WO2020081891A1 - Photocurable resin composition, photocurable resin article, and methods of fabricating the article - Google Patents
Photocurable resin composition, photocurable resin article, and methods of fabricating the article Download PDFInfo
- Publication number
- WO2020081891A1 WO2020081891A1 PCT/US2019/056862 US2019056862W WO2020081891A1 WO 2020081891 A1 WO2020081891 A1 WO 2020081891A1 US 2019056862 W US2019056862 W US 2019056862W WO 2020081891 A1 WO2020081891 A1 WO 2020081891A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylate
- meth
- photocurable resin
- article
- resin
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 175
- 229920005989 resin Polymers 0.000 title claims abstract description 175
- 238000000034 method Methods 0.000 title claims description 45
- 239000011342 resin composition Substances 0.000 title abstract description 98
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 66
- 238000010146 3D printing Methods 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 98
- 239000007787 solid Substances 0.000 claims description 55
- -1 poly(ethylene glycol) Polymers 0.000 claims description 50
- 239000011248 coating agent Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 42
- 239000011148 porous material Substances 0.000 claims description 31
- 230000036316 preload Effects 0.000 claims description 28
- 239000003381 stabilizer Substances 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 13
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 7
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- BFYJDHRWCNNYJQ-UHFFFAOYSA-N oxo-(3-oxo-3-phenylpropoxy)-(2,4,6-trimethylphenyl)phosphanium Chemical compound CC1=CC(C)=CC(C)=C1[P+](=O)OCCC(=O)C1=CC=CC=C1 BFYJDHRWCNNYJQ-UHFFFAOYSA-N 0.000 claims description 5
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 5
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 claims description 3
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 claims description 3
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 claims description 3
- 229940014772 dimethyl sebacate Drugs 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229940116351 sebacate Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 114
- 239000012948 isocyanate Substances 0.000 abstract description 43
- 150000002513 isocyanates Chemical class 0.000 abstract description 43
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 238000006116 polymerization reaction Methods 0.000 abstract description 23
- 239000000463 material Substances 0.000 description 73
- 238000007639 printing Methods 0.000 description 35
- 239000000203 mixture Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000002985 plastic film Substances 0.000 description 21
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 239000003637 basic solution Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 14
- 238000011282 treatment Methods 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000013461 design Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000011417 postcuring Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000012815 thermoplastic material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 4
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 206010061274 Malocclusion Diseases 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- 229940113165 trimethylolpropane Drugs 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BITHHVVYSMSWAG-KTKRTIGZSA-N (11Z)-icos-11-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCC(O)=O BITHHVVYSMSWAG-KTKRTIGZSA-N 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
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- 150000008065 acid anhydrides Chemical class 0.000 description 2
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 2
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- 238000013459 approach Methods 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
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- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
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- 230000008021 deposition Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
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- 238000010348 incorporation Methods 0.000 description 2
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- 238000009966 trimming Methods 0.000 description 2
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 description 1
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- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- UNSRRHDPHVZAHH-YOILPLPUSA-N (5Z,8Z,11Z)-icosatrienoic acid Chemical compound CCCCCCCC\C=C/C\C=C/C\C=C/CCCC(O)=O UNSRRHDPHVZAHH-YOILPLPUSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
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- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
Definitions
- Dental malocclusion affects approximately 60% to 75% (or 4.6 to 5.7 billion) of the global population. Consequently, there is a tremendous global demand for orthodontic treatments to correct malocclusion. Approximately, 15% of these cases are treated with orthodontic clear aligners (690 to 855 million patients per year), representing a market size of $1.5 billion. This market segment has an expected growth of 12.16% compounded annually from 2018-2021 and is likely to reach $2.7 billion by 2021.
- Aligners are manufactured through the following procedure: 1) a dental impression of the patient is taken with a 3D scanner; 2) the dental impression is digitalized and converted into an STL file, compatible with stereolithography CAD software; 3) an orthodontic treatment plan is created by software, where 3D models of the patient’s teeth representing the different stages of treatment are obtained, ranging from the current state of the teeth up to the perfect smile; 4) the models are 3D printed by stereolithography; 5) a sheet of a thermoplastic material is heated up and vacuumed onto the 3D printed models, resulting in aligners resembling the designed treatment plan; 6) the aligners are trimmed with a milling machine and polished afterwards;
- the aligners are packaged and sent to the orthodontists or directly to the patient.
- thickness and mechanical strength are properties homogenous within clear orthodontic aligners, since they are made by heat pressing a piece of plastic sheet onto a preformed mold resembling the shape of the desired aligner.
- each tooth to be moved would require a different amount of force in order to be relocated to its natural position.
- an aligner would have to feature different localized strengths to manipulate each individual tooth with the required forced for its relocation. This is not achieved by current thermoplastic aligners due to the homogeneity of the material.
- the present invention relates to a photocurable resin comprising 75 - 85 weight percent of a urethane (meth)acrylate, 10 - 25 weight percent of a
- the urethane (meth)acrylate comprises a diisocyanate and a hydroxy (meth)acrylate.
- the diisocyanate is selected from the group consisting of: 2,4-toluene diisocyanate, 2,5-toluene diisocyanate, 2,6-toluene diisocyanate, and 4,4’- methylenebis(phenyl isocyanate);
- the hydroxy (meth)acrylate is selected from the group consisting of: poly(ethylene glycol) methacrylate, poly(ethylene glycol) acrylate, polypropylene glycol) methacrylate, polypropylene glycol) acrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.
- the di(meth)acrylate is selected from the group consisting of: triethylene glycol dimethacrylate, dipthylene glycol)dimethacrylate, propylene glycol dimethacrylate, and dipropylene glycol) dimethacrylate.
- the photoinitiator is selected from the group consisting of: diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide; 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide; and bis(2,4,6- trimethylbenzoyl)-phenyl-phosphine oxide.
- the composition further comprises a stabilizer selected from the group consisting of: bis(2,2,6,6-tetramethyl-l- octyloxy-4-piperidyl) sebacate; bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate; methyl l,2,2,6,6-pentamethyl-4-piperidyl sebacate; dimethyl sebacate; and bis(2,2,6,6-tetramethyl-4- piperidyl) sebacate.
- a stabilizer selected from the group consisting of: bis(2,2,6,6-tetramethyl-l- octyloxy-4-piperidyl) sebacate; bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate; methyl l,2,2,6,6-pentamethyl-4-piperidyl sebacate; dimethyl sebacate; and bis(2,2,6,6-tetramethyl-4- piperidyl) sebacate.
- the composition further comprises a second photocurable resin composition comprising a second urethane (meth)acrylate, a second di(meth)acrylate, a triacrylate, and a second photoinitiator.
- a second photocurable resin composition comprising a second urethane (meth)acrylate, a second di(meth)acrylate, a triacrylate, and a second photoinitiator.
- the second urethane methacrylate, a second di(meth)acrylate, a triacrylate, and a second photoinitiator.
- (meth)acrylate of the second photocurable resin comprises a diisocyanate and a hydroxy (meth)acrylate; wherein the diisocyanate is selected from the group consisting of: 2,4-toluene diisocyanate, 2,5-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4’-methylenebis(phenyl isocyanate), and combinations thereof; and wherein the hydroxy (meth)acrylate is selected from the group consisting of: poly(ethylene glycol) methacrylate, poly(ethylene glycol) acrylate, polypropylene glycol) methacrylate, polypropylene glycol) acrylate, 2- hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxypropyl acrylate, 2- hydroxypropyl methacrylate, and combinations thereof.
- the second di(meth)acrylate of the second photocurable resin is selected from the group consisting of: tri
- the triacrylate is l,l-trimethylolpropane triacrylate. In one embodiment, the second
- photoinitiator of the second photocurable resin is selected from the group consisting of: diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide; 2,4,6- trimethylbenzoylethoxyphenylphosphine oxide; and bis(2,4,6-trimethylbenzoyl)-phenyl- phosphine oxide.
- the present invention also relates in part to a method of fabricating an article comprising the steps of: providing a photocurable resin comprising 75 - 85 weight percent of a urethane (meth)acrylate, 10 - 25 weight percent of a di(meth)acrylate, and less than 5 weight percent of a photoinitiator; 3D printing the photocurable resin to form an article; and curing the article.
- the step of providing a photocurable resin comprises the step of providing a second photocurable resin comprising a second urethane
- step of 3D printing the photocurable resin comprises the step of 3D printing the second photocurable resin.
- the present invention further relates in part to a 3D printed resin article wherein the article comprises an inner microarchitecture comprising a photocured resin and a solid coating comprising a second photocured resin; wherein the solid coating encapsulates the inner microarchitecture.
- the microarchitecture comprises pores having an inner diameter of 0.5 mm to 5 mm.
- the microarchitecture comprises a photocured resin having a thickness of 0.1 mm to 3 mm.
- the article when tested with a preload of 0.01 N, has an initial stress of between 0.45 MPa and 1.6 MPa.
