CN115043987B - Composition for 3D printing, printing method and device - Google Patents
Composition for 3D printing, printing method and device Download PDFInfo
- Publication number
- CN115043987B CN115043987B CN202210886181.7A CN202210886181A CN115043987B CN 115043987 B CN115043987 B CN 115043987B CN 202210886181 A CN202210886181 A CN 202210886181A CN 115043987 B CN115043987 B CN 115043987B
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- composition
- acrylate
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- photo
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- 239000000203 mixture Substances 0.000 title claims abstract description 108
- 238000010146 3D printing Methods 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000007639 printing Methods 0.000 title claims abstract description 42
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 78
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 238000000016 photochemical curing Methods 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000003086 colorant Substances 0.000 claims abstract description 10
- -1 N-methacryloyloxyethyl-tert-butylamino Chemical group 0.000 claims description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000002041 carbon nanotube Substances 0.000 claims description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 229920002635 polyurethane Polymers 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
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- 239000011347 resin Substances 0.000 claims description 14
- 230000001588 bifunctional effect Effects 0.000 claims description 12
- 125000004386 diacrylate group Chemical group 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 239000005062 Polybutadiene Substances 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 125000000732 arylene group Chemical group 0.000 claims description 11
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- 239000002134 carbon nanofiber Substances 0.000 claims description 11
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
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- 229920002857 polybutadiene Polymers 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 6
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
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- 239000002270 dispersing agent Substances 0.000 claims description 5
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- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 4
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- 150000001412 amines Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
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- 150000002170 ethers Chemical class 0.000 claims description 4
- 239000012949 free radical photoinitiator Substances 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- AHSDAFWRDMVHNG-UHFFFAOYSA-M [K].[OH-].C(CCC)[N+](CCCC)(CCCC)CCCC Chemical compound [K].[OH-].C(CCC)[N+](CCCC)(CCCC)CCCC AHSDAFWRDMVHNG-UHFFFAOYSA-M 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 3
- XNWSMNKRGNKRKP-UHFFFAOYSA-M propanoate;tetramethylazanium Chemical compound CCC([O-])=O.C[N+](C)(C)C XNWSMNKRGNKRKP-UHFFFAOYSA-M 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- WGYONVRJGWHMKV-UHFFFAOYSA-M tetrabutylazanium;benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.CCCC[N+](CCCC)(CCCC)CCCC WGYONVRJGWHMKV-UHFFFAOYSA-M 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
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- 238000000465 moulding Methods 0.000 abstract description 37
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- 239000000049 pigment Substances 0.000 description 22
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
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- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 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 description 2
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- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 1
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- QHKGDMNPQAZMKD-UHFFFAOYSA-N 2-amino-2-methylbutan-1-ol Chemical compound CCC(C)(N)CO QHKGDMNPQAZMKD-UHFFFAOYSA-N 0.000 description 1
- RQEMBJIJUZALLG-UHFFFAOYSA-N 2-amino-2-methylcyclohexan-1-ol Chemical compound CC1(N)CCCCC1O RQEMBJIJUZALLG-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- ASXUBTFFMUJOCR-UHFFFAOYSA-N 2-formyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC=O ASXUBTFFMUJOCR-UHFFFAOYSA-N 0.000 description 1
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 241000573484 Copsychus Species 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000004157 Nitrosyl chloride Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- RDHSUTIDSFVNJL-UHFFFAOYSA-N OC(=O)C=C.CCCCCCCCCCCC(O)=O Chemical compound OC(=O)C=C.CCCCCCCCCCCC(O)=O RDHSUTIDSFVNJL-UHFFFAOYSA-N 0.000 description 1
