (550) monoacrylate
- the light polymerizable component once polymerized, is one which can degrade (e.g, during heating or baking) to form a constituent for further (e.g, heat) cure. Thus, it is converted, in part, to a "Part B" thermally reactive component.
- the additional part B thermally reactive components e.g., chain extenders such as polyols and/or polyamines
- polyol e.g ., diol, triol
- chain extenders include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3 -propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydroquinone bis(2-hydroxy ethyl) ether (HQEE), glycerol, trimethylolpropane, trimethylolpropane ethoxylate (TPE), 1,2,6-hexanetriol, and pentaerythritol.
- HQEE hydroquinone bis(2-hydroxy ethyl) ether
- TPE trimethylolpropane ethoxylate
- TPE 1,
- Natural oil polyols may also be used.
- Such polyols may be derived, e.g., from vegetable oils (triglycerides), such as soybean oil, by known techniques. See, e.g. , U.S. Patent No. 6,433,121 to Petrovic et al.
- Polyamine ⁇ e.g., diamine, triamine chain extenders are known and include but are not limited to those described in US Patent Nos. 10,190,020; and 9,908,146.
- a particular example is 4,4’ -methyl enebis(2-methylcy cl ohexyl-amine) (or "MACM").
- the chain extender is or consists essentially of a polyol
- the organometallic catalyst is present
- the blocking agent is n-vinyl formamide (and optionally wherein the resin is packaged with all constituents mixed together in a single container, i.e., as a IK resin).
- one or more metal organometallic chelate catalysts such as non-tin catalysts, can be incorporated into the resin composition.
- metal organometallic chelate catalysts such as non-tin catalysts
- Such catalysts are known and described in, for example, US Patent No. 5,965,686 to Blank et al., 8,912,113 to Ravichandran et al.; 9,066,316 to Hsieh et al., and 10,023,764 to Hsieh et al.; and in W. Blank et al., Catalysis of the Isocyanate-Hydroxyl Reaction by Non-Tin Catalysts (1999); W.
- the catalyst comprises a metal carboxylate such as a zinc carboxylate and/or a bismuth carboxylate.
- the organometallic catalyst comprises a metal amidine complex and/or a second compound, wherein the second compound is a metal carboxylate or a carboxylic acid, and/or a third compound wherein the third compound is a metal chelate complex of an acetylacetonate ⁇ e.g., pentanedione), optionally wherein the metal of the metal amidine complex and the metal of the metal carboxylate and/or the metal of the metal acetylacetonate (when present) are not identical.
- the various organic groups can be substituted or unsubstituted.
- the acetylacetonate can be further substituted, for instance with one to six methyl groups or one to six fluorines at the 1 and 5 positions.
- the metal amidine complex is of the chemical formula metal(amidine) w (carboxylate) 2 , wherein w is an integer from 1 to 4.
- the metal of the metal amidine complex, the metal of the metal carboxylate, and the metal of the chelate complex are independently copper, zinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium, tin, hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.
- the metal of the metal amidine complex and the metal of the metal carboxylate are independently zinc or bismuth.
- the amidine is 1,1,3,3-tetramethyl guanidine or 1- methylimidazole.
- the chelate is pentanedione, hexafluoropentanedione or tetramethy 1 octanedi one .
- the carboxylate is octoate, neodecanoate, naphthenate, stearate, or oxalate.
- the second compound comprises a zinc carboxylate and/or a bismuth carboxylate.
- Suitable catalysts include, but are not limited to K-KAT® catalysts XK-348, XK-635, XK-651, XK-661, XK-672, and XK-678, available from King Industries, 1 Science Road, Norwalk, CT 06852 USA ( See generally King Industries, K- KAT® Guide to Tin-Free Catalysts for Urethane Coatings (2016)).
- Photoinitiators included in the polymerizable liquid (resin) can be any suitable photoiniator, including type I and type II photoinitiators and including commonly used UV photoinitiators, examples of which include but are not limited to such as acetophenones (diethoxyacetophenone for example), phosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide (PPO), Irgacure® 369, etc. See, e.g, US Patent No. 9,453,142 to Rolland et al.
- the liquid resin or polymerizable material can have solid particles suspended or dispersed therein. Any suitable solid particle can be used, depending upon the end product being fabricated.
- the particles can be metallic, organic/polymeric, inorganic, or composites or mixtures thereof.
- the particles can be nonconductive, semi-conductive, or conductive (including metallic and non-metallic or polymer conductors); and the particles can be magnetic, ferromagnetic, paramagnetic, or nonmagnetic.
- the particles can be of any suitable shape, including spherical, elliptical, cylindrical, etc.
- the particles can be of any suitable size (for example, ranging from 1 nm to 20 pm average diameter).
- the particles can comprise an active agent or detectable compound as described below, though these may also be provided dissolved or solubilized in the liquid resin as also discussed below.
- magnetic or paramagnetic particles or nanoparticles can be employed.
- the liquid resin can have additional ingredients solubilized therein, including pigments, dyes, diluents, active compounds or pharmaceutical compounds, detectable compounds (e.g ., fluorescent, phosphorescent, radioactive), etc., again depending upon the particular purpose of the product being fabricated.
- additional ingredients include, but are not limited to, proteins, peptides, nucleic acids (DNA, RNA) such as siRNA, sugars, small organic compounds (drugs and drug-like compounds), etc., including combinations thereof.
- polymerizable liquids for carrying out the present invention include a non-reactive pigment or dye that absorbs light, particularly UV light.
- Suitable examples of such light absorbers include, but are not limited to: (i) titanium dioxide (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), (ii) carbon black (e.g, included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or (iii) an organic ultraviolet light absorber such as a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, and/or benzotriazole ultraviolet light absorber (e.g, Mayzo BLS1326) (e.g, included in an amount of 0.001 or 0.005 to 1, 2 or 4 percent by weight).
- suitable organic ultraviolet light absorbers include, but are not limited to
- fillers may be solid or liquid, organic or inorganic, and may include reactive and non-reactive rubbers: siloxanes, acrylonitrile-butadiene rubbers; reactive and non-reactive thermoplastics (including but not limited to: poly(ether imides), maleimide-styrene terpolymers, polyarylates, polysulfones and polyethersulfones, etc.) inorganic fillers such as silicates (such as talc, clays, silica, mica), glass, carbon nanotubes, graphene, cellulose nanocrystals, etc., including combinations of all of the foregoing.
- Suitable fillers include tougheners, such as core-shell rubbers, as discussed below.
- Tougheners One or more polymeric and/or inorganic tougheners can be used as a filler in the present invention.
- the toughener may be uniformly distributed in the form of particles in the cured product. The particles could be less than 5 microns (pm) in diameter.
- Such tougheners include, but are not limited to, those formed from elastomers, branched polymers, hyperbranched polymers, dendrimers, rubbery polymers, rubbery copolymers, block copolymers, core-shell particles, oxides or inorganic materials such as clay, polyhedral oligomeric silsesquioxanes (POSS), carbonaceous materials (e.g., carbon black, carbon nanotubes, carbon nanofibers, fullerenes), ceramics and silicon carbides, with or without surface modification or functionalization.
- PES polyhedral oligomeric silsesquioxanes
- carbonaceous materials e.g., carbon black, carbon nanotubes, carbon nanofibers, fullerenes
- ceramics and silicon carbides with or without surface modification or functionalization.
- Core-shell rubbers are particulate materials (particles) having a rubbery core. Such materials are known and described in, for example, US Patent Application Publication No. 20150184039, as well as US Patent Application Publication No. 20150240113, and US Patent Nos. 6,861,475, 7,625,977, 7,642,316, 8,088,245, and elsewhere.
- the core-shell rubber particles are nanoparticles (i.e., having an average particle size of less than 1000 nanometers (nm)).
- the average particle size of the core-shell rubber nanoparticles is less than 500 nm, e.g., less than 300 nm, less than 200 nm, less than 100 nm, or even less than 50 nm.
- such particles are spherical, so the particle size is the diameter; however, if the particles are not spherical, the particle size is defined as the longest dimension of the particle.
- Suitable core-shell rubbers include, but are not limited to, those sold by Kaneka Corporation under the designation Kaneka Kane Ace, including the Kaneka Kane Ace 15 and 120 series of products, including Kaneka Kane Ace MX 120, Kaneka Kane Ace MX 153, Kaneka Kane Ace MX 154, Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170, Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
- Kaneka Kane Ace including the Kaneka Kane Ace 15 and 120 series of products, including Kaneka Kane Ace MX 120, Kaneka Kane Ace MX 153, Kaneka Kane Ace MX 154, Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170, Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
- diluents for use in the present invention are preferably reactive organic diluents; that is, diluents that will degrade, isomerize, cross-react, or polymerize, with themselves or a light polymerizable component, during the additive manufacturing step.
- the diluent(s) are included in an amount sufficient to reduce the viscosity of the polymerizable liquid or resin (e.g., to not more than 15,000, 10,000, 6,000, 5,000, 4,000, or 3,000 centipoise at 25 degrees Centigrade).