- the article, when tested with a preload of 0.01 N has a stress relaxation after 2 hours of between 50% and 65%.
- the article is a tooth aligner.
- Figure 1 is a flowchart of an exemplary method for making a photocurable resin composition.
- Figure 2 depicts the synthesis of MDI-PEGMA from 4,4’- methylenebis(phenyl isocyanate) (MDI) and poly(ethylene glycol) methacrylate (PEGMA).
- MDI 4,4’- methylenebis(phenyl isocyanate)
- PEGMA poly(ethylene glycol) methacrylate
- Figure 3 depicts a ⁇ NMR spectrum of MDI-PEGMA in DMSO.
- Figure 4 depicts the characterization of MDI-PEGMA using Fourier Transform Infrared Spectroscopy (FT-IR) analysis.
- Figure 4A depicts an FTIR analysis spectrum of MDI-PEGMA resin with free isocyanates groups.
- Figure 4B depicts an FT-IR analysis spectrum of MDI-PEGMA resin where isocyanates groups have been reacted.
- FT-IR Fourier Transform Infrared Spectroscopy
- Figure 5 depicts a square designed for top and bottom layers of plastic.
- Figure 6 comprising Figure 6A and Figure 6B, depicts beehive microarchitectures.
- Figure 6A depicts a 3.0 mm inner diameter beehive microarchitecture.
- Figure 6B depicts a 1.5 mm inner diameter beehive microarchitecture.
- Figure 7 depicts the printed parts and post-curing process.
- Figure 7A depicts a 3.0 mm inner diameter beehive.
- Figure 7B depicts a 1.5 mm inner diameter beehive.
- Figure 7C depicts a square structure placed between glass slides prepared for post-curing under UV light.
- Figure 7D depicts a UV light exposure to printed piece for strength enhancement.
- Figure 8, comprising Figure 8A, Figure 8B, and Figure 8C, depicts an assembly of plastic sheets for preparation of microarchitecture plastic sheets.
- Figure 8A depicts a square piece with thin layer of Bioink 2 on top.
- Figure 8B depicts a 3.0 mm beehive structure merge with bottom squared layer.
- Figure 8C depicts an addition of extra Bioink 2 to merge the top and bottom parts with the microarchitecture upon light exposure.
- Figure 9 depicts a sample preparation for dynamic mechanical analysis
- Figure 10 depicts 3D model of aligner and support material.
- Figure 10A depicts a top view of a 3D model of aligner with support material.
- Figure 10B depicts a bottom view of a 3D model of aligner with support material.
- Figure 10C depicts a side view of a 3D model of aligner with support material.
- Figure 10D depicts a front view of a 3D model of aligner with support material.
- Figure 11 depicts a 3D printed aligner with support material.
- Figure 11 A depicts a 3D printed aligner with support material attached to the 3D printer platform.
- Figure 11B depicts a top view of a 3D printed aligner with support material.
- Figure 11C depicts a front view of a 3D printed aligner with support material.
- Figure 11D depicts a side view of a 3D printed aligner with support material.
- Figure 12 depicts a 3D printed aligner with removed support material.
- Figure 12A depicts a side view of a 3D printed aligner with removed support material.
- Figure 12B depicts a top view of a 3D printed aligner with removed support material and cross-sectional view of aligner.
- Figure 12C depicts a cross-section position of a 3D printed aligner with removed support material.
- Figure 12D depicts a cross-sectional view of 3D printed aligner with removed support material.
- Figure 12E depicts a top view of a 3D printed aligner with removed support material.
- Figure 12F depicts an enlarged top view of a 3D printed aligner with removed support material.
- Figure 13 depicts polymerization of Bioinks for mechanical properties analysis.
- Figure 13A depicts a deposition of Bioink onto metal mold.
- Figure 13B depicts a Bioink material exposed to 415 nm light for 1 min.
- Figure 13C depicts a photopolymerized Bioink plastic sheet removed from metal mold.
- Figure 13D depicts the transparency of the photopolymerized Bioink plastic that can be noticed when placed on a white surface with a black line drawn. The line can be observed clearly on front and behind the material.
- Figure 14 depicts a stress relaxation of orthodontic aligner materials.
- Figure 15 comprising Figure 15A, Figure 15B, Figure 15C, Figure 15D,
- Figure 15E, and Figure 15F depicts a preparation of microarchitecture plastic sheets.
- Figure 15A depicts a Pattern B metal mold for preparation of microarchitecture plastic sheets.
- Figure 15B depicts a Pattern A metal mold for preparation of microarchitecture plastic sheets.
- Figure 15C depicts a Bioink 2 dispensed onto Pattern A mold. A red die was added to the formulation for visualization purposes within the final product.
- Figure 15D depicts a photopolymerization of Bioink 2 in Pattern A mold.
- Figure 15E depicts an addition of a layer of Bioink 1 on one side of the meshwork. This layer was polymerized, the piece was turned around and a second layer was dispensed and polymerized to completely embed the Bioink 2 meshwork within two Bioink 1 layers.
- Figure 15F depicts a photopolymerized plastic sheet of Bioink 1 with an embedded Pattern A microarchitecture composed of Bioink 2.
- Figure 16 depicts a stress relaxation of meshwork designs and SmartTrack.
- Figure 17, comprising Figure 17A and Figure 17B, depicts layering patterns.
- Figure 17A depicts a photopolymerized plastic sheet with Pattern C, composed of three layers of Bioink 1.
- Figure 17B depicts a photopolymerized plastic sheet with Pattern D, composed of one layer of Bioink 2 sandwiched between two layers of Bioink 1.
- Figure 18 depicts a stress relaxation of meshwork and layering designs.
- Figure 19 comprising Figure 19A, Figure 19B, Figure 19C, Figure 19D,
- Figure 19E, and Figure 19F depicts DMA results.
- Figure 19A depicts a stress of 3.0 mm beehive compared to Invisalign.
- Figure 19B depicts a stress of 1.5 mm beehive compared to Invisalign.
- Figure 19C depicts a stress comparison between microarchitecture structures and Invisalign.
- Figure 19D depicts a remaining stress percent of 3.0 mm beehive compared to Invisalign.
- Figure 19E depicts a remaining stress percent of 1.5 mm beehive compared to Invisalign.
- Figure 19F depicts a remaining stress percent comparison between
- Figure 20 depicts a stereolithography polymerization of photocurable resins by a bottom-up system with scanning laser (left) or top-down setup with digital light projection (right) (Chia et al, 2015, J. Biomed. Mater. Res. -Part B Appl. Biomater., 103: 1415-1423).
- the term“about” will be understood by persons of ordinary skill in the art and will vary to some extent depending on the context in which it is used. As used herein when referring to a measurable value such as an amount, a temporal duration, and the like, the term“about” is meant to encompass variations of ⁇ 20% or ⁇ 10%, more preferably ⁇ 5%, even more preferably ⁇ 1 %, and still more preferably ⁇ 0.1 % from the specified value, as such variations are appropriate to perform the disclosed methods.
- the invention relates to a photocurable resin composition.
- the present invention relates to method of making a photocurable resin composition.
- the present invention relates to a method of fabricating an article comprising the photocurable resin.
- the present invention relates to a method of assembling a 3D printed photocured resin to form an article.
- the present invention relates to a photocurable resin composition.
- the photocurable resin composition comprises a first compound comprising one or more double bonds susceptible to polymerization.
- the first compound comprises the reaction product of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond.
- Exemplary diisocyanates include, but are not limited to, 2, 2, 4-trimethylhexamethylene-l, 6-diisocyanate; hexamethylene-l, 6-diisocyanate (FIDI); cyclohexyl-l, 4-diisocyanate; 4,4'methylene- bis(cyclohexyl isocyanate); 1, l'-methylenebis(4-isocyanato) cyclohexane; isophorone diisocyanate; 4,4'-methylene diphenyl diisocyanate (MDI); l,4-tetramethylene diisocyanate; meta- and para-tetramethylxylene diisocyanate; l,4-phenylene diisocyanate; 2,4' and 4,4'- diphenylmethane diisocyanate; 3-methylhexane-l, 6-diisocyanate; 3-ethyl-l,6- hexanediisocyanate;
- the isocyanate reactive compound comprising a double bond comprises a hydroxy acrylate or hydroxy methacrylate (i.e. a hydroxy (meth)acrylate).
- hydroxy (meth)acrylates but are not limited to, 2-hydroxy ethyl (meth)acrylate; 2- hydroxypropyl (meth)acrylate; 3-hydroxypropyl (meth)acrylate; 4- hydroxy butyl (meth)acrylate; 8-hydroxy octyl (meth)acrylate; 12- hydroxydodecanyl (meth)acrylate; 2-hydroxy-3-chloropropyl (meth)acrylate; 2-hydroxy-3- acryloxypropyl (meth)acrylate; 2-hydroxy-B-methacryloxypropyl (meth)acrylate; 2-hydroxy- 3-allyloxypropyl (meth)acrylate; 2-hydroxy-3-cinnamylpropyl (meth)acrylate; 2-hydroxy-3- phenoxypropyl (meth)acrylate;
- polypropylene glycol) (meth)acrylate poly(ethylene glycol) (meth)acrylate; and combinations thereof.