- DCTLJGWMHPGCOS-UHFFFAOYSA-N Osajin Chemical compound C1=2C=CC(C)(C)OC=2C(CC=C(C)C)=C(O)C(C2=O)=C1OC=C2C1=CC=C(O)C=C1 DCTLJGWMHPGCOS-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- LFZDEAVRTJKYAF-UHFFFAOYSA-L barium(2+) 2-[(2-hydroxynaphthalen-1-yl)diazenyl]naphthalene-1-sulfonate Chemical compound [Ba+2].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21.C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 LFZDEAVRTJKYAF-UHFFFAOYSA-L 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000005724 cycloalkenylene group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WLDITALZKJVQDI-UHFFFAOYSA-N ethylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CCPC(=O)C1=C(C)C=C(C)C=C1C WLDITALZKJVQDI-UHFFFAOYSA-N 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RAWJTXJPOXFMLG-UHFFFAOYSA-N n-(dicyclohexylmethyl)butan-2-amine Chemical compound C1CCCCC1C(NC(C)CC)C1CCCCC1 RAWJTXJPOXFMLG-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 1
- 235000019392 nitrosyl chloride Nutrition 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 description 1
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 229940104573 pigment red 5 Drugs 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- 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
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/295—Heating elements
-
- 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
- B29C64/30—Auxiliary operations or equipment
- B29C64/386—Data acquisition or data processing for additive manufacturing
- B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- 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
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Abstract
The application provides a composition for 3D printing, a printing method and a device. The first aspect of the application provides a composition for 3D printing, which comprises, by weight, 20-60% of a blocked polyurethane prepolymer, 5-20% of an active hydrogen-containing compound, 5-40% of a photo-curing monomer, 5-40% of a photo-curing crosslinking agent, 0.5-5% of a photoinitiator, 0.1-3% of a catalyst, 0.1-5% of a filler, 0.1-2% of an auxiliary agent and 0.05-2% of a colorant. According to the 3D object printed by the composition for 3D printing, which is provided by the application, the 3D object has the characteristics of high molding precision and good mechanical property, and can meet the requirements of industrial application.
Description
Technical Field
The application relates to a composition for 3D printing, a printing method and a printing device, and relates to the technical field of 3D printing.
Background
The printing method of the 3D object mainly comprises the following steps: firstly, a digital model of a 3D object is obtained, slicing and layering are carried out on the digital model, then data processing and conversion are carried out on each slicing layer, printing data of each slicing layer are obtained, and finally, layer-by-layer printing and superposition are carried out according to the printing data of the slicing layers, so that the 3D object is obtained.
Thermoplastic polyurethane elastomer (TPU) has the characteristics of good elasticity, wear resistance, fatigue resistance, chemical resistance, low temperature resistance, good biocompatibility and the like, and is widely applied to the fields of automobiles, buildings, mining, aerospace, electronics, medical appliances, sports products and the like. The TPU is added into the photosensitive resin, so that the comprehensive performance of the photosensitive resin can be effectively improved, but in the existing 3D printing and curing system, the TPU is limited to be applied to the 3D printing composition due to lower strength and modulus and narrower mechanical property adjusting capability.
Disclosure of Invention
The application provides a composition for 3D printing, which has the characteristics of high precision and good mechanical property of a 3D object obtained by printing according to the composition, and can meet the requirements of industrial application.
The application also provides a 3D printing method and device, and the composition for 3D printing is used.
The first aspect of the application provides a composition for 3D printing, which comprises, by weight, 20-60% of a blocked polyurethane prepolymer, 5-20% of an active hydrogen-containing compound, 5-40% of a photo-curing monomer, 5-40% of a photo-curing crosslinking agent, 0.5-5% of a photo-initiator, 0.1-3% of a catalyst, 0.1-5% of a filler, 0.1-2% of an auxiliary agent and 0.05-2% of a colorant;
The blocked polyurethane prepolymer has a structure shown in formula 1:
in formula 1, R 1 One selected from carbon nanotubes, carbon nanofibers and boron nanofibers; r is R 2 And R is 3 Independently selected from one of ethers and esters; r is R 4 And R is 5 Independently selected from one of C1-C18 alkylene, C5-C18 alicyclic, C6-C18 arylene, C6-C20 arylalkylene and C6-C20 alkylarylene with straight chain or branched chain; r is R 6 And R is 7 Independently selected from one of N-methacryloyloxyethyl-tert-butylamino and methacryloyloxyethoxycarbonyl.
In a specific embodiment, the esters are selected from one of carbonates, caprolactams.
In one embodiment, R 2 And/or R 3 Has a molecular weight of 500-5000.
