GB2587424A - Three dimensional printed parts made by additive manufacturing using cyanoacrylates in post processing - Google Patents
Three dimensional printed parts made by additive manufacturing using cyanoacrylates in post processing Download PDFInfo
- Publication number
- GB2587424A GB2587424A GB1914088.8A GB201914088A GB2587424A GB 2587424 A GB2587424 A GB 2587424A GB 201914088 A GB201914088 A GB 201914088A GB 2587424 A GB2587424 A GB 2587424A
- Authority
- GB
- United Kingdom
- Prior art keywords
- cyanoacrylate
- activator
- organic solvent
- cyanoacrylates
- containing compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001651 Cyanoacrylate Polymers 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 title claims abstract description 20
- 230000000996 additive effect Effects 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000012805 post-processing Methods 0.000 title claims abstract description 9
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 41
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000012190 activator Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 5
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 claims abstract description 5
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical class CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- RPQUGMLCZLGZTG-UHFFFAOYSA-N octyl cyanoacrylate Chemical class CCCCCCCCOC(=O)C(=C)C#N RPQUGMLCZLGZTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZTYMNUBYYQNBFP-UHFFFAOYSA-N propyl 2-cyanoprop-2-enoate Chemical class CCCOC(=O)C(=C)C#N ZTYMNUBYYQNBFP-UHFFFAOYSA-N 0.000 claims abstract description 4
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011342 resin composition Substances 0.000 claims abstract description 3
- ZUGAIMFLQLPTKB-UHFFFAOYSA-N 3-pyridin-3-ylpropan-1-ol Chemical compound OCCCC1=CC=CN=C1 ZUGAIMFLQLPTKB-UHFFFAOYSA-N 0.000 claims abstract 3
- ITCZEZQMUWEPQP-UHFFFAOYSA-N prop-2-enyl 2-cyanoprop-2-enoate Chemical compound C=CCOC(=O)C(=C)C#N ITCZEZQMUWEPQP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000178 monomer Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- MXDRPNGTQDRKQM-UHFFFAOYSA-N 3-methylpyridazine Chemical compound CC1=CC=CN=N1 MXDRPNGTQDRKQM-UHFFFAOYSA-N 0.000 abstract description 2
- JYTXVMYBYRTJTI-UHFFFAOYSA-N 2-methoxyethyl 2-cyanoprop-2-enoate Chemical compound COCCOC(=O)C(=C)C#N JYTXVMYBYRTJTI-UHFFFAOYSA-N 0.000 abstract 1
- UHBAPGWWRFVTFS-UHFFFAOYSA-N 4,4'-dipyridyl disulfide Chemical compound C=1C=NC=CC=1SSC1=CC=NC=C1 UHBAPGWWRFVTFS-UHFFFAOYSA-N 0.000 abstract 1
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000010949 copper Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- 206010073306 Exposure to radiation Diseases 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000001010 compromised effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- RXWOHFUULDINMC-UHFFFAOYSA-N 2-(3-nitrothiophen-2-yl)acetic acid Chemical compound OC(=O)CC=1SC=CC=1[N+]([O-])=O RXWOHFUULDINMC-UHFFFAOYSA-N 0.000 description 1
- FLKHVLRENDBIDB-UHFFFAOYSA-N 2-(butylcarbamoyloxy)ethyl prop-2-enoate Chemical compound CCCCNC(=O)OCCOC(=O)C=C FLKHVLRENDBIDB-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OHMUBWQNHUTKMH-UHFFFAOYSA-L [OH-].[Cu+2].P(O)(O)(O)=O.[OH-] Chemical compound [OH-].[Cu+2].P(O)(O)(O)=O.[OH-] OHMUBWQNHUTKMH-UHFFFAOYSA-L 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical class [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical class [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- HZXGNBMOOYOYIS-PAMPIZDHSA-L copper;(z)-1,1,1,5,5,5-hexafluoro-4-oxopent-2-en-2-olate Chemical compound [Cu+2].FC(F)(F)C(/[O-])=C/C(=O)C(F)(F)F.FC(F)(F)C(/[O-])=C/C(=O)C(F)(F)F HZXGNBMOOYOYIS-PAMPIZDHSA-L 0.000 description 1
- LKHJQWNYQOFKBN-UHFFFAOYSA-N copper;2-hydroxy-3,5-di(propan-2-yl)benzoic acid;hydrate Chemical compound O.[Cu].CC(C)C1=CC(C(C)C)=C(O)C(C(O)=O)=C1.CC(C)C1=CC(C(C)C)=C(O)C(C(O)=O)=C1 LKHJQWNYQOFKBN-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical class [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- NOHDJXFJXJZYGO-UHFFFAOYSA-L copper;diformate;hydrate Chemical compound O.[Cu+2].[O-]C=O.[O-]C=O NOHDJXFJXJZYGO-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- JDPSPYBMORZJOD-UHFFFAOYSA-L copper;dodecanoate Chemical class [Cu+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O JDPSPYBMORZJOD-UHFFFAOYSA-L 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/188—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/30—Nitriles
- C08F122/32—Alpha-cyano-acrylic acid; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
- B29C2071/0027—Removing undesirable residual components, e.g. solvents, unreacted monomers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Abstract