- diluents include, but are not limited to, isobornyl methacrylate, TBAEMA (tert-butyl amino ethyl methacrylate), tetrahydrofurfuryl methacrylate, N, A-di methyl acryl a i de, A-vinyl-2- pyrrolidone, and A -vinyl formamide, or a mixture of two or more thereof.
- the diluent may be included in the polymerizable liquid in any suitable amount, typically from 1, 5 or 10 percent by weight, up to about 30 or 40 percent by weight, or more.
- Resin packaging The resin may be packaged as two separate precursors, which are mixed together and dispensed prior to use (sometimes referred to as "2K resins") or in some embodiments may be packaged in a premixed form, in the same chamber of a single container (sometimes referred to as a " IK” resin). In either case, the resin is dispensed into an additive manufacturing apparatus for production of a "green" intermediate object.
- Suitable additive manufacturing methods and apparatus in which resins as described herein can be used include bottom-up and top-down additive manufacturing apparatus, as known and described in, for example, U.S. Patent No. 5,236,637 to Hull, US Patent Nos. 5,391,072 and 5,529,473 to Lawton, U.S. Patent No. 7,438,846 to John, US Patent No. 7,892,474 to Shkolnik, U.S. Patent No. 8,110,135 to El-Siblani, U.S. Patent Application Publication No. 2013/0292862 to Joyce, and US Patent Application Publication No. 2013/0295212 to Chen et al.
- the disclosures of these patents and applications are incorporated by reference herein in their entirety.
- the additive manufacturing step is carried out by one of the family of methods sometimes referred to as continuous liquid interface production (CLIP).
- CLIP is known and described in, for example, US Patent Nos. 9,211,678; 9,205,601; 9,216,546; and others; in J. Tumbleston et al., Continuous liquid interface production of 3D Objects, Science 347, 1349-1352 (2015); and in R. Janusziewcz et al., Layerless fabrication with continuous liquid interface production, Proc. Natl. Acad. Sci. USA 113, 11703-11708 (2016).
- Other examples of methods and apparatus for carrying out particular embodiments of CLIP include, but are not limited to: Batchelder et al., US Patent Application Pub. No.
- objects can, if desired, be cleaned (e.g ., wiped, washed, spun to centrifugally separate unpolymerized resin from the object, etc.) and further cured (e.g., by baking), in accordance with known techniques.
- cleaned e.g ., wiped, washed, spun to centrifugally separate unpolymerized resin from the object, etc.
- further cured e.g., by baking
- the resins and methods described herein can be used to make a variety of objects, including but not limited to cushions, bumpers, and shock absorbers, with particular examples including helmet pads and liners, seat cushions, bed cushions, body pads such as shoulder pads, knee pads, and shin guards, balls having cores or internal layers with different tensile properties than the outer shell thereof, etc. and the like.
- the object includes at least two portions having different glass transition temperatures, each portion comprising: (a) a light polymerization product of (i) a reactive blocked prepolymer, (ii) a volatile reactive monomer, and (iii) optionally, a crosslinker; and (b) a heat polymerization product of: (i) a polyol and/or a polyamine, and (ii) a deblocked prepolymer produced by the thermal degradation of the light polymerization product.
- Each portion may differ from one another in: (i) the degree of incorporation of the volatile reactive monomer and/or crosslinker into the light polymerization product, and (ii) the amount of heat polymerization product present, with (iii) the amount of heat polymerization product present in each portion inversely related to the degree of incorporation of the volatile reactive monomer and/or crosslinker into the light polymerization product in that portion.
- the at least two portions meet one another at a non-planar (e.g, curved, angled, or combinations thereof) boundary zone.
- the at least two portions meet one another at a boundary zone having an average thickness of at least one, two, or three millimeters, where said different glass transition temperatures change to one another gradually across said boundary zone.
- the at least two portions meet one another at a boundary zone comprised of an open cell lattice.
- one of the at least two portions is contained within another of the at least two portions.
- the regions or portions of the object with different tensile properties can join to one another as a homogeneous lattice structure (that is, without intervening walls or solid layers), as seen in Figure 2A, although it will be appreciated that various unit cells within the homogeneous lattice can differ from one another.
- a particular example is a helmet liner that transitions from an elastomeric internal (or body facing) portion to a rigid external portion.
- the regions or portions of the object with different tensile properties can connect to one another along a gradual or extended transition zone (in contrast to the more sudden transition obtained when switching cassettes with different resins as described in Rolland et al., noted above).
- the object 201 can have different portions or regions 202, 203, 204, 205 of different tensile properties (e.g rigid versus elastomeric versus flexible) that join to one another at a non-planar interface, such as a curved interface, and can have one region fully or partially contained within another region (for example, as regions 202 is contained within region 203, as region 203 is contained within region 204, as region 204 is contained within region 205).
- tensile properties e.g rigid versus elastomeric versus flexible
- Still more complicated patterns of interrelated regions can be obtained, including checkerboard, spiral, and other intertwined regions, with the variation of tensile properties being attainable by varying light intensity or dose on a voxel-by-voxel basis during additive manufacturing of the object.
- the following examples describe a single resin that is capable of producing a gradient of properties depending on the amount of UV light exposure during the printing process.
- an ABPU normally used for the production of elastomeric objects ATB7 ABPU
- IBOMA rigid objects
- IPDI isophorone diisocyanate
- TB or TBAEMA tert-butylaminoethyl methacrylate
- P03G2K 2 kiloDalton poly(trimethylene ether)glycol (a polyether polyol produced by the self condensation polymerization of 1,3-propanediol (PDO));
- ATB7 ABPU a reactive methacrylate blocked polyurethane prepolymer, prepared as described in J. Rolland et al., US Patent No.9,598,606, from the above ingredients in a molar ratio of IPDI:PO3G2K:TB of 3:1:4);
- IBOMA Isobornyl methacrylate, a reactive, volatile monomer
- TPO Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, a photoinitiator
- DBA 9,10-dibromoanthracene, an ultraviolet light absorber.
- a resin was prepared by adding 50g IBOMA, 0.2g DBA, and 1.6g TPO to a 300mL THINKYTM mixer cup and mixing the components together in a planetary centrifugal mixer (Thinky Corporation) for 10-20 minutes, until solids are dissolved.131g of the ATB7 ABPU was then added and mixed for another 4 minutes. Lastly, 17.2g of MACM was added and 15 mixed for 2 minutes. The resin was then tested for basic properties, such as viscosity and dose-to-cure, and prepared for printing by filtering the resin and placing it into the window cassette of a Carbon Inc. M1 printer. EXAMPLE 2
- Print script were constructed that applied an intensity mask to different areas of the build platform during production of one or more objects on the same carrier platform, at the same time, from the same resin.
- a first script had a gradient of 100% to 10% of the initial exposure intensity in 10% 25 bands along the X axis, as shown in Figure 1A.
- Another script used had 4 different quadrants which were respectively 25%, 50%, 75% and 100% of the initial exposure intensity in the upper right, upper left, lower left and lower right quadrants of the build platform, as shown in Figure 1B, from which four different objects were produced at the same time, from the same pool of resin on the window cassette.
- Exposure time was kept constant for each slice in this example, but many other methods for controlling dose can be used to achieve these gradient properties, such as by varying intensity in the "Z" or vertical dimension during production of an object, or by using exposure time differences in the Z dimension in combination with an intensity map in the XY dimensions during production of the object.
- the script was applied to the relevant test print, in this case, a set of lattices. The print parameters were adjusted to allow for printing even in the lowest-dose areas, and the lattice objects produced from a resin as described in EXAMPLE 1 above.
Abstract
Provided herein according to some embodiments is a dual cure additive manufacturing resin useful to produce objects with mixed tensile properties. The resin may have: (a) light polymerizable component comprising: (i) a reactive blocked prepolymer, said prepolymer comprised of a rigid or elastic polyurethane, polyurea, or copolymer thereof; and (ii) a volatile (meth)acrylate monomer, wherein said monomer is rigid when said prepolymer is elastic, or said monomer is elastic when said prepolymer is rigid; and (b) a heat polymerizable component comprising: (i) a chain extender selected from the group consisting of polyols, polyamines, and combinations thereof. Methods of making a three-dimensional object having at least two portions with different glass transition temperatures, and objects so produced, are also provided.
Description
DUAL CURE ADDITIVE MANUFACTURING RESINS FOR THE
PRODUCTION OF OBJECTS WITH MIXED TENSILE PROPERTIES
Field of the Invention
The present invention concerns additive manufacturing resins, methods of using the same, and products made from such resins.
Background of the Invention
The introduction of more rapid additive manufacturing processes sometimes referred to as "continuous liquid interface production" (or "CLIP"), coupled with the introduction of dual cure additive manufacturing resins that produce objects with practical functional properties, have accelerated the transition of additive manufacturing from a tool for producing prototype objects, to a tool for making objects suitable for real-world use. See J. Tumbleston et al., Continuous liquid interface production of 3D objects , SCIENCE 347, 1349-1352 (2015); US Patent Nos. 9,211,678; 9,205,601; and 9,216,546 to DeSimone et al.; and R. Janusziewicz, et al., Layerless fabrication with continuous liquid interface production, PNAS 113, 11703-11708 (2016); See also Rolland et al., US Patent Nos. 9,676,963, 9,453,142 and 9,598,606; J. Poelma and J. Rolland, Rethinking digital manufacturing with polymers, SCIENCE 358, 1384-1385 (2017).