- the isocyanate reactive compound comprising a double bond comprises an unsaturated carboxylic acid.
- unsaturated carboxylic acids include, but are not limited to, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itanconic acid, glutaconic acid, muconic acid, aconitic acid, crotonic acid, alpha-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, bnoleic acid, gamma- bnolenic acid, dihomo-gamma-bnolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, paulbnic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid, and combinations thereof.
- the isocyanate reactive compound comprising a double bond comprises an unsaturated anhydride.
- unsaturated anhydrides include, but are not limited to, maleic anhydride, fumaric anhydride, citraconic anhydride, itaconic anhydride, chloromaleic anhydride, methoxymaleic anhydride, ethylmaleic anhydride, and combinations thereof.
- the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1 : 1 and 20: 1. In one embodiment, the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1 : 1 and 18: 1. In one embodiment, the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1 : 1 and 16: 1. In one embodiment, the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1 : 1 and 14: 1.
- the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1: 1 and 12: 1. In one embodiment, the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1 : 1 and 10: 1. In one embodiment, the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1: 1 and 8: 1. In one embodiment, the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1 : 1 and 6: 1. In one embodiment, the molar ratio of the isocyanate reactive compound comprising a double bond to diisocyanate is between 1: 1 and 4: 1. In one embodiment, the molar ratio the isocyanate reactive compound comprising a double bond to diisocyanate is between 2: 1 and 3: 1.
- the photocurable resin composition comprises a second compound comprising one or more double bonds susceptible to polymerization.
- the second compound comprises a diacrylate or dimethacrylate (i.e. a di(meth)acrylate).
- exemplary di(meth)acrylates include, but are not limited to, triethylene glycol di(meth)acrylate (TEG DMA), di(ethylene glycol)di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, di(propylene
- glycol)di(meth)acrylate butane glycol di(meth)acrylate, glycerol di(meth)acrylate, bisphenol A di(meth)acrylate, 1 ,4-phenylene di(meth)acrylate, butanediol di(meth)acrylate, hexanediol dimethacrylate, and combinations thereof.
- the second compound comprises a triacrylate or a trimethacrylate (i.e. a tri(meth)acrylate).
- exemplary tri(meth)acrylates include, but are not limited to, l,l-trimethylolpropane tri(meth)acrylate; ethoxy lated or propoxylated 1,1,1- trimethylolpropanetri(meth)acrylate; ethoxylated or propoxylated glycerol tri(meth)acrylate; pentaerythritol monohydroxy tri(meth)acrylate; ethoxylated tri methylolpropane
- tri(meth)acrylate ethoxylated (9) trimethylol propane tri(meth)acrylate; pentaerythritol tri(meth)acrylate, propoxylated (3) glyceryl tri(meth)acrylate; propoxylated (3) trimethylol propane tri(meth)acrylate; tris (2-hydroxylethyl) isocyanurate tri(meth)acrylate; and combinations thereof.
- the second compound comprises an unsaturated carboxylic acid. Exemplary unsaturated carboxylic acids are described elsewhere herein. In one embodiment, the second compound comprises an unsaturated anhydride. Exemplary unsaturated anhydrides are described elsewhere herein.
- the photocurable resin composition comprises additional compounds comprising one or more double bonds susceptible to polymerization.
- additional compounds comprise unsaturated carboxylic acids, unsaturated acid anhydrides, di(meth)acrylates, tri(meth)acrylates, and combinations thereof.
- unsaturated carboxylic acids, unsaturated acid anhydrides, di(meth)acrylates, and tri(meth)acrylates are described elsewhere herein.
- the photocurable resin composition comprises one or more photoinitiators.
- photoinitiators include, but are not limited to, 1 -hydroxy- cyclohexyl-phenyl-ketone; diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide; 2,4,6- trimethylbenzoylethoxyphenylphosphine oxide; bis(2,4,6-trimethylbenzoyl)-phenyl- phosphine oxide and other acyl phosphines; phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO); 2-methyl- l-(4-methylthio)phenyl-2-(4-morpholinyl)-l-propanone; l-(4-(2- hydroxyethoxy)phenyl)-2-hydroxy-2-methylpropan-l-one; 2-benzyl 2-dimethylamino l-(4- morpholinophenyl)-butanone-
- the photocurable resin composition comprises one or more stabilizers.
- stabilizers include, but are not limited to, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine,
- diaminopentane diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, diaminooctane, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, methylpropylamine,
- ethylpropylamine propylbutylamine, ethylbutylamine, ethylpentylamine, propylpentylamine, butylpentylamine, tributylamine, trihexylamine, polyethylene glycols, polyvinylpyridine, polyninylpyrolidone, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, decanethiol, dodecanethiol, l,2-ethanedithiol, l,3-propanedithiol, l,4-butanedithiol, O- methylxanthate, O-ethylxanthate, O-propylxanthic acid, O-butylxanthic acid, O-pentylxanthic acid, O-hexylxanthic acid
- the photocurable resin composition comprises one or more dyes.
- dyes include, but are not limited to, chromium-cobalt-aluminum oxide; ferric ammonium citrate; pyrogallol; logwood extract; l,4-bis[(2-hydroxy- ethyl)amino]-9,l0-anthracenedione bis(2-propenoic)ester copolymers; 1 ,4-bis [(2- methylphenyl)amino] -9,l0-anthracenedione; l,4-bis[4- (2-methacryloxyethyl) phenylamino] anthraquinone copolymers; carbazole violet; chlorophyllin-copper complex; chromium oxide greens; C.I.
- Vat Orange 1 2-[[2, 5-diethoxy- 4-[(4-methylphenyl)thiol] phenyl]azo] -1,3,5- benzenetriol; 7,l6-dichloro-6,l5-dihydro- 5,9,l4,l8-anthrazinetetrone; Reactive Black 5; Reactive Blue 21; Reactive Orange 78; Reactive Yellow 15; Reactive Blue No. 19; Reactive Blue No. 4; C.I. Reactive Red 11; C.I. Reactive Yellow 86; C.I. Reactive Blue 163; C.I.
- Reactive Red 180 4-[(2,4-dimethylphenyl)azo]- 2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol- 3-one; 6-ethoxy-2- (6-ethoxy-3-oxobenzo[b] thien-2(3H)- ylidene) benzo[b]thiophen- 3(2H)- one; phthalocyanine green; iron oxides; titanium dioxide; and combinations thereof.
- the photocurable resin composition comprises a first photocurable resin composition and a second photocurable resin composition.
- the first photocurable resin composition comprises between 100 wt % and 50 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond.
- the first photocurable resin composition comprises between 100 wt % and 60 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond.
- the first photocurable resin composition comprises between 100 wt % and 70 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond. In one embodiment, the first photocurable resin composition comprises between 90 wt % and 70 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond. In one embodiment, the first photocurable resin composition comprises between 85 wt % and 75 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond. In one embodiment, the first photocurable resin comprises a compound formed from reaction of one or more diisocyanates with one or more hydroxy (meth)acrylates. Exemplary hydroxy
- the compound formed from the reaction of one or more diisocyanates with one or more hydroxy (meth)acrylates comprises a urethane (meth)acrylate.
- the first photocurable resin composition comprises between 5 wt % and 50 wt % of the second compound comprising one or more double bonds. In one embodiment, the first photocurable resin composition comprises between 5 wt % and 45 wt % of the second compound comprising one or more double bonds. In one embodiment, the first photocurable resin composition comprises between 5 wt % and 40 wt % of the second compound comprising one or more double bonds. In one embodiment, the first photocurable resin composition comprises between 5 wt % and 35 wt % of the second compound comprising one or more double bonds. In one embodiment, the first photocurable resin composition comprises between 5 wt % and 30 wt % of the second compound comprising one or more double bonds.
- the first photocurable resin composition comprises between 5 wt % and 25 wt % of the second compound comprising one or more double bonds. In one embodiment, the first photocurable resin composition comprises between 10 wt % and 25 wt % of the second compound comprising one or more double bonds. In one embodiment, the first photocurable resin composition comprises a second compound comprising a di(meth)acrylate. Exemplary di(meth)acrylates are described elsewhere herein.
- the first photocurable resin composition comprises less than 30 wt % photoinitiator. In one embodiment, the first photocurable resin composition comprises less than 25 wt % photoinitiator. In one embodiment, the first photocurable resin composition comprises less than 20 wt % photoinitiator. In one embodiment, the first photocurable resin composition comprises less than 15 wt % photoinitiator. In one embodiment, the first photocurable resin composition comprises less than 10 wt % photoinitiator. In one embodiment, the first photocurable resin composition comprises less than 5 wt % photoinitiator.