A method of preparing a three-dimensional printed part comprises performing additive manufacture using a curable (meth)acrylate composition to form a three-dimensional part on a build substrate, optionally removing the part from the build substrate, optionally contacting the part with an activator, and contacting the part with a cyanoacrylate composition. The activator may comprise a nitrogen-containing compound, e.g. 1,2-di(4-pyridyl ethane), 4,4’-dipyridyl disulphide, 3-(3-hydroxypropyl)pyridine, pyridazine, or methylpyridazine, in an organic solvent having a boiling point of 30-100ºC. The cyanoacrylate composition may comprise methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates, allyl cyanoacrylate, or β-methoxyethyl cyanoacrylate in an organic solvent having a boiling point of 30-100ºC. A method of post-processing a three-dimensional printed part comprises providing a three-dimensional printed part made by additive manufacture from a photocurable resin composition and contacting a surface of the part with a cyanoacrylate composition and optionally an activator to form a coating over the surface.
Description
THREE DIMENSIONAL PRINTED PARTS MADE BY ADDITIVE
MANUFACTURING USING CYANOACRYLATES IN POST PROCESSING
BACKGROUND
Field
[0001] Provided herein are methods for making three dimensional printed parts by additive manufacturing using cyanoacrylates in post processing.
Brief Description of Related Technology
[0002] Additive manufacturing is fast becoming a viable alternative to traditional manufacturing techniques and in some cases the only practical alternative for making complex parts.
[0003] One draw back to additive manufacturing is with the use of photocurable resins. There the end user runs the risk of incomplete cure and thus part formation. Sometimes with incomplete cure residual photocuable resin can remain on the surface of the printed part. When that happens and the surface contains residual resin, surface imperfections may be observed, surface tackiness may be created and/or the quality of the surface finish in the intended function of the part may be compromised. Attempts have been made in the past to address the issue.
[0004] For instance, US Patent Application Publication No. US 2017/0173872 provides a method of forming a 3D object, comprising: (a) providing a carrier and a fill level, and optionally an optically transparent member having a build surface defining the fill level, the carrier and the fill level having a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light (through the optically transparent member when present), to form a solid polymer scaffold from the first component and also advancing the carrier away from the build surface to form a 3D intermediate having the same shape as, or a shape to be imparted to, the 3D object and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; (d) washing the 3D intermediate; and (e) concurrently with or subsequent to the irradiating step and/or the washing step, solidifying and/or curing the second solidifiable component in the 3D intermediate to form the 3D object. In one of the more focused and relevant sections of the '872 publication, the washing step according to the '872 publication uses "[a]ny suitable wash liquid" and lists BlO-SOLVTM solvent replacement; PURPLE POWERTM degreaser/cleaner; SIMPLE GREEN® all purpose cleaner; a 50:50 volume:volume mixture of water and isopropanol as possible choices.
[0005] To date none are believed to be without their own draw backs. For instance, many known wash liquids or cleaners are believed to comprise isopropanol and other solvents with low flash points and high volatile organic compounds.
[0006] Thus, notwithstanding the state of the art it would be desirable to facilitate the facile post processing of the three dimensional printed part.
SUMMARY
[0007] These desires are satisfied by the present invention.
[0008] Accordingly, through the use of the inventive method, three dimensional printed parts may be produced more efficiently with a cleaner surface finish, substantially free of deleterious matter and/or with little to no unwanted resin left on the surface. This is no small matter because in the past either the end user was left with a compromised surface finish on the three dimensional printed part or had to take extra measures to prepare manually the surface finish (assuming that the entirety of the surface was accessible to the end user). Thus, it is seen that the inventive method significantly contributes to the advancement of three dimensional printing into more prevalent use.