Current dual cure additive manufacturing resins are tailored to the production of objects with a particular set of tensile properties, such as rigid objects, flexible objects, and elastomeric objects. Examples of such resins include the RPU, FPU, EPU, and MPU family of resins available from Carbon Inc. (Redwood City, California). There are, however, situations where it would be desirable to produce an object with different tensile properties in different regions thereof. Previously, such objects could be produced by switching the resin (e.g, by swapping window cassettes containing different resins) during the course of producing an object (see, e.g, Rolland et al., above). It would speed and simplify production of such objects to have a single resin that could produce an object with different tensile properties in different regions thereof, and, where necessary, produce an object where the transition between those regions is not planar (as is necessarily the case where windows containing the resin are switched during production).
Summary
Provided herein according to some embodiments is a dual cure additive manufacturing resin useful to produce objects with mixed tensile properties, the resin comprising: (a) light polymerizable component comprised of: (i) a reactive blocked prepolymer, said prepolymer comprised of a rigid or elastic polyurethane, polyurea, or copolymer thereof ( e.g ., in an amount of from 5, 10, or 20 percent by weight to 70, 80, or 90 percent by weight); (ii) a volatile (meth)acrylate monomer, wherein said monomer is rigid when said prepolymer is elastic, or said monomer is elastic when said prepolymer is rigid (e.g., in an amount of from 90, 80, or 70 percent by weight to 20, 10, or 5 percent by weight); (Hi) a photoinitiator (e.g, in an amount of from 0.1 to 4 percent by weight); and (iv) optionally, but preferably, an ultraviolet light absorber and/or pigment (e.g, in an amount when present of from 0.01 or 0.1 to 1 or 2 percent by weight); (v) optionally, a crosslinker (e.g, a volatile or non-volatile (meth)acrylate, acrylamide, or vinyl crosslinker, which can be rigid or elastomeric) (e.g, in an amount when present of from 0.1 or 1 percent by weight to 30 or 50 percent by weight); said resin further comprising: (b) a heat polymerizable component comprised of: (i) a chain extender selected from the group consisting of polyols, polyamines, and combinations thereof (e.g, in an amount of from 5 or 10 percent by weight to 30 or 40 percent by weight); and (ii) optionally, an organometallic catalyst (e.g, in an amount when present of 0.01 or 0.1 percent by weight to 2 or 3 percent by weight).
In some embodiments, the reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, alcohol (meth)acrylate, maleimide, or n-vinyl formamide blocking agent. In some embodiments, the reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, maleimide, or n-vinyl formamide blocking agent.
In some embodiments, the glass transition temperature of a polymer formed only from one of said elastomeric monomers, prepolymers, or crosslinkers is 25 degrees Celsius or less; and the glass transition temperature of a polymer formed from only one of said rigid monomers, prepolymers, or crosslinkers is 50 degrees Celsius or more.
In some embodiments, the volatile monomer is rigid (e.g, is isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), 3,3,5-trimethylcyclohexyl methacrylate; 2- phenoxyethyl methacrylate or a combination thereof); and/or said crosslinker is present and rigid (e.g, is neopentyl glycol dimethacrylate (NPGDMA), ethoxylated bisphenol A dimethacrylate; acrylate ester; 1,4-butanediol dimethacrylate; di ethylene glycol diacrylate;
tricyclodecane dimethanol diacrylate; pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, or a combination thereof).
In some embodiments, the volatile monomer is elastomeric ( e.g . lauryl methacrylate (LMA), rnethoxy polyethylene glycol (550) monoacrylate; 2(2-ethoxyethoxy) ethyl acrylate; cyclic Trimethylolpropane formal acrylate; caprolactone acrylate; or a combination thereof); and/or said crosslinker is present and is elastomeric (e.g., a polyethylene glycol dimethacrylate crosslinker such as di (ethylene glycol) methyl ether methacrylate (DEGMA); alkoxylated neopentyl glycol diacrylate; polypropylene glycol (400) dimethacrylate; 1,12- dodecanediol dimethacrylate; tetraethylene glycol dimethacrylate, or a combination thereof).
In some embodiments, the chain extender consists essentially of a polyol, said organometallic catalyst is present, and said blocking agent is n-vinyl formamide (and optionally wherein said resin is packaged with ail constituents mixed together in a single container, i.e., as a IK resin).
Also provided is a method of making a three-dimensional object having at least two portions with different glass transition temperatures, comprising: (a) producing an intermediate object by light polymerization of a resin as taught herein in an additive manufacturing process (e.g, stereolithography), with each of the at least two portions receiving a different dose of light during said producing; (b) optionally cleaning said intermediate object; and then (c) heating said intermediate object to produce said 3D object, with the glass transition temperature of each portion defined by the dose of light received by that portion during said producing step.
In some embodiments, one of said portions is rigid, and the other of said portions is flexible or elastomeric.
In some embodiments, the manufacturing process comprises bottom-up stereolithography (e.g, continuous liquid interface production).
Also provided is a three-dimensional object produced by a method as taught herein.
Further provided is a three-dimensional object produced by additive manufacturing from a single dual cure resin, the object comprising at least two portions having different glass transition temperatures, each of said at least two portions comprising: (a) a light polymerization product of (i) a reactive blocked prepolymer, (ii) a volatile reactive monomer, and (iii) optionally, a crosslinker; and (b) a heat polymerization product of: (i) a polyol and/or a polyamine, and (ii) a deblocked prepolymer produced by the thermal degradation of said light polymerization product; with each of said portions differing from one another in: (i) the degree of incorporation of said volatile reactive monomer and/or said crosslinker into said
light polymerization product, and (ii) the amount of said heat polymerization product present, with (Hi) the amount of heat polymerization product present in each portion inversely related to the degree of incorporation of said volatile reactive monomer and/or crosslinker into said light polymerization product in that portion.
In some embodiments, the at least two portions meet one another at a non-planar ( e.g curved, angled, or combinations thereof) boundary zone.
In some embodiments, the at least two portions meet one another at a boundary zone having an average thickness of at least one, two, or three millimeters, where said different glass transition temperatures change to one another gradually across said boundary zone.
In some embodiments, the at least two portions meet one another at a boundary zone comprised of an open cell lattice.
In some embodiments, one of said at least two portions is contained within another of said at least two portions.
The foregoing and other objects and aspects of the present invention are explained in greater detail in the drawings herein and the specification set forth below. The disclosures of all United States patent references cited herein are to be incorporated herein by reference.
Brief Descrption of the Drawings
Figure 1A illustrates a first light exposure script for producing objects as described herein.
Figure IB illustrates a second light exposure script for producing objects as described herein.
Figure 2A illustrates an object produced with a script of Figure 1 A following baking thereof.
Figure 2B illustrates an object produced with a script of Figure 1B following baking thereof.
Figure 3A is a partial cut-away illustration of an object produced as described herein. Figure 3B is a partial cut-away illustration of an object produced as described herein.
Detailed Description of Illustrative Embodiments
The present invention is now described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this
disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a," "an" and "the" are intended to include plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components and/or groups or combinations thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and/or groups or combinations thereof.
As used herein, the term "and/or" includes any and all possible combinations or one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative ("or").
The transitional phrase "consisting essentially of' means that the scope of a claim is to be interpreted to encompass the specified materials or steps recited, and also additional materials or steps that do not materially affect the basic and novel characteristics of the claimed invention as described herein.
Provided herein according to some embodiments is a dual cure additive manufacturing resin useful to produce objects with mixed tensile properties. The resin may have: (a) light polymerizable component comprising: (i) a reactive blocked prepolymer, said prepolymer comprised of a rigid or elastic polyurethane, polyurea, or copolymer thereof; and (ii) a volatile (meth)acrylate monomer, wherein said monomer is rigid when said prepolymer is elastic, or said monomer is elastic when said prepolymer is rigid; and (b) a heat polymerizable component comprising: (i) a chain extender selected from the group consisting of polyols, polyamines, and combinations thereof. The resin may also include a photoinitiator, an ultraviolet light absorber and/or pigment, and/or a crosslinker. An organometallic catalyst may be included in the resin in some embodiments.
In some embodiments, the reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, alcohol (meth)acrylate, maleimide, or n-vinyl formamide blocking agent. In some embodiments, the reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, maleimide, or n-vinyl formamide blocking agent.
In some embodiments, the glass transition temperature of a polymer formed only from one of said elastomeric monomers, prepolymers, or crosslinkers is 25 degrees Celsius or less;
and the glass transition temperature of a polymer formed from only one of said rigid monomers, prepolymers, or crosslinkers is 50 degrees Celsius or more.
"ABPU" or "reactive blocked polyurethane" as used herein refers to UV-curable, (meth)acrylate blocked, polyurethane/polyurea (i.e., reactive blocked polyurethane) such as described in US Patent Nos. 9,453,142 and 9,598,606 to Rolland et al. A particular example of a suitable reactive (or UV-curable) blocking agent is a tertiary amine-containing (meth)acrylate (e.g., /-butyl ami noethyl methacrylate, t-BAEMA).