In one embodiment, the carbon nanotubes have an outer diameter of 1-50nm and an aspect ratio of 20-2000;
and/or the outer diameter of the carbon nanofiber is 20-200nm, and the length-diameter ratio of the carbon nanofiber is 50-500;
and/or the external diameter of the boron nanofiber is 10-100nm, and the length-diameter ratio of the boron nanofiber is 100-1000.
In a specific embodiment, the carbon nanotube is one of a single-walled carbon nanotube and a multi-walled carbon nanotube.
In one embodiment, the deblocking temperature of the blocked polyurethane prepolymer is 40-200 ℃.
In one embodiment, the deblocking temperature of the blocked polyurethane prepolymer is at least 20 ℃ greater than the printing temperature of the 3D printing composition.
In one embodiment, the active hydrogen-containing compound is selected from one or more of polyols, polyamines, polyalcohol amines, liquid unsaturated polyester resins, liquid epoxy resins, liquid phenolic resins, liquid silicone resins containing active hydrogen, and liquid rubbers containing active hydrogen at the end groups.
In one embodiment, the photo-curable monomer is selected from one or two of a photo-curable monofunctional soft monomer with vinyl group and a photo-curable monofunctional hard monomer with vinyl group.
In one embodiment, the vinyl-containing photocurable monofunctional soft monomer is capable of producing a homopolymer having a glass transition temperature of less than 25 ℃, and the vinyl-containing photocurable monofunctional hard monomer is capable of producing a homopolymer having a glass transition temperature of greater than 25 ℃.
In one embodiment, the vinyl-containing photocurable monofunctional soft monomer is selected from one or more of alkyl (meth) acrylate, alkoxylated (meth) acrylate, cyclic (meth) acrylate, and urethane-containing (meth) acrylate.
In one embodiment, the vinyl-containing photo-curable monofunctional hard monomer is selected from one or more of cycloalkyl (meth) acrylate, heterocyclic (meth) acrylate, benzene ring structure-containing (meth) acrylate, and acryloylmorpholine.
In a specific embodiment, the photocuring crosslinking agent is one or two selected from a bifunctional resin and a bifunctional monomer, wherein the bifunctional resin is a polymer containing two (methyl) acryloyloxy groups in a molecular structure, and the bifunctional monomer is a monomer containing two (methyl) acryloyloxy groups in the molecular structure.
In a specific embodiment, the difunctional resin is selected from one or more of difunctional polyurethane (meth) acrylate, difunctional polyester (meth) acrylate, difunctional epoxy (meth) acrylate, polybutadiene (meth) acrylate.
In a specific embodiment, the difunctional monomer is selected from one or more of triethylene glycol dimethacrylate, tricyclodecane amine dimethanol diacrylate, polyethylene glycol (300) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) dimethacrylate, polypropylene glycol (400) diacrylate, 4-ethoxy-bisphenol a diacrylate, polypropylene glycol (750) diacrylate, 1, 12-dodecyl dimethacrylate, (10) ethoxylated bisphenol a dimethacrylate, (30) ethoxylated bisphenol a dimethacrylate, (ethoxylated 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate.
In one embodiment, the photoinitiator is a free radical photoinitiator.
In a specific embodiment, the catalyst is selected from one or more of triethylamine hydrogen, triethylenediamine, dibutyltin dilaurate, stannous octoate, sodium oxide, potassium hydroxide, tributylammonium potassium hydroxide, tetrabutylammonium potassium hydroxide, tri-n-butylphosphine, tetramethylammonium propionate, tetrabutylammonium benzoate.
In a specific embodiment, the filler is selected from one or more of silica, carbon black, barium sulfate, aluminum hydroxide, kaolin, talc.
In a specific embodiment, the auxiliary agent is selected from one or more of polymerization inhibitor, leveling agent, defoamer and dispersant.
A second aspect of the present application provides a 3D printing method, including the steps of:
filling an area to be printed with the composition for 3D printing provided in the first aspect of the present application;
providing energy to the area to be printed according to the layer printing data, and solidifying to form a slice layer;
and repeatedly executing the steps to obtain a plurality of sequentially laminated slice layers to form the 3D object.