[0009] In one aspect, provided herein is a method of preparing a three-dimensional printed part made by additive manufacturing, comprising the steps of: A. Performing additive manufacturing using a curable (meth)acrylate composition to form a three-dimensional part on a build substrate, where the three-dimensional printed part made according to data indicating a pre-determined pattern; and B. Optionally, removing the so-formed part from the build substrate; and Optionally, contacting at least some of the part with an activator; and Contacting the part with a cyanoacrylate composition.
DETAILED DESCRIPTION
[0010] As noted above, a method of preparing a three dimension printed pad made by additive manufacturing is provided herein.
[0011] The method includes the steps of: A. Performing additive manufacturing using a curable (meth)acrylate composition to form a three-dimensional part on a build substrate; and B. Optionally, removing the so-formed part from the build substrate; and C. Optionally, contacting at least some of the part with an activator; and D. Contacting the part with a cyanoacrylate composition.
[0012] Additive manufacturing is performed to form the three dimensional printed part according to data indicating a pre-determined pattern.
[0013] The photocurable resin used to form the three dimensional printed part from an additive manufacturing technique should cure through exposure to radiation in the electromagnetic spectrum, such as IR, VIS, UV and UV/VIS.
[0014] Indeed, radiation at one portion of the electromagnetic spectrum may be used initially, oftentimes followed by radiation in another portion of the electromagnetic spectrum. Or, radiation in the electromagnetic spectrum may be used together with exposure to elevated temperature conditions. The elevated temperature should be chosen with an eye toward the cure temperature of the resin used and its cure profile with the cure package selected. The elevated temperature condition is chosen to either (1) drive further the reaction initiated by exposure to radiation in the electromagnetic spectrum toward completion or (2) in some cases, initiate a secondary cure reaction in the three dimensional print resin. Where an elevated temperature condition is chosen to advance cure of the resin, the temperature chosen should be greater than room temperature plus about 70°C, though desirably less than about 180°C.
[0015] Here, depending on the physical properties desired from the three dimension printed part, the subsequent energy exposure step may be avoided in lieu of the provision of the cyanoacrylate coating formed through the inventive methods.
[0016] Depending on the chemistry of the three dimensional print resin, the cure package may vary widely in both nature and amount. For instance, the cure package may be chosen to be one triggered by exposure to radiation in the electromagnetic spectrum or elevated temperature conditions, or both.
[0017] After conducting the inventive method, the part should possess at least one of improved surface finish, improved transparancy and reduced tackiness. In addition, the part should emit little to no odor.
[0018] When used in the inventive method, the activator is a species capable of initiating anionic polymerization. Broad examples of the activator thus include nitrogen-containing components and transition metal compounds.
[0019] Where the activator is a nitrogen-containing compound, that compound may be in a solution. The activator should be applied to the part before the cyanacrylate composition. But in some instances it may be applied after the cyanoacrylate composition instead.
[0020] The activator may be a nitrogen-containing compound, such as an alkyl or aryl amine, like a tertiary amine for instance a trialkyl amine. Other examples include 1,2-cli(1.-pyridy1ethane), 4.4-apyridyl disulfide, 3-(3-hydroxypropy1)pyridine, 1,2-bis(diphenylphosphino)-ethane, pyridazine, methylpyridazine or 4,4'-dipyhdyl, [0021] When used in a solution, the amine should be used in an amount of about 0.5 to about 5 percent by weight in an organic solvent. The organic solvent should have a boiling point between about 30'C and 100 -C, such as about 45 C to 75' C, desirably about 50" C to about 65" C. The organic solvent may be selected from acetonitrile, alkyl alcohols (such as methanol and isopropanol), alkyl esters (such as ethyl acetate), alkanes (such as pentane and cyclopentane, hexane, and heptane), halogenated alkanes (such as dichloromethane and chloroform), and combinations thereof.
[0022] Useful transition metal compounds include ones based on copper, vanadium, cobalt and iron.