Polyisocyanates (including diisocyanates) useful in carrying out the present invention include, but are not limited to, l,l'-methylenebis(4-isocyanatobenzene) (MDI), 2,4- diisocyanato-l-methylbenzene (TDI), methylene-bis(4-cyclohexylisocyanate) (HI2MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), polymeric MDI, 1,4- phenylene diisocyanate (PPDI), and o-tolidine diisocyanate (TODI). In some embodiments, a preferred diisocyanate is HI2MDI, such as Desmodur W, supplied by Covestro AG. Additional examples include but are not limited to those given in US Patent No. 3,694,389 to Levy.
Reactive blocking agents useful in the present invention include amine (meth)acrylate monomer blocking agents (e.g., tertiary -butylaminoethyl methacrylate (TBAEMA), tertiary pentylaminoethyl methacrylate (TPAEMA), tertiary hexylaminoethyl methacrylate (THAEMA), tertiary-butylaminopropyl methacrylate (TBAPMA), acrylate analogs thereof, and mixtures thereof (see, e.g, US Patent Application Publication No. 20130202392). There are, however, many blocking agents for isocyanate, and those skilled in the art can couple (meth)acrylate groups to other blocking agents to create additional blocking agents that can be used to carry out the present invention, such as an alcohol (meth)acrylate, maleimide or substituted maleimide, or n-vinyl formamide blocking agent. See, e.g., U.S. Pat. No. 3,947,426 to Lander.
"Diluents" as used herein includes both UV-curable diluents (for example monoacrylates, mono-methacrylates, poly acrylates, polymethacrylates, acrylamides, methacrylamides, etc.), and non-UV-curable diluents (for example, plasticizers such as bis(2- ethylhexyl) phthalate, bis(2-propylheptyl) phthalate, diisononyl phthalate, tri-(2-ethylhexyl) trimellitate, bis(2-ethylhexyl) adipate, diisononyl adipate, dibutyl sebacate, diisobutyl maleate, etc.).
1. Dual cure additive manufacturing resins containing ABPUs.
Dual cure additive manufacturing resins containing ABPUs are described in, for example, US Patent Nos. 9,453,142 and 9,598,606 to Rolland et al., the contents of which are incorporated by reference herein.
A. Light-polymerizable monomers and/or prepolymers. Sometimes also referred to as "Part A" of a dual cure resin, these are monomers and/or prepolymers that can be polymerized by exposure to actinic radiation or light. This resin can comprise difunctional or polyfunctional monomers, but can also include monofunctional monomers (to act as "chain stoppers" to control molecular weight). Examples of reactive end groups suitable for Part A constituents, monomers, or prepolymers include, but are not limited to: acrylates, methacrylates, a-olefms, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
In some embodiments, Part A includes monomers that are volatile (i.e., they will volatize, especially upon heating).
In some embodiments, the volatile monomer is rigid ( e.g ., is isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), 3,3,5-trimethylcyclohexyl methacrylate; 2- phenoxyethyl methacrylate or combinations thereof); and/or a crosslinker is present and rigid (e.g., is neopentyl glycol dimethacrylate (NPGDMA), ethoxylated bisphenol A dimethacrylate; acrylate ester; 1,4-butanediol dimethacrylate; di ethylene glycol diacrylate; tricyclodecane dimethanol diacrylate; pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, or combinations thereof).
In some embodiments, the volatile monomer is elastomeric (e.g. lauryl methacrylate (LMA), methoxy polyethylene glycol (550) monoacrylate; 2(2-ethoxyethoxy) ethyl acrylate; cyclic Trimethylolpropane formal acrylate; caprolactone acrylate; or a combination thereof); and/or a crosslinker is present and is elastomeric (e.g, a polyethylene glycol dimethacrylate crosslinker such as diiethylene glycol) methyl ether methacrylate (DEGMA); alkoxylated neopentyl glycol diacrylate; polypropylene glycol (400) dimethacrylate; 1,12-dodecanediol dimethacrylate; tetraethylene glycol dimethacrylate, or a combination thereof).
In some embodiments, the light polymerizable component, once polymerized, is one which can degrade (e.g, during heating or baking) to form a constituent for further (e.g, heat) cure. Thus, it is converted, in part, to a "Part B" thermally reactive component. In some embodiments, the additional part B thermally reactive components (e.g., chain extenders such
as polyols and/or polyamines) are carried in the green, light cured, object, where they can participate in a subsequent cure to impart desired physical properties to the object.
Chain extenders. Examples of polyol ( e.g ., diol, triol) chain extenders include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3 -propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydroquinone bis(2-hydroxy ethyl) ether (HQEE), glycerol, trimethylolpropane, trimethylolpropane ethoxylate (TPE), 1,2,6-hexanetriol, and pentaerythritol. Natural oil polyols (biopolyols) may also be used. Such polyols may be derived, e.g., from vegetable oils (triglycerides), such as soybean oil, by known techniques. See, e.g. , U.S. Patent No. 6,433,121 to Petrovic et al.
Polyamine {e.g., diamine, triamine) chain extenders are known and include but are not limited to those described in US Patent Nos. 10,190,020; and 9,908,146. A particular example is 4,4’ -methyl enebis(2-methylcy cl ohexyl-amine) (or "MACM").
In some embodiments, the chain extender is or consists essentially of a polyol, the organometallic catalyst is present, and the blocking agent is n-vinyl formamide (and optionally wherein the resin is packaged with all constituents mixed together in a single container, i.e., as a IK resin).
Catalysts. In the present invention, one or more metal organometallic chelate catalysts, such as non-tin catalysts, can be incorporated into the resin composition. Such catalysts are known and described in, for example, US Patent No. 5,965,686 to Blank et al., 8,912,113 to Ravichandran et al.; 9,066,316 to Hsieh et al., and 10,023,764 to Hsieh et al.; and in W. Blank et al., Catalysis of the Isocyanate-Hydroxyl Reaction by Non-Tin Catalysts (1999); W. Blank et al., Catalysis of Blocked Isocyanates with Non-Tin Catalysts (2000); J. Florio et al., Novel Bismuth Carboxylate Catalysts with Good Hydrolytic Stability and HFO Compatibility (2017); the disclosures of which are incorporated herein by reference in their entirety.
In some embodiments, the catalyst comprises a metal carboxylate such as a zinc carboxylate and/or a bismuth carboxylate.
In some embodiments, the organometallic catalyst comprises a metal amidine complex and/or a second compound, wherein the second compound is a metal carboxylate or a carboxylic acid, and/or a third compound wherein the third compound is a metal chelate complex of an acetylacetonate {e.g., pentanedione), optionally wherein the metal of the metal amidine complex and the metal of the metal carboxylate and/or the metal of the metal acetylacetonate (when present) are not identical. Note that the various organic groups can be
substituted or unsubstituted. For example, the acetylacetonate can be further substituted, for instance with one to six methyl groups or one to six fluorines at the 1 and 5 positions.
In some embodiments, the metal amidine complex is of the chemical formula metal(amidine)w(carboxylate)2, wherein w is an integer from 1 to 4.
In some embodiments, the metal of the metal amidine complex, the metal of the metal carboxylate, and the metal of the chelate complex are independently copper, zinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium, tin, hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.
In some embodiments, the metal of the metal amidine complex and the metal of the metal carboxylate are independently zinc or bismuth.
In some embodiments, the amidine is 1,1,3,3-tetramethyl guanidine or 1- methylimidazole.
In some embodiments, the chelate is pentanedione, hexafluoropentanedione or tetramethy 1 octanedi one .
In some embodiments, the carboxylate is octoate, neodecanoate, naphthenate, stearate, or oxalate.
In some embodiments, the second compound comprises a zinc carboxylate and/or a bismuth carboxylate.
Particular examples of suitable catalysts include, but are not limited to K-KAT® catalysts XK-348, XK-635, XK-651, XK-661, XK-672, and XK-678, available from King Industries, 1 Science Road, Norwalk, CT 06852 USA ( See generally King Industries, K- KAT® Guide to Tin-Free Catalysts for Urethane Coatings (2018)).
Photoinitiators. Photoinitiators included in the polymerizable liquid (resin) can be any suitable photoiniator, including type I and type II photoinitiators and including commonly used UV photoinitiators, examples of which include but are not limited to such as acetophenones (diethoxyacetophenone for example), phosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide (PPO), Irgacure® 369, etc. See, e.g, US Patent No. 9,453,142 to Rolland et al.
The liquid resin or polymerizable material can have solid particles suspended or dispersed therein. Any suitable solid particle can be used, depending upon the end product being fabricated. The particles can be metallic, organic/polymeric, inorganic, or composites or mixtures thereof. The particles can be nonconductive, semi-conductive, or conductive
(including metallic and non-metallic or polymer conductors); and the particles can be magnetic, ferromagnetic, paramagnetic, or nonmagnetic. The particles can be of any suitable shape, including spherical, elliptical, cylindrical, etc. The particles can be of any suitable size (for example, ranging from 1 nm to 20 pm average diameter).