In one embodiment, the method further comprises: and heating a plurality of sequentially laminated slice layers to obtain the 3D object.
In one embodiment, the heating is performed by means of gradient heating.
In one embodiment, the gradient heating comprises four stages, wherein the temperature of the first stage is 50-70 ℃ for 1-3 hours; the temperature of the second stage is increased to 70-90 ℃ for 2-4h; the temperature in the third stage is increased to 90-110 ℃ for 1-3h; and the temperature in the fourth stage is increased to 110-130 ℃ for 2-4h.
A third aspect of the present application provides an apparatus for performing any of the above 3D printing methods, the apparatus comprising a build platform, a material container, an energy generator, and a forming surface, wherein:
the material container is used for containing the composition provided in the first aspect of the application;
the molding surface is positioned at the bottom of the material container, and the molding surface and the construction platform are used for determining a molding area of the 3D object;
the energy generator is configured to provide energy to the composition of the molding surface to cure to form the sliced layer based on the layer print data.
In one embodiment, the apparatus further comprises a heater for heating a plurality of sliced layers stacked in sequence.
The implementation of the present application has at least the following advantages:
1. The 3D printing composition can stably exist under the light-shielding condition, and the higher stability is beneficial to long-time transportation and storage. In the 3D printing process, a photocuring system consisting of a photocuring monomer, a photocuring crosslinking agent and a photoinitiator can generate a photocuring reaction to form a high-precision 3D object molding frame with certain mechanical properties, and as the temperature of the molding frame rises, a closed polyurethane prepolymer dispersed in the molding frame generates an deblocking reaction to generate a polyurethane prepolymer with isocyanate groups and nano materials and a compound containing the closed groups, the isocyanate groups of the polyurethane prepolymer and the compound containing active hydrogen generate a thermal polymerization reaction to generate polyurethane, and the nano materials in the polyurethane are matched to endow the 3D object with excellent mechanical properties, in particular to the tensile strength, the elongation at break and the tearing strength of the 3D object, and the compound with the closed groups can be grafted onto a photocuring crosslinking network, so that the influence of the existence of the sealing agent on the molding precision of the 3D object is avoided. In summary, the 3D object printed by the composition for 3D printing provided by the application has the characteristics of high molding precision and good mechanical property, and can meet the requirements of industrial application.
2. The application also provides a 3D printing method and device, and the 3D object printed by the method and device has the characteristics of high precision and good mechanical property, and can meet the industrial application requirements by using the composition for 3D printing.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, a brief description will be given below of the drawings that are needed in the embodiments or the prior art descriptions, it being obvious that the drawings in the following description are some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort to a person skilled in the art.
Fig. 1 is a schematic flow chart of a 3D printing method according to an embodiment of the present application;
fig. 2 is a schematic structural diagram of a 3D printing device according to an embodiment of the present application.
Reference numerals illustrate:
1-build platform, 2-materials container, 3-energy generator, 4-3D printing composition, 5-forming surface, 6-3D object.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described in the following in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
The first aspect of the application provides a composition for 3D printing, which comprises, by weight, 20-60% of a blocked polyurethane prepolymer, 5-20% of an active hydrogen-containing compound, 5-40% of a photo-curing monomer, 5-40% of a photo-curing crosslinking agent, 0.5-5% of a photoinitiator, 0.1-3% of a catalyst, 0.1-5% of a filler, 0.1-2% of an auxiliary agent and 0.05-2% of a colorant;
the blocked polyurethane prepolymer has a structure shown in formula 1:
in formula 1, R 1 One selected from carbon nanotubes, carbon nanofibers and boron nanofibers; r is R 2 And R is 3 Independently selected from one of ethers and esters; r is R 4 And R is 5 Independently selected from one of C1-C18 alkylene, C5-C18 alicyclic, C6-C18 arylene, C6-C20 arylalkylene and C6-C20 alkylarylene with straight chain or branched chain; r is R 6 And R is 7 Independently selected from one of N-methacryloyloxyethyl-tert-butylamino and methacryloyloxyethoxycarbonyl.