- the first photocurable resin composition comprises less than 30 wt % stabilizer. In one embodiment, the first photocurable resin composition comprises less than 25 wt % stabilizer. In one embodiment, the first photocurable resin composition comprises less than 20 wt % stabilizer. In one embodiment, the first photocurable resin composition comprises less than 15 wt % stabilizer. In one embodiment, the first photocurable resin composition comprises less than 10 wt % stabilizer. In one embodiment, the first photocurable resin composition comprises less than 5 wt % stabilizer.
- the second photocurable resin composition comprises between 10 wt % and 60 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond. In one embodiment, the second photocurable resin composition comprises between 20 wt % and 60 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond. In one embodiment, the second photocurable resin composition comprises between 30 wt % and 60 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond.
- the second photocurable resin composition comprises between 40 wt % and 60 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond. In one embodiment, the second photocurable resin composition comprises between 45 wt % and 55 wt % of the compound formed from the reaction of one or more diisocyanates with one or more isocyanate reactive compounds comprising a double bond. In one embodiment, the second photocurable resin comprises a compound formed from reaction of one or more diisocyanates with one or more hydroxy (meth)acrylates. Exemplary hydroxy (meth)acrylates are described elsewhere herein. In one embodiment, the compound formed from the reaction of one or more diisocyanates with one or more hydroxy (meth)acrylates comprises a urethane (meth)acrylate.
- the second photocurable resin composition comprises between 5 wt % and 50 wt % of the second compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 5 wt % and 45 wt % of the second compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 5 wt % and 40 wt % of the second compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 5 wt % and 35 wt % of the second compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 5 wt % and 30 wt % of the second compound comprising one or more double bonds.
- the second photocurable resin composition comprises between 5 wt % and 25 wt % of the second compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 10 wt % and 25 wt % of the second compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 12 wt % and 22 wt % of the second compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises a second compound comprising a
- di(meth)acrylate Exemplary di(meth)acrylates are described elsewhere herein.
- the second photocurable resin composition comprises an additional compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 5 wt % and 50 wt % of the additional compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 10 wt % and 50 wt % of the additional compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 15 wt % and 50 wt % of the additional compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 20 wt % and 50 wt % of the additional compound comprising one or more double bonds.
- the second photocurable resin composition comprises between 25 wt % and 50 wt % of the additional compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 25 wt % and 45 wt % of the additional compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 25 wt % and 40 wt % of the additional compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises between 25 wt % and 35 wt % of the additional compound comprising one or more double bonds. In one embodiment, the second photocurable resin composition comprises an additional compound comprising a
- tri(meth)acrylate Exemplary tri(meth)acrylates are described elsewhere herein.
- the second photocurable resin composition comprises less than 30 wt % photoinitiator. In one embodiment, the second photocurable resin composition comprises less than 25 wt % photoinitiator. In one embodiment, the second photocurable resin composition comprises less than 20 wt % photoinitiator. In one embodiment, the second photocurable resin composition comprises less than 15 wt % photoinitiator. In one embodiment, the second photocurable resin composition comprises less than 10 wt % photoinitiator. In one embodiment, the second photocurable resin composition comprises less than 5 wt % photoinitiator.
- the second photocurable resin composition comprises less than 30 wt % stabilizer. In one embodiment, the second photocurable resin composition comprises less than 25 wt % stabilizer. In one embodiment, the second photocurable resin composition comprises less than 20 wt % stabilizer. In one embodiment, the second photocurable resin composition comprises less than 15 wt % stabilizer. In one embodiment, the second photocurable resin composition comprises less than 10 wt % stabilizer. In one embodiment, the second photocurable resin composition comprises less than 5 wt % stabilizer.
- the present invention relates to a method of making a photocurable resin composition.
- Exemplary process 100 is shown in Figure 1.
- a diisocyanate is provided.
- an isocyanate reactive compound comprising a double bond is provided.
- the diisocyanate and isocyanate reactive compound are combined and react to form a first compound comprising one or more double bonds susceptible to polymerization.
- the first compound is mixed with a second compound comprising one or more double bonds susceptible to polymerization to form a mixture.
- a photoinitiator is added to the mixture.
- the diisocyanate may be any diisocyanate known to those of skill in the art. Exemplary diisocyanates are described elsewhere herein. In one embodiment, the diisocyanate is a solid. In one embodiment, the diisocyanate is mixed with a solvent. In one embodiment, the diisocyanate is mixed with an organic solvent. Exemplary organic solvents include, but are not limited to, pentane, hexane, diethyl ether, tetrahydrofuran, acetone, benzene, toluene, methanol, ethanol, isopropanol, ethyl acetate, DMF, dichloromethane, chloroform, and combinations thereof.
- the diisocyanate is heated. In one embodiment, the diisocyanate is heated such that it melts. In one embodiment, the diisocyanate is heated between 10 °C and 100 °C. In one embodiment, the diisocyanate is heated between 10 °C and 90 °C. In one embodiment, the diisocyanate is heated between 10 °C and 80 °C. In one embodiment, the diisocyanate is heated between 10 °C and 70 °C. In one embodiment, the diisocyanate is heated between 20 °C and 70 °C. In one embodiment, the diisocyanate is heated between 30 °C and 70 °C. In one embodiment, the diisocyanate is heated between 40 °C and 70 °C. In one embodiment, the diisocyanate is heated between 50 °C and 70 °C. In one embodiment, the diisocyanate is heated between 55 °C and 65 °C.
- the isocyanate reactive compound comprising a double bond may be any isocyanate reactive compound comprising a double bond known to those of skill in the art. Exemplary isocyanate reactive compounds are described elsewhere herein. In one embodiment, the isocyanate reactive compound is mixed with a solvent. In one embodiment, the isocyanate reactive compound is mixed with an organic solvent. Exemplary organic solvents are described elsewhere herein.
- the diisocyanate and the isocyanate reactive compound comprising a double bond can be combined using any method known to those of skill in the art.
- the isocyanate reactive compound is added dropwise to the diisocyanate.
- the isocyanate reactive compound is added all at once to the diisocyanate.
- the diisocyanate is stirred while the isocyanate reactive compound is added.
- the diisocyanate and the isocyanate reactive compound react at room temperature.
- the diisocyanate and the isocyanate reactive compound react at an elevated temperature. In one embodiment, the reaction occurs at a temperature between 10 °C and 100 °C.
- the reaction occurs at a temperature between 10 °C and 90 °C. In one embodiment, the reaction occurs at a temperature between 10 °C and 80 °C. In one embodiment, the reaction occurs at a temperature between 10 °C and 70 °C. In one embodiment, the reaction occurs at a temperature between 20 °C and 70 °C. In one embodiment, the reaction occurs at a temperature between 30 °C and 70 °C. In one embodiment, the reaction occurs at a temperature between 40 °C and 70 °C. In one embodiment, the reaction occurs at a temperature between 50 °C and 70 °C. In one embodiment, the reaction occurs at a temperature between 55 °C and 65 °C.
- solvent that is present during the reaction between the diisocyanate and the isocyanate reactive compound is removed.
- the solvent can be removed using any method known to a person of skill in the art.
- the solvent is removed using filtration.
- the solvent is removed by rotary evaporation.
- the second compound comprising one or more double bonds susceptible to polymerization may be any compound comprising one or more double bonds susceptible to polymerization known to those of skill in the art. Exemplary compounds comprising one or more double bonds susceptible to polymerization are described elsewhere herein.
- the second compound is mixed with a solvent. In one embodiment, the second compound is mixed with an organic solvent. Exemplary organic solvents are described elsewhere herein.
- the step of mixing the first compound with a second compound comprising one or more double bonds susceptible to polymerization to form a mixture further comprises step 142, wherein an additional compound comprising one or more double bonds susceptible to polymerization is added to the mixture.
- the additional compound comprising one or more double bonds susceptible to polymerization may be any compound comprising one or more double bonds susceptible to polymerization known to those of skill in the art. Exemplary additional compounds are described elsewhere herein.
- the additional compound is mixed with a solvent.
- the additional compound is mixed with an organic solvent. Exemplary organic solvents are described elsewhere herein.
- the photoinitiator may be any photoinitiator known to those of skill in the art. Exemplary photoinitiators are described elsewhere herein. In one
- the photoinitiator is mixed with a solvent. In one embodiment, the
- photoinitiator is mixed with an organic solvent.
- organic solvents are described elsewhere herein.
- the step of adding a photoinitiator to the mixture further comprises step 152, wherein a stabilizer is added to the mixture.
- the stabilizer may be any stabilizer known to those of skill in the art. Exemplary stabilizers are described elsewhere herein.
- the stabilizer is mixed with a solvent. In one embodiment, the stabilizer is mixed with an organic solvent. Exemplary organic solvents are described elsewhere herein.
- the step of adding a photoinitiator to the mixture further comprises step 154, wherein a dye is added to the mixture.