The particles can comprise an active agent or detectable compound as described below, though these may also be provided dissolved or solubilized in the liquid resin as also discussed below. For example, magnetic or paramagnetic particles or nanoparticles can be employed.
The liquid resin can have additional ingredients solubilized therein, including pigments, dyes, diluents, active compounds or pharmaceutical compounds, detectable compounds ( e.g ., fluorescent, phosphorescent, radioactive), etc., again depending upon the particular purpose of the product being fabricated. Examples of such additional ingredients include, but are not limited to, proteins, peptides, nucleic acids (DNA, RNA) such as siRNA, sugars, small organic compounds (drugs and drug-like compounds), etc., including combinations thereof.
Dyes/non-reactive light absorbers. In some embodiments, polymerizable liquids for carrying out the present invention include a non-reactive pigment or dye that absorbs light, particularly UV light. Suitable examples of such light absorbers include, but are not limited to: (i) titanium dioxide (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), (ii) carbon black (e.g, included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or (iii) an organic ultraviolet light absorber such as a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, and/or benzotriazole ultraviolet light absorber (e.g, Mayzo BLS1326) (e.g, included in an amount of 0.001 or 0.005 to 1, 2 or 4 percent by weight). Examples of suitable organic ultraviolet light absorbers include, but are not limited to, those described in US Patent Nos. 3,213,058; 6,916,867; 7,157,586; and 7,695,643, the disclosures of which are incorporated herein by reference.
Fillers. Any suitable filler may be used in connection with the present invention, depending on the properties desired in the part or object to be made. Thus, fillers may be solid or liquid, organic or inorganic, and may include reactive and non-reactive rubbers: siloxanes, acrylonitrile-butadiene rubbers; reactive and non-reactive thermoplastics (including but not limited to: poly(ether imides), maleimide-styrene terpolymers, polyarylates, polysulfones and polyethersulfones, etc.) inorganic fillers such as silicates (such as talc, clays, silica, mica), glass, carbon nanotubes, graphene, cellulose nanocrystals, etc.,
including combinations of all of the foregoing. Suitable fillers include tougheners, such as core-shell rubbers, as discussed below.
Tougheners. One or more polymeric and/or inorganic tougheners can be used as a filler in the present invention. The toughener may be uniformly distributed in the form of particles in the cured product. The particles could be less than 5 microns (pm) in diameter. Such tougheners include, but are not limited to, those formed from elastomers, branched polymers, hyperbranched polymers, dendrimers, rubbery polymers, rubbery copolymers, block copolymers, core-shell particles, oxides or inorganic materials such as clay, polyhedral oligomeric silsesquioxanes (POSS), carbonaceous materials (e.g., carbon black, carbon nanotubes, carbon nanofibers, fullerenes), ceramics and silicon carbides, with or without surface modification or functionalization.
Core-shell rubbers. Core-shell rubbers are particulate materials (particles) having a rubbery core. Such materials are known and described in, for example, US Patent Application Publication No. 20150184039, as well as US Patent Application Publication No. 20150240113, and US Patent Nos. 6,861,475, 7,625,977, 7,642,316, 8,088,245, and elsewhere. In some embodiments, the core-shell rubber particles are nanoparticles (i.e., having an average particle size of less than 1000 nanometers (nm)). Generally, the average particle size of the core-shell rubber nanoparticles is less than 500 nm, e.g., less than 300 nm, less than 200 nm, less than 100 nm, or even less than 50 nm. Typically, such particles are spherical, so the particle size is the diameter; however, if the particles are not spherical, the particle size is defined as the longest dimension of the particle. Suitable core-shell rubbers include, but are not limited to, those sold by Kaneka Corporation under the designation Kaneka Kane Ace, including the Kaneka Kane Ace 15 and 120 series of products, including Kaneka Kane Ace MX 120, Kaneka Kane Ace MX 153, Kaneka Kane Ace MX 154, Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170, Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
Organic diluents. In some embodiments, diluents for use in the present invention are preferably reactive organic diluents; that is, diluents that will degrade, isomerize, cross-react, or polymerize, with themselves or a light polymerizable component, during the additive manufacturing step. In general, the diluent(s) are included in an amount sufficient to reduce the viscosity of the polymerizable liquid or resin (e.g., to not more than 15,000, 10,000, 6,000, 5,000, 4,000, or 3,000 centipoise at 25 degrees Centigrade). Suitable examples of diluents include, but are not limited to, isobornyl methacrylate, TBAEMA (tert-butyl amino ethyl methacrylate), tetrahydrofurfuryl methacrylate, N, A-di methyl acryl a i de, A-vinyl-2-
pyrrolidone, and A -vinyl formamide, or a mixture of two or more thereof. The diluent may be included in the polymerizable liquid in any suitable amount, typically from 1, 5 or 10 percent by weight, up to about 30 or 40 percent by weight, or more.
Resin packaging. The resin may be packaged as two separate precursors, which are mixed together and dispensed prior to use (sometimes referred to as "2K resins") or in some embodiments may be packaged in a premixed form, in the same chamber of a single container (sometimes referred to as a " IK" resin). In either case, the resin is dispensed into an additive manufacturing apparatus for production of a "green" intermediate object.
2. Methods.
Suitable additive manufacturing methods and apparatus in which resins as described herein can be used include bottom-up and top-down additive manufacturing apparatus, as known and described in, for example, U.S. Patent No. 5,236,637 to Hull, US Patent Nos. 5,391,072 and 5,529,473 to Lawton, U.S. Patent No. 7,438,846 to John, US Patent No. 7,892,474 to Shkolnik, U.S. Patent No. 8,110,135 to El-Siblani, U.S. Patent Application Publication No. 2013/0292862 to Joyce, and US Patent Application Publication No. 2013/0295212 to Chen et al. The disclosures of these patents and applications are incorporated by reference herein in their entirety.
In some embodiments, the additive manufacturing step is carried out by one of the family of methods sometimes referred to as continuous liquid interface production (CLIP). CLIP is known and described in, for example, US Patent Nos. 9,211,678; 9,205,601; 9,216,546; and others; in J. Tumbleston et al., Continuous liquid interface production of 3D Objects, Science 347, 1349-1352 (2015); and in R. Janusziewcz et al., Layerless fabrication with continuous liquid interface production, Proc. Natl. Acad. Sci. USA 113, 11703-11708 (2016). Other examples of methods and apparatus for carrying out particular embodiments of CLIP include, but are not limited to: Batchelder et al., US Patent Application Pub. No. US 2017/0129169; Sun and Lichkus, US Patent Application Pub. No. US 2016/0288376; Willis et al., US Patent Application Pub. No. US 2015/0360419; Lin et al., US Patent Application Pub. No. US 2015/0331402; D. Castanon, US Patent Application Pub. No. US 2017/0129167. B. Feller, US Pat App. Pub. No. US 2018/0243976 (Aug 30, 2018); M. Panzer and J. Tumbleston, US Pat App Pub. No. US 2018/0126630 (May 10, 2018); and K. Willis and B. Adzima, US Pat App Pub. No. US 2018/0290374 (Oct. 11, 2018).
Following additive manufacturing, objects can, if desired, be cleaned ( e.g ., wiped, washed, spun to centrifugally separate unpolymerized resin from the object, etc.) and further cured (e.g., by baking), in accordance with known techniques.
3. Objects.
The resins and methods described herein can be used to make a variety of objects, including but not limited to cushions, bumpers, and shock absorbers, with particular examples including helmet pads and liners, seat cushions, bed cushions, body pads such as shoulder pads, knee pads, and shin guards, balls having cores or internal layers with different tensile properties than the outer shell thereof, etc. and the like.
In some embodiments, the object includes at least two portions having different glass transition temperatures, each portion comprising: (a) a light polymerization product of (i) a reactive blocked prepolymer, (ii) a volatile reactive monomer, and (iii) optionally, a crosslinker; and (b) a heat polymerization product of: (i) a polyol and/or a polyamine, and (ii) a deblocked prepolymer produced by the thermal degradation of the light polymerization product. Each portion may differ from one another in: (i) the degree of incorporation of the volatile reactive monomer and/or crosslinker into the light polymerization product, and (ii) the amount of heat polymerization product present, with (iii) the amount of heat polymerization product present in each portion inversely related to the degree of incorporation of the volatile reactive monomer and/or crosslinker into the light polymerization product in that portion.
In some embodiments, the at least two portions meet one another at a non-planar (e.g, curved, angled, or combinations thereof) boundary zone.
In some embodiments, the at least two portions meet one another at a boundary zone having an average thickness of at least one, two, or three millimeters, where said different glass transition temperatures change to one another gradually across said boundary zone.
In some embodiments, the at least two portions meet one another at a boundary zone comprised of an open cell lattice.
In some embodiments, one of the at least two portions is contained within another of the at least two portions.
The regions or portions of the object with different tensile properties can join to one another as a homogeneous lattice structure (that is, without intervening walls or solid layers), as seen in Figure 2A, although it will be appreciated that various unit cells within the homogeneous lattice can differ from one another.
A particular example is a helmet liner that transitions from an elastomeric internal (or body facing) portion to a rigid external portion.