[0023] For instance, as regards copper compounds, copper compounds where copper enjoys a 1+ or 2+ valence state are desirable. For instance, copper carboxylates, copper naphthenates, copper acetates, copper octoates, copper laurates, copper benzoates, fatty add salts of copper, copper formates, copper metal, copper acetyl acetonates, 2,4-pentanedione copper complex, any other analogous copper compounds, alloys, amalgams, and copper derivatives known to those skilled in the art may be used. A non-exhaustive list of examples of such copper (1) and (II) compounds include copper (II) 3,5-diisopropylsalicylate hydrate, copper bis(2,2,6,6-tetramethy1-3,5-heptanedionate), copper (II) hydroxide phosphate, copper (II) chloride, copper (II) acetate monohydrate, tetrakis(acetonitrile)copper (1) hexafluorophosphate, copper (II) formate hydrate, tetrakisacetonitrile copper (1) triflate, copper(I1)tetrafluoroborate, copper (II) perchlorate, tetrakis(acetonitrile)copper (I) tetrafluoroborate, copper (II) hydroxide, copper (II) hexafluoroacetylacetonate hydrate and copper (II) carbonate. These copper (1) and (II) compounds should be used in an amount of about 100 ppm to about 5,000 ppm, such as about 500 ppm to about 2,500 ppm, for instance about 1,000 ppm.
[0024] As regards vanadium compounds, vanadium compounds where vanadium enjoys a 2+ and 3+ valence state are desirable. Examples of such vanadium (111) compounds include vanadyl naphthanate and vanadyl acetylacetonate. These vanadium (111) compounds should be used in an amount of 50 ppm to about 5,000 ppm, such as about 500 ppm to about 2,500 ppm, for instance about 1,000 ppm.
[0025] As regards cobalt compounds, cobalt compounds where cobalt enjoys a 2+ valence state are desirable. Examples of such cobalt (II) compounds include cobalt naphthenate, cobalt tetrafluoroborate and cobalt acetylacetonate. These cobalt (II) compounds should be used in an amount of about 100 ppm to about 1000 ppm.
[0026] As regards iron compounds, iron compounds where iron enjoys a 3+ valence state are desirable. Examples of such iron (111) compounds include iron acetate, iron acetylacetonate, iron tetrafluoroborate, iron perchlorate, and iron chloride. These iron compounds should be used in an amount of about 100 ppm to about 1000 ppm.
[0027] The cyanoacrylate composition comprises a cyanoacrylate monomer within the following structure: H2C=C(CN)-COOR, where R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl groups.
[0028] More specifically, the cyanoacrylate composition comprises a cyanoacrylate monomer selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates, ally! cyanoacrylate, 11-methoxyethyl cyanoacrylate and combinations thereof.
[0029] The cyanoacrylate composition may be used in a solution. In such case, the cyanoacrylate composition is used in an amount of about 0.5 to about 10 percent by weight. As above, the organic solvent should have a boiling point between about 30 C and 100 C, such as about 45 'C to 75 C, desirably about 50 'C to about 65 C. The organic solvent may be selected from acetonitrile, alkyl alcohols (such as methanol and isopropanol), alkyl esters (such as ethyl acetate), alkanes (such as pentane and cyclopentane, hexane, and heptane), halogenated alkanes (such as dichloromethane and chloroform), and combinations thereof [0030] Significantly though the chosen organic solvent should not readily solubilize poly cyanoacryalte at room temperature.
[0031] The organic solvent used with the activator and the organic solvent used with the cyanoacrylate may be the same or different.
[0032] The activator and/or cyanoacrylate composition may be applied to the three dimesional printed part by spraying, dipping, rolling, immersing, or vapor exposure, among other techniques.
[0033] It may be desirable in some instances to provide onto at least a portion of a surface of a build substrate of the printer a release coating material to facilitate removal of the three dimensional printed part once formed from the build substrate.
[0034] The release coating material may be present at a concentration in the liquid carrier in an amount of about 0.05 to about 10 percent by weight, such as about 2.5 to about 5 percent by weight.
[0035] The chosen release coating material should have a contact angle measurement of greater than about 75° but less than about 108°.
[0036] Alternatively, the inventive method of post processing a three dimensional printed part made by additive manufacturing, comprise the steps of: A. Providing an additive manufacturing-made three dimensional printed part having at least one surface, said three dimensional printed part made from a photocurable resin composition; and B. The time during which the various steps occur may range from about 2 minutes to about 60 minutes, such as about 2 minutes to about 10 minutes, desirably about 5 minutes to about 10 minutes.
[0037] The temperature at which the various steps occur may range from about 15°C to about 60°C, such as about 20°C to about 55°C, desirably about 25°C to about 45°C.
[0038] The following example is illustrative.