The 3D printing composition comprises, by weight, 20-60% of a closed polyurethane prepolymer, 5-20% of an active hydrogen-containing compound, 5-40% of a photo-curing monomer, 5-40% of a photo-curing cross-linking agent, 0.5-5% of a photo-initiator, 0.1-3% of a catalyst, 0.1-5% of a filler, 0.1-2% of an auxiliary agent and 0.05-2% of a colorant, wherein the closed polyurethane prepolymer has a certain deblocking temperature, and after the temperature reaches the deblocking temperature, the closed polyurethane prepolymer is subjected to the deblocking temperature The urethane prepolymer will be deblocked to form a polymer comprising end capping groups R 6 And R is 7 The polyurethane elastomer is generated by thermochemical reaction of isocyanate groups exposed at two ends of the polyurethane prepolymer and a compound containing active hydrogen, and forms an interpenetrating network of a photocuring crosslinking network and a polymer crosslinking network together with a photocuring monomer, a photocuring crosslinking agent, a photoinitiator and a partial auxiliary agent in a photocuring system, so that the mechanical properties of the 3D object, in particular the tensile strength, the elongation at break, the impact toughness and the tearing resistance are improved; comprising end capping groups R 6 And R is 7 The photo-curable compound can react with a photo-curing system and be grafted to a photo-curing crosslinking network, so that a sealing agent is not separated out after curing is finished, and the influence of the existence of the sealing agent on the molding precision of the 3D object is avoided; before deblocking reaction of the blocked polyurethane prepolymer, isocyanate groups are blocked by a group R 6 And R is 7 The polyurethane prepolymer is blocked, so that the polymerization reaction with the photo-curing monomer does not occur to cause the increase of the viscosity of the composition, and the problem of poor stability of the composition caused by the increase of the viscosity is avoided; in addition, the polyurethane prepolymer comprises a nanomaterial R 1 The mechanical property of the 3D object is further improved; in conclusion, the 3D object printed by using the composition provided by the application has the characteristics of high molding precision and mechanical properties, in particular, good tensile strength, elastic modulus, elongation at break and tearing strength.
By adjusting the selection and weight percentages of the individual components, the person skilled in the art can obtain a composition for 3D printing for stereolithography or digital light processing, each of which is described in detail below:
in one embodiment, the weight of the blocked polyurethane prepolymer is 20-60% of the total weight of the composition, having the structure of formula 1:
in formula 1, R 1 The nano material has strong mechanical properties, is widely ground and applied to epoxy resin, polyurethane and acrylic resin, but has poor compatibility and interface interaction with polyurethane, is difficult to uniformly disperse in polyurethane and easily forms aggregation, and can be separated from the polyurethane in an interface in the using process, so that the mechanical properties and the service life of a 3D object are greatly influenced, and the nano material is subjected to interface modification and is introduced into a polyurethane prepolymer by covalent grafting, non-covalent modification and other methods to enhance the mechanical properties of polyurethane, and further, the outer diameter of the carbon nano tube is 1-50nm, the length-diameter ratio of the carbon nano tube is 20-2000, and the carbon nano tube can be selected from single-wall carbon nano tubes or multi-wall carbon nano tubes; the outer diameter of the carbon nanofiber is 20-200nm, and the length-diameter ratio of the carbon nanofiber is 50-500; the outer diameter of the boron nanofiber is 10-100nm, the length-diameter ratio of the boron nanofiber is 100-1000, and the property non-uniformity of the formed 3D object in the XY direction and the Z direction can be effectively reduced by selecting the nanomaterial with a certain outer diameter and length-diameter ratio, so that the problem that the strength of the 3D object in the Z direction is lower than that in the XY direction is solved.
R 2 And R is 3 The ether is a group comprising an oxygen atom in a molecular structure, and the oxygen atom is connected with the same or different hydrocarbon groups or aromatic hydrocarbon groups, the ester is a group comprising-COO-in the molecular structure, and the ester is further one of carbonic acid esters and caprolactone esters; r is R 2 And/or R 3 Has a molecular weight of 500-5000.