The regions or portions of the object with different tensile properties can connect to one another along a gradual or extended transition zone (in contrast to the more sudden transition obtained when switching cassettes with different resins as described in Rolland et al., noted above).
As illustrated in the non-limiting Examples of Figures 3A-3B, the object 201 can have different portions or regions 202, 203, 204, 205 of different tensile properties ( e.g rigid versus elastomeric versus flexible) that join to one another at a non-planar interface, such as a curved interface, and can have one region fully or partially contained within another region (for example, as regions 202 is contained within region 203, as region 203 is contained within region 204, as region 204 is contained within region 205). Still more complicated patterns of interrelated regions can be obtained, including checkerboard, spiral, and other intertwined regions, with the variation of tensile properties being attainable by varying light intensity or dose on a voxel-by-voxel basis during additive manufacturing of the object.
The present invention is explained in greater detail in the following non-limiting Examples.
EXAMPLES
The following examples describe a single resin that is capable of producing a gradient of properties depending on the amount of UV light exposure during the printing process. In these examples, an ABPU normally used for the production of elastomeric objects (ATB7 ABPU) was mixed with a monomer normally used for the production of rigid objects (IBOMA). Since the Tg of the reactive monomer was high, when incorporated into the part at a higher level (high light dose areas) it causes that area to have a higher Tg, versus when incorporated at lower levels (low light dose areas) the polyurethane (PU) network is more prevalent and forms a lower Tg.
The following materials and abbreviations are used herein:
IPDI: isophorone diisocyanate;
TB or TBAEMA: tert-butylaminoethyl methacrylate;
P03G2K: 2 kiloDalton poly(trimethylene ether)glycol (a polyether polyol produced by the self condensation polymerization of 1,3-propanediol (PDO));
ATB7 ABPU: a reactive methacrylate blocked polyurethane prepolymer, prepared as described in J. Rolland et al., US Patent No.9,598,606, from the above ingredients in a molar ratio of IPDI:PO3G2K:TB of 3:1:4);
IBOMA: Isobornyl methacrylate, a reactive, volatile monomer;
5 MACM: 4,4’-methylenebis(2-methylcyclohexyl-amine), a polyamine (Part B);
TPO: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, a photoinitiator; DBA: 9,10-dibromoanthracene, an ultraviolet light absorber. EXAMPLE 1
10 Resin Formulation
A resin was prepared by adding 50g IBOMA, 0.2g DBA, and 1.6g TPO to a 300mL THINKY™ mixer cup and mixing the components together in a planetary centrifugal mixer (Thinky Corporation) for 10-20 minutes, until solids are dissolved.131g of the ATB7 ABPU was then added and mixed for another 4 minutes. Lastly, 17.2g of MACM was added and 15 mixed for 2 minutes. The resin was then tested for basic properties, such as viscosity and dose-to-cure, and prepared for printing by filtering the resin and placing it into the window cassette of a Carbon Inc. M1 printer. EXAMPLE 2
Print script were constructed that applied an intensity mask to different areas of the build platform during production of one or more objects on the same carrier platform, at the same time, from the same resin.
A first script had a gradient of 100% to 10% of the initial exposure intensity in 10% 25 bands along the X axis, as shown in Figure 1A.
Another script used had 4 different quadrants which were respectively 25%, 50%, 75% and 100% of the initial exposure intensity in the upper right, upper left, lower left and lower right quadrants of the build platform, as shown in Figure 1B, from which four different objects were produced at the same time, from the same pool of resin on the window cassette. 30 Exposure time was kept constant for each slice in this example, but many other methods for controlling dose can be used to achieve these gradient properties, such as by varying intensity in the "Z" or vertical dimension during production of an object, or by using exposure time differences in the Z dimension in combination with an intensity map in the XY dimensions during production of the object.
The script was applied to the relevant test print, in this case, a set of lattices. The print parameters were adjusted to allow for printing even in the lowest-dose areas, and the lattice objects produced from a resin as described in EXAMPLE 1 above.
After production, the "green" objects were washed in isopropyl alcohol for between 5 30 seconds and five minutes, to remove excess resin.
After washing, the objects were baked for about 12 hours at 120 degrees Centigrade in a Yamato convection oven to allow full formation of the thermal network, and to encourage evaporation of the ultraviolet network in the "green" object formed during the additive manufacturing step. The different objects, shown in Figure 2A-2B, had clear 10 differences in feel and properties. The foregoing is illustrative of the present invention, and is not to be construed as limiting thereof. The invention is defined by the following claims, with equivalents of the claims to be included therein.
15
Claims
1. A dual cure additive manufacturing resin, comprising:
(a) light polymerizable component comprised of:
(i) a reactive blocked prepolymer, said prepolymer comprised of a rigid or elastic polyurethane, polyurea, or copolymer thereof ( e.g ., in an amount of from 5, 10, or 20 percent by weight to 70, 80, or 90 percent by weight);
(ii) a volatile (meth)acrylate monomer, wherein said monomer is rigid when said prepolymer is elastic, or said monomer is elastic when said prepolymer is rigid (e.g., in an amount of from 90, 80, or 70 percent by weight to 20, 10, or 5 percent by weight);
(iii) a photoinitiator (e.g, in an amount of from 0.1 to 4 percent by weight); and
(iv) optionally, but preferably, an ultraviolet light absorber and/or pigment (e.g, in an amount when present of from 0.01 or 0.1 to 1 or 2 percent by weight);
(v) optionally, a crosslinker (e.g, a volatile or non-volatile (meth)acrylate, acrylamide, or vinyl crosslinker, which can be rigid or elastomeric)(e.g., in an amount when present of from 0.1 or 1 percent by weight to 30 or 50 percent by weight);
said resin further comprising:
(b) a heat polymerizable component comprised of:
(i) a chain extender selected from the group consisting of polyols, polyamines, and combinations thereof (e.g, in an amount of from 5 or 10 percent by weight to 30 or 40 percent by weight); and
(ii) optionally, an organometallic catalyst (e.g, in an amount when present of 0.01 or 0.1 percent by weight to 2 or 3 percent by weight).
2. The resin of claim 1, wherein said reactive blocked prepolymer is produced by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, alcohol (meth)acrylate, maleimide, or n-vinyl formamide blocking agent.
3. The resin of any preceding claim, wherein:
the glass transition temperature of a polymer formed only from one of said
elastomeric monomers, prepolymers, or crosslinkers is 25 degrees Celsius or less; and
the glass transition temperature of a polymer formed from only one of said rigid monomers, prepolymers, or crosslinkers is 50 degrees Celsius or more.
4. The resin of any preceding claim, wherein said volatile monomer is rigid ( e.g ., is isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), 3,3,5-trimethylcyclohexyl methacrylate; 2-phenoxy ethyl methacrylate or combinations thereof),
and/or said crosslinker is present and rigid (e.g., is neopentyl glycol dimethacrylate (NPGDMA), ethoxylated bisphenol A dimethacrylate; acrylate ester; 1,4-butanediol dimethacrylate; diethylene glycol diacrylate; tricyclodecane dimethanol diacrylate;
pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, or combinations thereof).
5. The resin of any preceding claim, wherein said volatile monomer is elastomeric (e.g. lauryl methacrylate (LMA), methoxy polyethylene glycol (550) monoacrylate; 2(2- ethoxyethoxy) ethyl acrylate; cyclic Trimethylolpropane formal acrylate; caprolactone acrylate; or a combination thereof),
and/or said crosslinker is present and is elastomeric (e.g, a polyethylene glycol dimethacrylate crosslinker such as di(ethylene glycol) methyl ether methacrylate (DEGMA); alkoxylated neopentyl glycol diacrylate; polypropylene glycol (400) dimethacrylate; 1,12- dodecanediol dimethacrylate; tetraethylene glycol dimethacrylate, or a combination thereof).
6. The resin of any preceding claim, wherein said chain extender consists essentially of a polyol, wherein said organometallic catalyst is present, and wherein said blocking agent is n-vinyl formamide (and optionally wherein said resin is packaged with all constituents mixed together in a single container, i.e., as a IK resin).
7. A method of making a three-dimensional object having at least two portions with different glass transition temperatures, comprising:
(a) producing an intermediate object by light polymerization of a resin of any preceding claim in an additive manufacturing process (e.g, stereolithography), with each of the at least two portions receiving a different dose of light during said producing;
(b) optionally cleaning said intermediate object; and then
(c) heating said intermediate object to produce said 3D object, with the glass transition temperature of each portion defined by the dose of light received by that portion during said producing step.
8. The method of claim 7, wherein one of said portions is rigid, and the other of said portions is flexible or elastomeric.
9. The method of claim 7 or claim 8, wherein said manufacturing process comprises bottom-up stereolithography ( e.g ., continuous liquid interface production).