- the dye may be any dye known to those of skill in the art. Exemplary dyes are described elsewhere herein.
- the dye is mixed with a solvent.
- the dye is mixed with an organic solvent. Exemplary organic solvents are described elsewhere herein.
- the dye is mixed with an aqueous solvent. Exemplary aqueous solvents include, but are not limited to water, distilled water, deionized water, salt water, and combinations thereof.
- the present invention relates to a method of 3D printing a photocurable resin composition.
- the 3D printing technology may be any known to a person of skill in the art.
- Exemplary 3D printing technologies include, but are not limited to, continuous liquid interface production (CLIP), stereolithography, digital light processing, fused deposition modeling, selective laser sintering, selective laser melting, laminated object manufacturing, digital beam melting, carbon printing, and material jetting (such as Polyjet 3D printing).
- the photocurable resin is printed using stereolithography.
- the stereolithography printer is a bottom-up system comprising a scanning laser.
- the stereolithography printer is a top-down system comprising digital light projection.
- the photocurable resin is printed using material jetting.
- the 3D printer uses STL format software. In one embodiment, the 3D printer uses ML format software. In one embodiment, the 3D printer prints an impression taken using a 3D scanner that is then digitized and converted to an STL or ML file.
- the printing speed is between 1 mm/hr and 100 mm/hr. In one embodiment, the printing speed is between 1 mm/hr and 90 mm/hr. In one embodiment, the printing speed is between 1 mm/hr and 80 mm/hr. In one embodiment, the printing speed is between 1 mm/hr and 70 mm/hr. In one embodiment, the printing speed is between 1 mm/hr and 60 mm/hr. In one embodiment, the printing speed is between 1 mm/hr and 50 mm/hr. In one embodiment, the printing speed is between 1 mm/hr and 40 mm/hr. In one embodiment, the printing speed is between 1 mm/hr and 30 mm/hr. In one embodiment, the printing speed is between 10 mm/hr and 30 mm/hr. In one embodiment, the printing speed is between 12 mm/hr and 25 mm/hr.
- the photocurable resin is printed/deposited onto a support.
- the support may be any support known to a person of skill in the art.
- the photocurable resin is printed to form a support structure before the desired photocurable resin structure is printed onto a support structure.
- the desired printed photocurable resin structure is held to the support structure using support pillars.
- the support structure is attached to a 3D printing platform.
- the photocurable resin is irradiated during the printing process. In one embodiment, the photocurable resin is irradiated with UV light. In one embodiment, the photocurable resin is irradiated with visible light. In one embodiment, the photocurable resin is irradiated with light between 380 nm and 750 nm. In one embodiment, the photocurable resin is irradiated with light between 380 nm and 700 nm. In one embodiment, the photocurable resin is irradiated with light between 380 nm and 650 nm. In one embodiment, the photocurable resin is irradiated with light between 380 nm and 600 nm.
- the photocurable resin is irradiated with light between 380 nm and 550 nm. In one embodiment, the photocurable resin is irradiated with light between 380 nm and 500 nm. In one embodiment, the photocurable resin is irradiated with light between 380 nm and 450 nm. In one embodiment, the photocurable resin is irradiated with light between 395 nm and 415 nm. In one embodiment, the irradiation is provided from a laser. In one embodiment, the photocurable resin composition is continuously irradiated during printing.
- the photocurable resin composition is non-continuously irradiated during printing. In one embodiment, the irradiation photopolymerizes the photocurable
- the irradiation cures the photocurable composition.
- the photocurable composition forms thin layers as the composition is irradiated.
- the layers are between 5 pm and 500 pm in height. In one embodiment, the layers are between 5 pm and 450 pm in height. In one embodiment, the layers are between 5 pm and 400 pm in height. In one embodiment, the layers are between 5 pm and 350 pm in height. In one embodiment, the layers are between 5 pm and 300 pm in height. In one embodiment, the layers are between 5 pm and 250 pm in height. In one embodiment, the layers are between 5 pm and 200 pm in height. In one embodiment, the layers are between 5 pm and 150 pm in height. In one embodiment, the layers are between 5 pm and 100 pm in height. In one embodiment, the layers are between 40 pm and 100 pm in height. In one embodiment, the layers are between 40 pm and 60 pm in height.
- the length of irradiation of each layer of photocurable resin depends on the desired height of the resin layer.
- a layer of between 40 pm and 60 pm high is irradiated for 1 second to 1 minute.
- a layer of between 40 pm and 60 pm high is irradiated for 1 second to 50 seconds.
- a layer of between 40 pm and 60 pm high is irradiated for 1 second to 40 seconds.
- a layer of between 40 pm and 60 pm high is irradiated for 1 second to 30 seconds.
- a layer of between 40 pm and 60 pm high is irradiated for 1 second to 20 seconds.
- a layer of between 40 pm and 60 pm high is irradiated for 5 seconds to 15 seconds.
- the photocurable resin is printed to form a solid structure.
- the photocurable resin is printed to form a solid coating.
- both a solid structure and a solid coating are printed.
- the photocurable resin used to print the solid coating has a different composition than the photocurable resin used to print the solid structure.
- the photocurable resin used to print the solid structure comprises a mixture of two or more photocurable resins with different compositions.
- the photocurable resin used to print the solid coating comprises a mixture of two or more photocurable resins with different compositions.
- the photocurable resin used to print the solid structure comprises a gradient of two or more photocurable resins with different compositions. In one embodiment, the photocurable resin used to print the solid coating comprises a gradient of two or more photocurable resins with different compositions. In one embodiment, the solid coating and solid structure are 3D printed separately and then assembled after printing. In one embodiment, the solid structure is printed to form an inner structure and then the solid coating is printed in the form of a coating/covering over one or more sides of the inner structure.
- the photocurable resin composition is printed to form a structure comprising a specific microarchitecture.
- the microarchitecture is continuous throughout the 3D printed structure.
- the microarchitecture is discontinuous throughout the 3D printed structure.
- microarchitecture comprises areas of a specific microarchitecture that are connected to areas lacking a specific microarchitecture.
- the microarchitecture comprises pores or openings.
- the microarchitecture comprises a meshwork structure.
- a both solid coating and a microarchitecture are printed. The solid coating is described elsewhere herein.
- the photocurable resin used to print the microarchitecture has a different composition than the photocurable resin used to print the solid coating.
- the photocurable resin used to print the microarchitecture comprises a mixture of two or more photocurable resins with different compositions.
- the photocurable resin used to print the microarchitecture comprises a gradient of two or more photocurable resins with different compositions.
- the solid coating and microarchitecture are 3D printed separately and then assembled after printing.
- the microarchitecture is printed to form an inner structure and then the solid coating is printed in the form of a coating/covering over one or more sides of the inner structure.
- the microarchitecture may be created during the 3D printing process.
- the microarchitecture may be created by chemical means, by physical means, by biological means, and combinations thereof.
- the microarchitecture is formed during the 3D printing process.
- microarchitecture are formed by irradiating certain areas of the photocurable resin. In one embodiment, pores or openings in the microarchitecture are formed by not irradiating certain areas of the photocurable resin.
- the microarchitecture is created by chemical means. In one embodiment, the chemical means comprise voxel level printing. In one embodiment, the chemical means comprise sub-voxel level printing. In one embodiment, the microarchitecture can be created by physical means. Exemplary physical means include, but are not limited to, mechanical means, optical means, thermal means, electrical means, electromagnetic manipulation, and combinations thereof. In one embodiment, the microarchitecture can be created by biological means.
- Exemplary biological means include, but are not limited to, biochemical reactions, enzymatic reactions, living biological cells, synthetic biological cells, viruses, vesicles, and combinations thereof.
- the biological means respond to external stimuli.
- the biological means respond to local stimuli.
- an inner structure is printed and a solid coating over one or more sides of the inner structure is printed at the same time.
- the inner structure comprises a microarchitecture.
- the inner structure comprises a solid structure.
- the inner structure comprises a mixture of
- the inner structure and the solid coating are printed using stereolithography.
- the inner structure and the solid coating comprise different photocurable resin compositions.
- the different photocurable resin compositions are placed in the same 3D printing bath.
- the different photocurable resins comprise different photoinitiators that polymerize the photocurable resins at different wavelengths.
- the different photocurable resins comprise different photoinitiators that cure the photocurable resins at different wavelengths.
- the different photocurable resin compositions are placed in separate 3D printing baths.
- a layer of inner structure is 3D printed from one bath of photocurable resin and then a layer of coating is 3D printed from a second, separate bath.
- the inner structure and the solid coating are printed using material jetting.
- the inner structure and solid coating can be printed as described elsewhere herein using material jetting.
- the inner structure and solid coating can be printed using material jetting at the same time using one or more print heads.
- material jetting deposits small droplets of one or more photocurable resins which are then polymerized and/or cured immediately after they are deposited.
- material jetting deposits small droplets of one or more photocurable resins which are then polymerized and/or cured as they are deposited.