R 4 And R is 5 Independently selected from one of C1-C18 alkylene having a straight or branched chain, C5-C18 alicyclic group, C6-C18 arylene group, C6-C20 arylalkylene group, and C6-C20 alkylarylene group, wherein the C1-C18 alkylene having a straight or branched chain means a group having the formula-C n H 2n - (1.ltoreq.n.ltoreq.18) groups, e.g. -CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、-CH(CH 3 )CH 2 -and the like; C5-C18 alicyclic group means a group in which two hydrogen atoms are less in the alicyclic hydrocarbon molecule of C5-C18, such as cycloalkylene group, cycloalkenylene group, etc.; C6-C18 arylene means a radical which results from the removal of two hydrogen atoms from a C6-C18 aromatic hydrocarbon molecule, e.g. -C 6 H 4 -、-C 6 H 3 (CH 3 ) -and the like; C6-C20 arylalkylene or C6-C20 alkylarylene refers to a group of 6-20 carbon atoms, including arylalkylene or alkylarylene in the structure, arylalkylene refers to an aryl group attached to an alkylene group, and alkylarylene refers to an alkyl group attached to an arylene group.
R 6 And R is 7 Independently selected from one of N-methacryloyloxyethyl-tert-butylamino and methacryloyloxyethoxycarbonyl, wherein the N-methacryloyloxyethyl-tert-butylamino has a structure represented by formula 2 and the methacryloyloxyethoxycarbonyl has a structure represented by formula 3:
since the blocked polyurethane prepolymer can be unblocked at a certain temperature, the polyurethane prepolymer comprising a blocking group R is released 6 And R is 7 The photo-curable compound of (a) and the polyurethane prepolymer having isocyanate groups, and thus, the deblocking temperature of the blocked polyurethane prepolymer is known to have a positive effect on printing of 3D objects, in particular, the deblocking temperature of the blocked polyurethane prepolymer is not lower than 40 ℃, if the deblocking temperature of the blocked polyurethane prepolymer is too low, once the storage or transportation environment is overheated, the blocked polyurethane prepolymer may be subjected to deblocking reaction to initiate thermal polymerization, and stability of the composition is reduced.
In addition, the deblocking temperature of the blocked polyurethane prepolymer is not too high, specifically, the deblocking temperature of the blocked polyurethane prepolymer is not higher than 200 ℃, otherwise, in the 3D printing process, the temperature above 200 ℃ is needed to be provided to trigger the deblocking reaction of the blocked polyurethane prepolymer, so that not only can larger energy loss be caused, but also the 3D object is easy to age at 200 ℃, and the mechanical property is reduced.
In order to avoid deblocking of the blocked polyurethane prepolymer prior to printing, the deblocking temperature of the blocked polyurethane prepolymer should be at least 20 ℃ higher than the printing temperature of the 3D printing composition to ensure stability of the composition in the container.
The application also provides a preparation method for preparing the closed polyurethane prepolymer, which specifically comprises the following steps:
firstly, the nano material is dispersed in an organic solvent after being treated for 6-8 hours under the condition of strong acid, and then an acyl chloride compound is added, and the nano material grafted with the acyl chloride functional group is obtained after the reaction; then, the nano material grafted with the acyl chloride functional group reacts with the polyol for 12-60 hours at the temperature of 60-100 ℃ to obtain the polyol containing the nano material; then, reacting the polyol containing the nano material with isocyanate to obtain polyurethane prepolymer; and finally, reacting the polyurethane prepolymer with a blocking agent to obtain the blocked polyurethane prepolymer.
In the specific implementation process, the strong acid can be one or two of concentrated hydrochloric acid and concentrated nitric acid; the organic solvent can be one or more of N, N-dimethylformamide, tetrahydrofuran, styrene, perchloroethylene, trichloroethylene and ethylene glycol ether; the acyl chloride compound may be one or more of thionyl chloride, nitrosyl chloride, acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, and trichloroacetyl chloride.