10. A three-dimensional object produced by the method of any one of claims 7-9.
11. A three-dimensional object produced by additive manufacturing from a single dual cure resin, the object comprising at least two portions having different glass transition temperatures, each of said at least two portions comprising:
(a) a light polymerization product of (i) a reactive blocked prepolymer, (ii) a volatile reactive monomer, and (iii) optionally, a crosslinker;
(b) a heat polymerization product of: (i) a polyol and/or a polyamine, and (ii) a deblocked prepolymer produced by the thermal degradation of said light polymerization product;
with each of said portions differing from one another in: (i) the degree of
incorporation of said volatile reactive monomer and/or said crosslinker into said light polymerization product, and (ii) the amount of said heat polymerization product present, with (iii) the amount of heat polymerization product present in each portion inversely related to the degree of incorporation of said volatile reactive monomer and/or crosslinker into said light polymerization product in that portion.
12. The object of claim 11, wherein said at least two portions meet one another at a non-planar (e.g., curved, angled, or combinations thereof) boundary zone.
13. The object of claim 11 or claim 12, wherein said at least two portions meet one another at a boundary zone having an average thickness of at least one, two, or three millimeters, where said different glass transition temperatures change to one another gradually across said boundary zone.
14. The object of any one of claims 11-13, wherein said at least two portions meet one another at a boundary zone comprised of an open cell lattice.
15. The object of any one of claims 11-14, wherein one of said at least two portions is contained within another of said at least two portions.
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---|---|---|---|---|
DE102021131634A1 (en) | 2021-12-01 | 2023-06-01 | Bayerische Motoren Werke Aktiengesellschaft | Process for the additive manufacturing of a component |
DE102022110120A1 (en) | 2022-04-27 | 2023-11-02 | Bayerische Motoren Werke Aktiengesellschaft | Method for the additive production of a three-dimensional object |
Citations (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3213058A (en) | 1960-12-19 | 1965-10-19 | American Cyanamid Co | Polymers reacted with benzotriazole uv absorbers |
US3694389A (en) | 1970-08-06 | 1972-09-26 | Rohm & Haas | Thermosetting coatings based on oxime-blocked isocyanates |
US3947426A (en) | 1974-04-12 | 1976-03-30 | Story Chemical Corporation | Solid particle-form polymerizable polymeric material and compositions, structures and methods of employing and producing the same |
US5236637A (en) | 1984-08-08 | 1993-08-17 | 3D Systems, Inc. | Method of and apparatus for production of three dimensional objects by stereolithography |
US5391072A (en) | 1990-10-29 | 1995-02-21 | E. I. Du Pont De Nemours And Company | Solid imaging apparatus having a semi-permeable film |
US5529473A (en) | 1990-07-05 | 1996-06-25 | E. I. Du Pont De Nemours And Company | Solid imaging system using differential tension elastomerc film |
US5965686A (en) | 1997-03-19 | 1999-10-12 | King Industries, Inc. | Zirconium urethane catalysts |
US6433121B1 (en) | 1998-11-06 | 2002-08-13 | Pittsburg State University | Method of making natural oil-based polyols and polyurethanes therefrom |
US6861475B2 (en) | 2002-10-16 | 2005-03-01 | Rohm And Haas Company | Smooth, flexible powder coatings |
US6916867B2 (en) | 2000-04-04 | 2005-07-12 | Ciba Specialty Chemicals Corporation | Synergistic mixtures of UV-absorbers in polyolefins |
US7157586B2 (en) | 2000-02-01 | 2007-01-02 | Ciba Specialty Chemcials Corporation | Bloom-resistant benzotriazole UV absorbers and compositions stabilized therewith |
US7438846B2 (en) | 2001-04-23 | 2008-10-21 | Envisiontec Gmbh | Apparatus and method for the non-destructive separation of hardened material layers from a flat construction plane |
US7625977B2 (en) | 2007-06-20 | 2009-12-01 | Dow Global Technologies Inc. | Adhesive of epoxy resin, toughener and blocked isocyanate polytetrahydrofuran toughener |
US7642316B2 (en) | 2004-10-14 | 2010-01-05 | Dow Global Technologies, Inc. | Rubber modified monovinylidene aromatic polymers and fabricated articles prepared therefrom |
US7695643B2 (en) | 2005-02-02 | 2010-04-13 | Ciba Specialty Chemicals Corporation | Long wavelength shifted benzotriazole UV-absorbers and their use |
US7892474B2 (en) | 2006-11-15 | 2011-02-22 | Envisiontec Gmbh | Continuous generative process for producing a three-dimensional object |
US8088245B2 (en) | 2007-04-11 | 2012-01-03 | Dow Global Technologies Llc | Structural epoxy resins containing core-shell rubbers |
US8110135B2 (en) | 2007-10-26 | 2012-02-07 | Envisiontec Gmbh | Process and freeform fabrication system for producing a three-dimensional object |
US20130202392A1 (en) | 2011-08-11 | 2013-08-08 | Daifuku Co., Ltd. | Article Transport Facility |
US20130292862A1 (en) | 2012-05-03 | 2013-11-07 | B9Creations, LLC | Solid Image Apparatus With Improved Part Separation From The Image Plate |
US20130295212A1 (en) | 2012-04-27 | 2013-11-07 | University Of Southern California | Digital mask-image-projection-based additive manufacturing that applies shearing force to detach each added layer |
US8912113B2 (en) | 2011-03-06 | 2014-12-16 | King Industries, Inc. | Compositions of a metal amidine complex and second compound, coating compositions comprising same |
US9066316B2 (en) | 2007-11-19 | 2015-06-23 | Qualcomm Incorporated | Diagnostic monitoring by a wireless device |
US20150184039A1 (en) | 2012-08-27 | 2015-07-02 | Dow Global Technologies Llc | Accelerated and toughened two part epoxy adhesives |
US20150240113A1 (en) | 2012-09-17 | 2015-08-27 | 3N Innovative Properties Company | Powder coating epoxy compositions, methods, and articles |
US20150331402A1 (en) | 2014-05-13 | 2015-11-19 | Autodesk, Inc. | Intelligent 3d printing through optimization of 3d print parameters |
US9205601B2 (en) | 2013-02-12 | 2015-12-08 | Carbon3D, Inc. | Continuous liquid interphase printing |
US20150360419A1 (en) | 2014-05-13 | 2015-12-17 | Autodesk, Inc. | 3d print adhesion reduction during cure process |
WO2016126796A2 (en) * | 2015-02-05 | 2016-08-11 | Carbon3D, Inc. | Method of additive manufacturing by intermittent exposure |
WO2016140891A1 (en) * | 2015-03-05 | 2016-09-09 | Carbon3D, Inc. | Continuous liquid interface production with sequential patterned exposure |
US9453142B2 (en) | 2014-06-23 | 2016-09-27 | Carbon3D, Inc. | Polyurethane resins having multiple mechanisms of hardening for use in producing three-dimensional objects |
US20160288376A1 (en) | 2015-03-31 | 2016-10-06 | Dentsply Sirona Inc. | Three-dimensional fabricating systems for rapidly producing objects |
US20170129169A1 (en) | 2015-11-06 | 2017-05-11 | Stratasys, Inc. | Continuous liquid interface production system with viscosity pump |
US20170129167A1 (en) | 2015-04-30 | 2017-05-11 | Raymond Fortier | Stereolithography system |
US9908146B2 (en) | 2011-03-30 | 2018-03-06 | 3M Innovative Properties Company | Composition comprising cyclic secondary amine and methods of coating drinking water pipelines |
US20180126630A1 (en) | 2016-11-04 | 2018-05-10 | Carbon, Inc. | Continuous liquid interface production with upconversion photopolymerization |
WO2018094131A1 (en) * | 2016-11-21 | 2018-05-24 | Carbon, Inc. | Method of making three-dimensional object by delivering reactive component for subsequent cure |
US10023764B2 (en) | 2012-01-25 | 2018-07-17 | Basf Coatings Gmbh | Zinc (1-methylimidazole)bis(2-ethylhexanoate) complex catalyzed coating material composition |
US20180243976A1 (en) | 2015-09-30 | 2018-08-30 | Carbon, Inc. | Method and Apparatus for Producing Three- Dimensional Objects |
US20180290374A1 (en) | 2014-09-08 | 2018-10-11 | Holo, Inc. | Three dimensional printing adhesion reduction using photoinhibition |
WO2019006266A1 (en) * | 2017-06-30 | 2019-01-03 | 3M Innovative Properties Company | Three-dimensional article and method of making a three-dimensional article |
US10190020B2 (en) | 2014-10-22 | 2019-01-29 | The United States Of America, As Represented By The Secretary Of The Navy | Siloxane-based coatings containing polymers with urea linkages and terminal alkoxysilanes |