EXAMPLE
[0039] Here, a LOCTITE PR-10 Printer was used with LOCTITE 3D 3870 Black resin to print the specimens for evaluation. The LOCTITE PR-10 Printer was set at a print resolution of 0.1 mm, which is the thickness of each layer of the print. The print takes about 2-4 hours to complete at this setting. The printed part in each case is a three dimensional rectangle that is 1" x 2" x 0.125" in size.
[0040] As noted, LOCTITE 3D 3870 Black resin was used to make three dimensional printed parts in the LOCTITE PR-10 Printer. LOCTITE 3D 3870 Black resin is promoted as a black, opaque, light cure, low viscosity, acrylic resin that may be used for prototyping via stereolithography. It cures with very short exposure to monochromatic light sources such as LED or laser. Printed articles exhibit good print resolution and high flexibility. It is printable at room temperature across various laser SLA and DLP platforms. The manufacturer reports that LOCTITE 3D 3870 Black resin contains 2-[[(Butylamino)carbonyl]oxy]ethyl acrylate, 20 -30 percent by weight; 2-Hydroxyethyl acrylate, polymer with aEpichlorohydrin, phthalic anhydride, 4,41-Bisphenol A and e-Caprolactone, 20 -30 percent by weight; lsobornyl acrylate, 20 -30 percent by weight; 2-Propenoic acid, 2-hydroxyethyl ester, polymer with 1,1-methylenebis[4-isocyanatocyclohexane] and a,a',a"-1,2,3-propanetriyltris[, 10 -20 percent by weight; Diacrylate ester, 1 -5 percent by weight; and 2-Hydroxyethyl acrylate, 0.1 -1 percent by weight.
[0041] Three dimensional printed parts in the shape of dog bones were made with LOCTITE 3D 3870 Black resin using the LOCTITE PR-10 Printer with the printing parameters set forth below in Table A.
Table A
Printing Parameters 2 Initial Layers Initial: Default: Layer Thickness (mm) 0.1 0.05 Rehab Time (secs) 2 2 Curing Time (secs) 45 4.5 Retraction Height 7 7 Retraction Speed Up 50 50 Time at Top 2 2 Retraction Speed Down 200 200 Light Intensity 100 100 [0042] To the so made parts, an activator (5 percent by weight of triethyl amine in hexane) was applied over the surface and once the hexane evaporated a cyanoacrylate composition (5 percent by weight of ethyl cyanoacrylate in acetonitrile) was applied thereover. When the acetonitrile evaporated, the parts had a tack free surface which was more optically clear than prior to post processing.
Claims (24)
- What is Claimed is: 1. A method of preparing a three-dimensional printed part made by additive manufacturing, comprising the steps of: A. Performing additive manufacturing using a curable (meth)acrylate composition to form a three-dimensional part on a build substrate, said three-dimensional printed part made according to data indicating a pre-determined pattern; and B. Optionally, removing the so-formed part from the build substrate; and C. Optionally, contacting at least some of the part with an activator; and D. Contacting the part with a cyanoacrylate composition.
- 2. The method of Claim 1, wherein the part after performing the method steps possesses at least one of improved surface finish, improved transparancy and reduced tackiness.
- 3. The method of any preceding Claim, wherein the activator is a nitrogen-containing compound or a transition metal containing compound.
- 4. The method of any preceding Claim, wherein the activator is a nitrogen-containing compound in a solution.
- 5. The method of any preceding Claim, wherein the activator is a nitrogen containing compound selected from the group consisting of 1,2-di-(4.-pyridyl-ethane), 4,4?-dpyridy: disulfide; 3-(3-hydroxypropyl)pyridine, 1,2-bis(diphenylphosphino)-ethane, pyridazine, n-tethylpyridazine or 4,4'-dipyridyl.
- 6. The method of any preceding Claim, wherein the activator is a nitrogen containing compound in an amount of about 0.5 to about 5 percent by weight in an organic solvent having a boiling point between about 30'C and about 100 C.
- 7. The method of any preceding Claim, wherein the cyanoacrylate composition comprises a cyanoacrylate monomer within the following structure: H2C=C(CN)-COOR, wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl groups.
- 8. The method of any preceding Claim, wherein the cyanoacrylate composition comprises a cyanoacrylate monomer selected from the group consisting of methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates, allyl cyanoacrylate, fl-methoxyethyl cyanoacrylate and combinations thereof.
- 9. The method of any preceding Claim, wherein the cyanoacrylate composition is in a solution.