- the inner structure and the solid coating are printed using carbon printing. In one embodiment, the inner structure and solid coating can be printed as described elsewhere herein using carbon printing.
- the photocurable resin can be printed using carbon printing from one bath of a first photocurable resin. In one embodiment, the photocurable resin can be printed using carbon printing from one bath of a first photocurable resin wherein the bath comprises one or more print heads. In one embodiment, the one or more print heads dispense one or more additional photocurable resins into the bath. In one embodiment, the additional photocurable resin(s) have a different composition than the first photocurable resin but are miscible with the first photocurable resin.
- the one or more print heads dispense different amounts of the one or more additional photocurable resins into the bath throughout the printing process such that a gradient of first photocurable resin to additional photocurable resin(s) is formed throughout the resulting 3D printed article.
- the photocurable resin is printed using 3D printing to form an article comprising a microarchitecture, a solid coating structure, or a combination of the two structures. In one embodiment, the photocurable resin is printed using 3D printing to form an article comprising a solid structure, a solid coating structure, or a combination of the two structures. In one embodiment, the article is washed with a solvent to remove excess resin after printing is complete.
- the solvent can be any solvent known to a person of skill in the art.
- Exemplary solvents include, but are not limited to, water, distilled water, deionized water, hexanes, diethyl ether, acetone, methanol, ethanol, isopropanol, dichloromethane, toluene, THF, benzene, ethyl acetate, and combinations thereof.
- the 3D printed article is removed from the support by cutting the support pillars. In one embodiment, the surface of the 3D printed article is smoothed after the support pillars are cut. In one embodiment, the surface of the 3D printed article is smoothed by sanding. In one embodiment, the surface of the 3D printed article is smoothed using a dental drill. In one embodiment, the dental drill comprises a rubber point. In one embodiment, the dental drill comprises one or more disc attachments. In one embodiment, the support is dissolved. In one embodiment, the support is dissolved in an acidic solution.
- Exemplary acids include, but are not limited to, hydrochloric acid, sulfuric acid, acetic acid, nitric acid, citric acid, phosphoric acid, carbonic acid, boric acid, and combinations thereof.
- the support is dissolved in a basic solution comprising a base.
- Exemplary bases include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium bicarbonate, lithium hydroxide, calcium hydroxide, ammonia, and combinations thereof.
- the basic solution comprises between 0.1 wt % and 50 wt % sodium hydroxide. In one embodiment, the basic solution comprises between 0.1 wt % and 40 wt % sodium hydroxide.
- the basic solution comprises between 0.1 wt % and 30 wt % sodium hydroxide. In one embodiment, the basic solution comprises between 0.1 wt % and 20 wt % sodium hydroxide. In one embodiment, the basic solution comprises between 0.1 wt % and 10 wt % sodium hydroxide. In one embodiment, the basic solution comprises between 1 wt % and 5 wt % sodium hydroxide. In one embodiment, the basic solution further comprises a silicate. In one embodiment, the basic solution comprises between 0.1 wt % and 50 wt % sodium silicate. In one embodiment, the basic solution comprises between 0.1 wt % and 40 wt % sodium silicate.
- the basic solution comprises between 0.1 wt % and 30 wt % sodium silicate. In one embodiment, the basic solution comprises between 0.1 wt % and 20 wt % sodium silicate. In one embodiment, the basic solution comprises between 0.1 wt % and 10 wt % sodium silicate. In one embodiment, the basic solution comprises between 0.1 wt % and 3 wt % sodium silicate.
- the 3D printed article is post-cured. In one embodiment, the 3D printed article is post-cured for 10 seconds to 60 minutes. In one embodiment, the 3D printed article is post-cured for 10 seconds to 50 minutes. In one embodiment, the 3D printed article is post-cured for 10 seconds to 40 minutes. In one embodiment, the 3D printed article is post-cured for 10 seconds to 30 minutes. In one embodiment, the 3D printed article is post-cured for 10 seconds to 20 minutes. In one embodiment, the 3D printed article is post- cured for 10 seconds to 10 minutes. In one embodiment, the 3D printed article is post-cured for 30 seconds to 2 minutes. In one embodiment, the 3D printed article is post-cured by irradiation with UV light.
- the 3D printed article is post-cured by irradiation with visible light. In one embodiment, the 3D printed article is post-cured by irradiation with UV light and visible light. In one embodiment, the wavelength of light used for post-curing is determined by the absorption capacity of the photoinitiator used.
- 3D printed and photocured resin structures are assembled after printing to form an article.
- the solid coating structure is connected to the microarchitecture after 3D printing such that it covers the microarchitecture on one or more sides to form the desired 3D printed article.
- the solid coating structure is connected to the solid structure after 3D printing such that it covers the solid structure on one or more sides to form the desired 3D printed article.
- the desired 3D printed article comprises an inner structure comprising a specific microarchitecture or comprising a solid structure covered on one or more sides by the solid coating.
- the solid coating structure is held to the inner structure using additional photocurable resin.
- the additional photocurable resin is applied to the solid coating structure and then the inner structure is placed on top to form a two-layered article.
- the two-layered article is irradiated to adhere the inner structure to the solid coating.
- the two-layered article is irradiated between 10 seconds and 60 minutes.
- the two-layered article is irradiated between 10 seconds and 50 minutes.
- the two-layered article is irradiated between 10 seconds and 40 minutes.
- the two-layered article is irradiated between 10 seconds and 30 minutes.
- the two-layered article is irradiated between 10 seconds and 20 minutes.
- the two-layered article is irradiated between 10 seconds and 10 minutes. In one embodiment, the two-layered article is irradiated between 10 seconds and 1 minute. In one embodiment, the two-layered article is irradiated with UV light. In one embodiment, the two-layered article is irradiated with visible light. In one embodiment, the two-layered article is irradiated with UV light. In one embodiment, the two-layered article is irradiated with both UV light and visible light.
- the wavelengths of UV and/or visible light that can be used to irradiate the two-layered article may be any wavelength disclosed elsewhere herein.
- a side of the inner structure not covered by a solid coating is covered with a second layer of solid coating structure, forming a three-layered article.
- the second layer of solid coating structure is held to the inner structure using additional photocurable resin.
- the inner structure comprises a microarchitecture and the pores in the microarchitecture are filled with additional photocurable resin and then the second solid coating structure is placed on top of the microarchitecture, forming a three-layered article.
- the three-layered article is irradiated to adhere the inner structure to the second solid coating structure. In one embodiment, the irradiation further strengthens the adherence of the first solid coating structure to the inner structure. In one embodiment, the three-layered article is irradiated between 10 seconds and 60 minutes.
- the three-layered article is irradiated between 10 seconds and 50 minutes. In one embodiment, the three-layered article is irradiated between 10 seconds and 40 minutes. In one embodiment, the three-layered article is irradiated between 10 seconds and 30 minutes. In one embodiment, the three layered article is irradiated between 10 seconds and 20 minutes. In one embodiment, the three-layered article is irradiated between 10 seconds and 10 minutes. In one embodiment, the three-layered article is irradiated between 30 seconds and 2 minutes.
- the three-layered article is irradiated with UV light. In one embodiment, the three-layered article is irradiated with visible light. In one embodiment, the three-layered article is irradiated with UV light. In one embodiment, the three-layered article is irradiated with both UV light and visible light.
- the wavelengths of UV and/or visible light that can be used to irradiate the three-layered article may be any wavelength disclosed elsewhere herein.
- the present invention relates to a 3D printed article.
- the 3D printed article may comprise any shape known to a person of skill in the art.
- the 3D printed article is a medical device.
- the 3D printed article is a dental article.
- the 3D printed article is a tooth aligner.
- the 3D printed article is transparent.
- the 3D printed article is colored.
- the 3D printed article comprises more than one photocurable resin composition that has been irradiated/photocured. Exemplary photocurable resin compositions are described elsewhere herein.
- the article comprises an inner layer comprising a first resin composition.
- the inner layer has a thickness of 0.1 mm to 1.5 mm.
- the inner layer has a thickness of 0.1 mm to 1.4 mm.
- the inner layer has a thickness of 0.1 mm to 1.3 mm.
- the inner layer has a thickness of 0.1 mm to 1.2 mm.
- the inner layer has a thickness of 0.1 mm to 1.1 mm.
- the inner layer has a thickness of 0.1 mm to 1.0 mm. In one embodiment, the inner layer has a thickness of 0.1 mm to 0.9 mm. In one embodiment, the inner layer has a thickness of 0.1 mm to 0.8 mm. In one embodiment, the inner layer has a thickness of 0.2 mm to 0.8 mm. In one embodiment, the inner layer has a thickness of 0.3 mm to 0.8 mm.
- the inner layer comprising the first resin composition comprises a microarchitecture. In one embodiment, the inner layer comprises areas of microarchitecture and areas lacking microarchitecture. In one embodiment, the
- microarchitecture comprises pores or openings.
- the pores are uniform in size. In one embodiment, the pores are various sizes.