WO2019112707A1 (en) * | 2017-12-08 | 2019-06-13 | Carbon, Inc. | Shelf stable, low tin concentration, dual cure additive manufacturing resins |
-
2020
- 2020-05-26 WO PCT/US2020/034521 patent/WO2020263480A1/en active Application Filing
Patent Citations (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3213058A (en) | 1960-12-19 | 1965-10-19 | American Cyanamid Co | Polymers reacted with benzotriazole uv absorbers |
US3694389A (en) | 1970-08-06 | 1972-09-26 | Rohm & Haas | Thermosetting coatings based on oxime-blocked isocyanates |
US3947426A (en) | 1974-04-12 | 1976-03-30 | Story Chemical Corporation | Solid particle-form polymerizable polymeric material and compositions, structures and methods of employing and producing the same |
US5236637A (en) | 1984-08-08 | 1993-08-17 | 3D Systems, Inc. | Method of and apparatus for production of three dimensional objects by stereolithography |
US5529473A (en) | 1990-07-05 | 1996-06-25 | E. I. Du Pont De Nemours And Company | Solid imaging system using differential tension elastomerc film |
US5391072A (en) | 1990-10-29 | 1995-02-21 | E. I. Du Pont De Nemours And Company | Solid imaging apparatus having a semi-permeable film |
US5965686A (en) | 1997-03-19 | 1999-10-12 | King Industries, Inc. | Zirconium urethane catalysts |
US6433121B1 (en) | 1998-11-06 | 2002-08-13 | Pittsburg State University | Method of making natural oil-based polyols and polyurethanes therefrom |
US7157586B2 (en) | 2000-02-01 | 2007-01-02 | Ciba Specialty Chemcials Corporation | Bloom-resistant benzotriazole UV absorbers and compositions stabilized therewith |
US6916867B2 (en) | 2000-04-04 | 2005-07-12 | Ciba Specialty Chemicals Corporation | Synergistic mixtures of UV-absorbers in polyolefins |
US7438846B2 (en) | 2001-04-23 | 2008-10-21 | Envisiontec Gmbh | Apparatus and method for the non-destructive separation of hardened material layers from a flat construction plane |
US6861475B2 (en) | 2002-10-16 | 2005-03-01 | Rohm And Haas Company | Smooth, flexible powder coatings |
US7642316B2 (en) | 2004-10-14 | 2010-01-05 | Dow Global Technologies, Inc. | Rubber modified monovinylidene aromatic polymers and fabricated articles prepared therefrom |
US7695643B2 (en) | 2005-02-02 | 2010-04-13 | Ciba Specialty Chemicals Corporation | Long wavelength shifted benzotriazole UV-absorbers and their use |
US7892474B2 (en) | 2006-11-15 | 2011-02-22 | Envisiontec Gmbh | Continuous generative process for producing a three-dimensional object |
US8088245B2 (en) | 2007-04-11 | 2012-01-03 | Dow Global Technologies Llc | Structural epoxy resins containing core-shell rubbers |
US7625977B2 (en) | 2007-06-20 | 2009-12-01 | Dow Global Technologies Inc. | Adhesive of epoxy resin, toughener and blocked isocyanate polytetrahydrofuran toughener |
US8110135B2 (en) | 2007-10-26 | 2012-02-07 | Envisiontec Gmbh | Process and freeform fabrication system for producing a three-dimensional object |
US9066316B2 (en) | 2007-11-19 | 2015-06-23 | Qualcomm Incorporated | Diagnostic monitoring by a wireless device |
US8912113B2 (en) | 2011-03-06 | 2014-12-16 | King Industries, Inc. | Compositions of a metal amidine complex and second compound, coating compositions comprising same |
US9908146B2 (en) | 2011-03-30 | 2018-03-06 | 3M Innovative Properties Company | Composition comprising cyclic secondary amine and methods of coating drinking water pipelines |
US20130202392A1 (en) | 2011-08-11 | 2013-08-08 | Daifuku Co., Ltd. | Article Transport Facility |
US10023764B2 (en) | 2012-01-25 | 2018-07-17 | Basf Coatings Gmbh | Zinc (1-methylimidazole)bis(2-ethylhexanoate) complex catalyzed coating material composition |
US20130295212A1 (en) | 2012-04-27 | 2013-11-07 | University Of Southern California | Digital mask-image-projection-based additive manufacturing that applies shearing force to detach each added layer |
US20130292862A1 (en) | 2012-05-03 | 2013-11-07 | B9Creations, LLC | Solid Image Apparatus With Improved Part Separation From The Image Plate |
US20150184039A1 (en) | 2012-08-27 | 2015-07-02 | Dow Global Technologies Llc | Accelerated and toughened two part epoxy adhesives |
US20150240113A1 (en) | 2012-09-17 | 2015-08-27 | 3N Innovative Properties Company | Powder coating epoxy compositions, methods, and articles |
US9216546B2 (en) | 2013-02-12 | 2015-12-22 | Carbon3D, Inc. | Method and apparatus for three-dimensional fabrication with feed through carrier |
US9211678B2 (en) | 2013-02-12 | 2015-12-15 | Carbon3D, Inc. | Method and apparatus for three-dimensional fabrication |
US9205601B2 (en) | 2013-02-12 | 2015-12-08 | Carbon3D, Inc. | Continuous liquid interphase printing |
US20150360419A1 (en) | 2014-05-13 | 2015-12-17 | Autodesk, Inc. | 3d print adhesion reduction during cure process |
US20150331402A1 (en) | 2014-05-13 | 2015-11-19 | Autodesk, Inc. | Intelligent 3d printing through optimization of 3d print parameters |
US9453142B2 (en) | 2014-06-23 | 2016-09-27 | Carbon3D, Inc. | Polyurethane resins having multiple mechanisms of hardening for use in producing three-dimensional objects |
US9598606B2 (en) | 2014-06-23 | 2017-03-21 | Carbon, Inc. | Methods of producing polyurethane three-dimensional objects from materials having multiple mechanisms of hardening |
US9676963B2 (en) | 2014-06-23 | 2017-06-13 | Carbon, Inc. | Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening |
US20180290374A1 (en) | 2014-09-08 | 2018-10-11 | Holo, Inc. | Three dimensional printing adhesion reduction using photoinhibition |
US10190020B2 (en) | 2014-10-22 | 2019-01-29 | The United States Of America, As Represented By The Secretary Of The Navy | Siloxane-based coatings containing polymers with urea linkages and terminal alkoxysilanes |
WO2016126796A2 (en) * | 2015-02-05 | 2016-08-11 | Carbon3D, Inc. | Method of additive manufacturing by intermittent exposure |
WO2016140891A1 (en) * | 2015-03-05 | 2016-09-09 | Carbon3D, Inc. | Continuous liquid interface production with sequential patterned exposure |
US20160288376A1 (en) | 2015-03-31 | 2016-10-06 | Dentsply Sirona Inc. | Three-dimensional fabricating systems for rapidly producing objects |
US20170129167A1 (en) | 2015-04-30 | 2017-05-11 | Raymond Fortier | Stereolithography system |
US20180243976A1 (en) | 2015-09-30 | 2018-08-30 | Carbon, Inc. | Method and Apparatus for Producing Three- Dimensional Objects |
US20170129169A1 (en) | 2015-11-06 | 2017-05-11 | Stratasys, Inc. | Continuous liquid interface production system with viscosity pump |
US20180126630A1 (en) | 2016-11-04 | 2018-05-10 | Carbon, Inc. | Continuous liquid interface production with upconversion photopolymerization |
WO2018094131A1 (en) * | 2016-11-21 | 2018-05-24 | Carbon, Inc. | Method of making three-dimensional object by delivering reactive component for subsequent cure |
WO2019006266A1 (en) * | 2017-06-30 | 2019-01-03 | 3M Innovative Properties Company | Three-dimensional article and method of making a three-dimensional article |
WO2019112707A1 (en) * | 2017-12-08 | 2019-06-13 | Carbon, Inc. | Shelf stable, low tin concentration, dual cure additive manufacturing resins |
Non-Patent Citations (8)
Title |
---|
"K-KA Tt Guide to Tin-Free Catalysts for Urethane Coatings", 2018, KING INDUSTRIES |
J. FLORIO ET AL., NOVEL BISMUTH CARBOXYLATE CATALYSTS WITH GOOD HYDROLYTIC STABILITY AND HFO COMPATIBILITY, 2017 |
J. POELMAJ. ROLLAND: "Rethinking digital manufacturing with polymers", SCIENCE, vol. 358, 2017, pages 1384 - 1385 |
J. TUMBLESTON ET AL.: "Continuous liquid interface production of 3D Objects", SCIENCE, vol. 347, 2015, pages 1349 - 1352, XP055247221, DOI: 10.1126/science.aaa2397 |
R. JANUSZIEWCZ ET AL.: "Layerless fabrication with continuous liquid interface production", PROC. NATL. ACAD. SCI. USA, vol. 113, 2016, pages 11703 - 11708, XP055542052, DOI: 10.1073/pnas.1605271113 |
R. JANUSZIEWICZ ET AL.: "Layerlessfabrication with continuous liquid interface production", PNAS, vol. 113, 2016, pages 11703 - 11708 |
W. BLANK ET AL., CATALYSIS OF BLOCKED ISOCYANATES WITH NON-TIN CATALYSTS, 2000 |
W. BLANK ET AL., CATALYSIS OF THE ISOCYANATE-HYDROXYL REACTION BY NON-TIN CATALYSTS, 1999 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102021131634A1 (en) | 2021-12-01 | 2023-06-01 | Bayerische Motoren Werke Aktiengesellschaft | Process for the additive manufacturing of a component |
DE102022110120A1 (en) | 2022-04-27 | 2023-11-02 | Bayerische Motoren Werke Aktiengesellschaft | Method for the additive production of a three-dimensional object |
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