- 10. The method of any preceding Claim, wherein the cyanoacrylate composition is in an amount of about 0.5 to about 10 percent by weight in an organic solvent having a boiling point between about 30'C and about 100 C.
- 11. The method of Claim 10, wherein the organic solvent used with the activator and the organic solvent used with the cyanoacrylate are the same.
- 12. The method of Claim 10, wherein the organic solvent used with the activator and the organic solvent used with the cyanoacrylate are different.
- 13. A method of post processing a three dimensional printed part made by additive manufacturing, comprising the step of: A. Providing an additive manufacturing-made three dimensional printed part having at least one surface, said three dimensional printed part made from a photocurable resin composition; and B. Contacting said surface of said additive manufacturing-made three dimen-sional printed part with (1) optionally an activator and (ii) a cyanoacrylate composition to form a coating over said surface.
- 14. The method of Claim 13, wherein the post processing imparts to the pad at least one of improved surface finish, improved transparancy and reduced tackiness.
- 15. The method of Claims 13 or 14, wherein the activator is a nitrogen-containing compound.
- 16. The method of any of Claims 13 to 15, wherein the activator is a nitrogen-containing compound in a solution.
- 17. The method of any of Claims 13 to 16, wherein the activator is wherein the activator is a nitrogen containing compound selected from the group consisting of 1,2-di(4-pp-idyl-ethane), 4,4'-dipyri1yl disulfide. 3-(3-hydroxypropyl)pyridine, 1,2-bis(diphe,-nylphosphino).-ethane, pyridazne, methylpyrdazine or 4,4-dipyridyl.
- 18. The method of any of Claims 13 to 17, wherein the activator is a nitrogen containing compound in an amount of about 0.5 to about 5 percent by weight in an organic solvent having a boiling point between about 30 C and about 100'C.
- 19. The method of any of Claims 13 to 18, wherein the cyanoacrylate composition comprises a cyanoacrylate monomer within the following structure: H2C=C(CN)-COOR, wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl groups.
- 20. The method of any of Claims 13 to 19, wherein the cyanoacrylate composition comprises a cyanoacrylate monomer selected from the group consisting of methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates, ally! cyanoacrylate, 11-methoxyethyl cyanoacrylate and combinations thereof.
- 21. The method of any of Claims 13 to 20, wherein the cyanoacrylate composition is in a solution.
- 22. The method of any of Claims 13 to 21, wherein the cyanoacrylate composition is in an amount of about 0.5 to about 10 percent by weight in an organic solvent having a boiling point between about 30 'C and about 100 ' C.
- 23. The method of Claim 22, wherein the organic solvent used with the activator and the organic solvent used with the cyanoacrylate are the same.
- 24. The method of Claim 22, wherein the organic solvent used with the activator and the organic solvent used with the cyanoacrylate are different.
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US6995227B2 (en) * | 2000-05-12 | 2006-02-07 | Loctite R&D Limited | Activator compositions for cyanoacrylate adhesives |
US7431793B2 (en) * | 2001-11-14 | 2008-10-07 | Loctite (R&D) Limited | Process for bonding substrates or parts and system including cyanoacrylate adhesive and accelerator composition |
FR2913909A1 (en) * | 2007-03-19 | 2008-09-26 | Axiatec | 3D PRINTING METHOD |
US20160243721A1 (en) * | 2015-02-23 | 2016-08-25 | Barristo Enterprises Inc. | Method for Strengthening 3D Printed Components |
TWI704194B (en) * | 2015-04-28 | 2020-09-11 | 日商東亞合成股份有限公司 | Hardenable composition and method for strengthening molded articles using the hardenable composition |
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EP3708370A1 (en) * | 2019-03-15 | 2020-09-16 | Henkel AG & Co. KGaA | 3d-printing method using gas-activated cyanoacrylates |
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2019
- 2019-09-30 GB GB1914088.8A patent/GB2587424B/en active Active
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2020
- 2020-09-25 WO PCT/EP2020/077002 patent/WO2021063845A1/en active Application Filing
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WO2015046217A1 (en) * | 2013-09-24 | 2015-04-02 | 株式会社アルテコ | Fabrication method for 3d shaped article, 3d shaped article, and coating agent for hot-melt resin laminating 3d printer |
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GB201914088D0 (en) | 2019-11-13 |
WO2021063845A1 (en) | 2021-04-08 |
GB2587424B (en) | 2023-12-13 |
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