- the pores comprise an inner diameter of 0.1 mm to 50 mm. In one embodiment, the pores comprise an inner diameter of 0.1 mm to 45 mm. In one embodiment, the pores comprise an inner diameter of 0.1 mm to 40 mm. In one embodiment, the pores comprise an inner diameter of 0.1 mm to 35 mm. In one embodiment, the pores comprise an inner diameter of 0.1 mm to 30 mm. In one embodiment, the pores comprise an inner diameter of 0.1 mm to 25 mm. In one embodiment, the pores comprise an inner diameter of 0.1 mm to 20 mm. In one embodiment, the pores comprise an inner diameter of 0.1 mm to 15 mm.
- the pores comprise an inner diameter of 0.1 mm to 10 mm. In one embodiment, the pores comprise an inner diameter of 0.1 mm to 5 mm. In one embodiment, the pores are not uniformly spaced. In one embodiment, the pores are uniformly spaced. In one embodiment, the microarchitecture comprises a honeycomb/beehive structure. In one embodiment, the microarchitecture comprises a meshwork structure.
- the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 50 mm. In one embodiment, the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 45 mm. In one embodiment, the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 40 mm. In one embodiment, the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 35 mm. In one embodiment, the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 30 mm. In one embodiment, the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 25 mm.
- the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 20 mm. In one embodiment, the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 15 mm. In one embodiment, the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 10 mm. In one embodiment, the microarchitecture comprises photocured resin having a thickness, between pores, of 0.1 mm and 3 mm.
- the inner layer is covered with a second photocurable resin that has been irradiated/photocured. In one embodiment, the second photocured resin covers both sides of the inner layer. In one embodiment, the second photocured resin covers one side of the inner layer.
- the photocured resin covering comprises a solid coating that does not have any pores or openings.
- the photocured resin covering has a thickness of 0.01 mm to 1 mm.
- the photocured resin covering has a thickness of 0.01 mm to 0.9 mm.
- the photocured resin covering has a thickness of 0.01 mm to 0.8 mm.
- the photocured resin covering has a thickness of 0.01 mm to 0.7 mm.
- the photocured resin covering has a thickness of 0.01 mm to 0.6 mm.
- the photocured resin covering has a thickness of 0.01 mm to 0.5 mm.
- the photocured resin covering has a thickness of 0.01 mm to 0.4 mm.
- the photocured resin covering is the same resin that is used for the inner layer. In one embodiment, the photocured resin covering is a different resin than the first photocured resin used for the inner layer. In one embodiment, the photocured resin covering comprises a gradient of photocurable resin compositions. In one embodiment, the inner layer comprises a gradient of photocurable resin compositions. In one embodiment, the photocured resin covering has a different mechanical strength than the photocured resin used to form the inner layer. In one embodiment, the photocured resin used to cover the inner layer has a lower mechanical strength than the photocured resin used to form the inner layer. In one embodiment, the photocured resin used to cover the inner layer has a higher mechanical strength than the photocured resin used to form the inner layer. In one embodiment, the inner layer has varied localized mechanical strengths at different locations of the article. In one embodiment, the covering has varied localized mechanical strengths at different locations of the article.
- the 3D printed article when tested with a preload of 0.01 N, has an initial stress of between 0.1 MPa and 50 MPa. In one embodiment, the 3D printed article, when tested with a preload of 0.01 N, has an initial stress of between 0.1 MPa and 45 MPa. In one embodiment, the 3D printed article, when tested with a preload of 0.01 N, has an initial stress of between 0.1 MPa and 40 MPa. In one embodiment, the 3D printed article, when tested with a preload of 0.01 N, has an initial stress of between 0.1 MPa and 35 MPa.
- the 3D printed article when tested with a preload of 0.01 N, has an initial stress of between 0.1 MPa and 30 MPa. In one embodiment, the 3D printed article, when tested with a preload of 0.01 N, has an initial stress of between 0.1 MPa and 25 MPa. In one embodiment, the 3D printed article, when tested with a preload of 0.01 N, has an initial stress of between 0.1 MPa and 20 MPa. In one embodiment, the 3D printed article, when tested with a preload of 0.01 N, has an initial stress of between 0.1 MPa and 15 MPa.
- the 3D printed article when tested with a preload of 0.01 N, has an initial stress of between 0.45 MPa and 10 MPa.
- the article when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 5% and 95%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 10% and 95%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 15% and 95%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 20% and 95%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 25% and 95%.
- the article when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 30% and 95%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 35% and 95%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 40% and 95%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 45% and 95%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 45% and 90%. In one embodiment, the article, when tested with a preload of 0.01 N, shows a stress relaxation after 2 hours of between 45% and 85%.
- MDI-PEGMA was synthesized using 4,4'-methylenebis(phenyl isocyanate) (MDI) (10.00 g, 40.00 mmol) which was added into a round bottom flask with inert atmosphere, stir bar, and heated to 60 °C. Upon melting of the MDI reagent, poly(ethylene glycol) methacrylate (PEGMA) (32.55 mL, 100.00 mmol) was added dropwise and allowed to react for 8 hr at 60 °C. Afterwards, the reaction was allowed to run overnight at room temperature.
- MDI 4,4'-methylenebis(phenyl isocyanate)
- MDI-PEGMA The compound synthesized (MDI-PEGMA) was collected using a positive displacement pipette and characterized by proton nuclear magnetic resonance spectroscopy ('H NMR) on a Bruker AV300 broad band FT NMR Spectrometer (Billerica, MA, USA) and by Fourier Transform Infrared Spectroscopy (FT-IR) on a PerkinElmer Spectrum Two FT-IR Spectrometer (Waltham, MA, USA).
- 'H NMR proton nuclear magnetic resonance spectroscopy
- FT-IR Fourier Transform Infrared Spectroscopy
- the photocurable resins (aka Bioinks) comprise a urethane containing compound which is synthesized in a reaction between diisocyanate groups and the hydroxyl groups of a hydroxy (meth)acrylate.
- Figure 2 shows a reaction scheme depicting how the synthesis performed. MDI was utilized as the diisocyanate agent and PEGMA was chosen as the hydroxyl group containing reagent, due to its acrylate group which adds photo-reactivity to the final product, MDI-PEGMA. The product was tested via 'H NMR to confirm the reaction between isocyanates and hydroxyl groups (Figure 3). The appearance of an aromatic peak at d 7.32 ppm (C) representing four aromatics protons confirms the reaction of MDI with PEGMA.
- Bioinks 1 and 2 are Synthesis of Bioinks Comprising MDI-PEGMA: Bioinks 1 and 2
- the photoinitiator diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide and the stabilizer bis(2,2,6,6-tetramethyl- 4-piperidyl) sebacate were added to MDI-PEGMA at a final concentration of 2% and 1%, respectively. Additionally, the compounds triethylene glycol dimethacrylate and
- Bioink 1 Two Bioinks were created using MDI-PEGMA as the resin’s main component.
- the first one (Bioink 1), designed to have a low mechanical strength, contained 80% MDI-PEGMA, 17% tri ethylene glycol dimethacrylate, 2% diphenyl(2,4,6- trimethylbenzoyl) phosphine oxide as photoinitiator, and 1% bis(2,2,6,6-tetramethyl-4- piperidyl) sebacate as stabilizer.
- Bioink 2 A stronger Bioink (Bioink 2) was designed including 50% MDI-PEGMA,
- diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide as photoinitiator
- bis(2, 2,6,6- tetramethyl-4-piperidyl) sebacate as stabilizer
- a stronger resin (Bioink 3) was synthesized utilizing tolylene-2, 4-diisocyanate (TDI) as diisocyanate and a combination of poly(ethylene glycol) methacrylate and 2- hydroxy ethyl acrylate as hydroxyl groups for the formation of an acrylated urethane containing compound.
- PEGMA poly(ethylene glycol) methacrylate
- 2-hydroxyethyl acrylate 32.97 mL, 287.1 mmol
- Bioink 3 resin was made out of triethylene glycol dimethacrylate (20%), diphenyl(2,4,6- trimethylbenzoyl) phosphine oxide as photoinitiator (2%), and bis(2,2,6,6-tetramethyl-4- piperidyl) sebacate as stabilizer (1%).
- Bioink 1 320 pL of Bioink 1 were added on top of the mesh, still located in the metal mold, and photopolymerized. Subsequently, the piece was turned over and 320 pL of Bioink 1 were added and polymerized on the other side of the mesh.
- the product a plastic sheet containing an internal scaffold composed of a stronger material, was cut to the dimensions specified in the previous section and tested by DMA analysis with a preload of 0.01 N for a period of 120 min.
- plastic sheets were made by photopolymerizing layer by layer combinations of Bioink 1 and Bioink 2, in order to test the effect of layering materials over stress relaxation and compare it with meshwork embedded materials. Two layering combinations were assessed for this analysis.
- 600 pL of Bioink 1 were pipetted onto the metal mold used in section 2 and photopolymerized. This layer was followed by the addition of two more layers of Bioink 1 for a total thickness of 0.8 mm and a plastic sheet composed of three layers of Bioink 1 stacked together.
- 600 pL of Bioink 1 were pipetted onto the metal mold utilized in section 2 and polymerized.
- 600 pL of Bioink 2 were added and polymerized on top of the polymerized Bioink 1.
- Bioink 1 600 pL was added on top of the previous two layers and polymerized for the formation of a plastic sheet composed of two soft layers on its top and bottom and a stronger middle layer.
- the two layered samples were tested by DMA analysis with a preload of 0.01 N for a period of 20 min.
- Bioink 2 strong MDI-PEGMA resin
- Bioink 3 TDI resin
- the middle layer was a sheet with a beehive structure made out of Bioink 3 via 3D printing. Two versions of this layer were fabricated, one with a beehive inner diameter of 3.0 mm ( Figure 6 A) and another one with an inner diameter of 1.5 mm ( Figure 6B). Furthermore, the lines used were of 1.0 mm and 0.5 mm in thickness, respectively.
- Figures 7A-7D show the three printed parts and demonstrate how each one of them was placed between glass slides prior to the post-curing process to maintain their flat structure and avoid bending of the material.
- An orthodontic clear aligner was built using Bioink 2 and a stereolithography 3D printer (Wanhao Duplicator 7 Plus Touch Screen UV DLP Resin 3D Printer). A light exposure time of 10 s at a wavelength of 405 nm was utilized for a layer thickness of 50 pm. Under these conditions, the process performed at a printing speed of 18 mm/hr. An STL file containing the 3D drawing of an aligner was loaded to the printer ( Figures 10A-10D) and a support structure was added to the piece, required for printing due to the nature of stereolithography. Considering this additional printed material, an aligner printing time ranges between 2 hours and 3 hours. After printing, the aligner and the supporting scaffold utilized for the 3D printing process were attached to the surface of the printing platform ( Figure 11 A).
- the inventive polymerized material resulted in a clear solid with good strength immediately after removal from the 3D printer and was ready for post-processing.
- the part was then removed from the platform and the excess resin was removed with an ethanol wash (Figure 11B).
- the support material was removed by trimming the scaffold attached to the aligner and/or using a dental drill.
- the support pillars that attach the aligner to the support scaffold can be seen in Figure 11C while Figure 11D shows the aligner after some of the support pillars have been trimmed.
- the aligner can then be left overnight in an ethanol bath and dried the next day under compressed air. No post-curing was required.
- the present invention relates in part to novel photocurable materials formed using the methods described herein and the use of these photocurable materials as superior plastics for production of orthodontic aligners.
- the instant invention based in part on the fabrication of photocurable resins Bioink 1, Bioink 2, and Bioink 3 and the formation of plastics with controlled patterns using these resins. This novel material microarchitecture and plastic composition results in reduced stress relaxation.
- Thermoplastic materials that are commonly used by companies that produce commercially available orthodontic aligners (Invisalign and Align Technologies (MC)) and aligners made of poly(ethylene terephthalate) (PETG) were tested via DMA (Figure 14) and compared to the bioinks of the present invention.
- the DMA results show a difference in initial stress and stress relaxation between Bioink 1 and Bioink 2, where Bioink 2 had a higher initial stress (3.62 MPa) and lower stress relaxation (91.18%), when compared with Bioink 1 (1.11 MPa, 98.36%) (Table 1).
- the Invisalign material, SmartTrack was also tested through the same DMA analysis and conditions showing an initial stress of 5.05 MPa and a stress relaxation of 88.95%.
- the present invention relates to the use of defined microarchitectures within polymeric sheets with the goal of reducing stress relaxation in materials for orthodontic clear aligner applications.
- Two approaches were tested to prove this methodology.
- Two metal molds with Pattern A and Pattern B were fabricated ( Figures 15A-15F) and filled with Bioink 2 for the formation of polymerized architectures.
- the polymerized structures were then sandwiched between two layers of the softer Bioink 1 in order to complete a plastic sheet. This was performed by pipetting a layer of Bioink 1 and polymerizing it on each side of the structure.
- the resulting plastic sheets were tested by DMA at a preload of 0.01 N and for a period of time of 120 min.
- Patterns A and B have stress relaxations of 56.57% and 60.51%, respectively which are significantly lower values when compared to the current market standard SmartTrack (Align Technologies), which showed a stress relaxation of 88.95% after 2 hours (Table 2).
- the first layering pattern (Pattern C) ( Figure 17A) was composed of three layers of Bioink 1, in order to test the pure effect of layering.
- the second pattern (Pattern D) ( Figure 17B) entailed one layer of Bioink 2 in between two layers of Bioink 1. This pattern was designed to test if only having a stronger material within the plastic sheet is enough to reduce the stress relaxation or if a microarchitecture is indeed required to obtain the desired effect.
- stereolithography is the printing technique currently being used, other one-step printing methods are also of interest.
- the modification of the inventive Bioinks towards a material jetting technique (Poly Jet 3D Printing) or a continuous liquid interface production (CLIP) would allow for faster polymerization due to constant light exposure and reduced aligner printing times.
- the support material removal process would be easier when compared to the support extraction under stereolithography, where the excess material has to be trimmed.
- the support material can be dissolved in a solution with basic pH.
- CLIP printing of the support material is not required.
- material jetting would allow for the incorporation of multiple materials in an aligner, letting us create a product with advanced mechanical properties and potential additional applications within the clear aligners field.
- This one-step fabrication process where the whole aligner is printed at once using 3D printing contrasts with other techniques, where a hollow lattice is 3D printed and subsequently filled by other conventional methods in a multi-step fabrication process.
- This fabrication difference allows the placement of multiple inks with varied mechanical properties to be controlled, which yields both unique results in terms of mechanical properties and aligners that can be customized to each patient.
- this process allows for the creation structures with features below 1 mm, which could result in further efficiency improvements.
- the present invention relates to the improvement of the current orthodontic aligners and their method of making.
- One improvement is the reduced costs per set of aligners: the direct 3D printing of aligners results in a cost reduction of the fabrication process due to the elimination of dental mold 3D printing prior to the thermoforming of aligners.
- Another improvement is the wider case application and enhanced treatment outcomes: 3D printing aligners allows the incorporation of more complex features and attachments for precise and advanced force delivery.
- different sections of aligners can now be printed with different thicknesses or materials, exerting the desired mechanical properties tailored to a single tooth, thus greatly enhancing the treatment efficacy by eliminating treatment discrepancies. Furthermore, this allows the treatment of more complex cases that current aligner products in the market are unable to treat.
- a third improvement is the introduction of microarchitectures for reduced stress relaxation: this technique would allow for the fabrication of aligners with softer and more comfortable materials that still exert the required mechanical strength towards the treatment of dental malocclusion.
- a fourth improvement is that the process is
- 3D printing has become an integral procedure used in producing the resin made models, onto which thermoplastic materials are impressed to form aligner trays.
- 25-50 aligners are delivered to patients.
- 25-50 sets of corresponding resin models are produced, each with graded minor changes geared towards the ultimate teeth moving outcome.
- these models become disposable waste.
- Different countries impose various rates of environmental taxes or fees related to resin model disposal wastes, which further increase the costs of production.
- the inventive technology would also reduce the cost of waste disposal regarding these 3D printed molds while being a more environmentally friendly manufacturing process.
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Abstract
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AU2019360258A AU2019360258A1 (en) | 2018-10-19 | 2019-10-18 | Photocurable resin composition, photocurable resin article, and methods of fabricating the article |
KR1020217014648A KR20210092211A (en) | 2018-10-19 | 2019-10-18 | A photocurable resin composition, a photocurable resin article, and a manufacturing method of the said article |
EP19874454.2A EP3866726A4 (en) | 2018-10-19 | 2019-10-18 | Photocurable resin composition, photocurable resin article, and methods of fabricating the article |
CN201980084824.2A CN113260332B (en) | 2018-10-19 | 2019-10-18 | Photocurable resin composition, photocurable resin product, and method for producing product |
BR112021007262-4A BR112021007262B1 (en) | 2018-10-19 | 2019-10-18 | 3D PRINTED RESIN ITEM |
CA3116562A CA3116562A1 (en) | 2018-10-19 | 2019-10-18 | Photocurable resin composition, photocurable resin article, and methods of fabricating the article |
JP2021521408A JP2022505404A (en) | 2018-10-19 | 2019-10-18 | A photocurable resin composition, a photocurable resin article, and a method for producing such an article. |
US17/234,304 US20210238335A1 (en) | 2018-10-19 | 2021-04-19 | Photocurable Resin Composition, Photocurable Resin Article, and Methods of Fabricating the Article |
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KR102690683B1 (en) | 2023-11-24 | 2024-08-05 | 국립창원대학교 산학협력단 | Method for manufacturing hydrophilic light-curable polymer structures with slippery surfaces |
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