The polyol is an alcohol containing at least two hydroxyl groups, and can be one or more selected from polyester polyol, poly epsilon-caprolactone polyol, polycarbonate polyol and polyether polyol; the molecular weight of the polyalcohol is 500-5000; the type, structure and average molecular weight of the polyol can influence the soft and hard aggregation structure of the polyurethane material, so that the performance of the polyurethane is influenced, and the polyol can be selected according to actual requirements and is not limited in the specification; the molar ratio of polyol to acid chloride functional group is (2-3): 1.
the isocyanate is a polyisocyanate containing at least two isocyanate groups and can be selected from one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), xylylene Diisocyanate (XDI), diphenylmethane diisocyanate (MDI), hydrogenated MDI (HMDI) and Hydrogenated XDI (HXDI); the molar ratio of polyol to isocyanate containing nanomaterial is 1: (2-2.5).
The blocking agent is a photo-curable blocking agent, and comprises a blocking group R generated in thermal blocking 6 And R is 7 The light-curable compound of (2) is present in the 3D object to affect molding accuracy, and the blocking agent can be selected from one of tert-butylaminoethyl methacrylate and 2-formyloxyethyl methacrylate; the molar ratio of blocking agent to isocyanate groups is (1-1.2): 1.
The active hydrogen-containing compound is used for reacting with polyurethane prepolymer formed after deblocking, and the weight of the active hydrogen-containing compound is 5-20% of the total weight of the composition, and the active hydrogen-containing compound can be one or more selected from polyalcohol, polyamine, polyalcohol amine, liquid unsaturated polyester resin, liquid epoxy resin, liquid phenolic resin, liquid organic silicon resin containing active hydrogen and liquid rubber containing active hydrogen at the end group.
Specifically, the polyol is selected from one or more of ethylene glycol, propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, cyclohexanedimethanol, 2-ethyl-1, 3-hexanediol, cyclohexanediol and oligomer polyol;
the oligomer polyol is one or more selected from polyester polyol, poly epsilon-caprolactone polyol, polycarbonate polyol, polyether polyol, polyoxyacrylic polyol and polytetrahydrofuran polyol;
the polyamine is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, cyclohexanediamine, hexamethylenediamine, 1, 8-diaminooctane, 2, 5-diamino-2, 5-dimethylhexane, 1-amino-3, 5-trimethyl-5-aminomethylcyclohexane, 4' -diamino dicyclohexylmethane, 4-bis (sec-butylamino) -dicyclohexylmethane and oligomer polyamine;
The oligomer polyamine is selected from one or more of polyether diamine, polyester diamine and aliphatic diamine;
the polyalcohol amine is selected from one or more of ethanolamine, aminoethylethanolamine, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2, 2-dimethylethanol, 2-amino-2-ethyl-1-3-propanediol, tris (hydroxymethyl) aminomethane, 1-amino-1-methyl-2-hydroxycyclohexane and 2-amino-2-methyl-1-butanol;
the liquid unsaturated polyester resin is selected from one or more of o-benzene unsaturated polyester resin, m-benzene unsaturated polyester resin, p-benzene unsaturated polyester resin and bisphenol A unsaturated polyester resin;
the liquid epoxy resin is selected from one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin;
the liquid phenolic resin is selected from one or more of alcohol-soluble phenolic resin, oil-soluble phenolic resin and modified phenolic resin;
the liquid organic silicon resin containing active hydrogen groups is selected from one or more of hydroxyl modified silicone oil, carboxyl modified silicone oil, amino modified silicone oil and mercapto modified silicone oil;
The liquid rubber with the end group containing active hydrogen groups is selected from one or more of hydroxyl-terminated polybutadiene liquid rubber, carboxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated nitrile rubber, carboxyl-terminated nitrile rubber, amino-terminated polybutadiene liquid rubber, amino-terminated nitrile liquid rubber, mercapto-terminated polybutadiene liquid rubber and mercapto-terminated nitrile rubber.
The photo-curing monomer is a small molecular compound containing vinyl in a molecular structure, can be subjected to polymerization reaction, is used for adjusting the viscosity and the performance of the composition, and can be selected from one or two of a photo-curing monofunctional soft monomer with vinyl and a photo-curing monofunctional hard monomer with vinyl, wherein the weight of the small molecular compound is 5-40% of the total weight of the composition.
In particular, the photo-curable monofunctional soft monomer with vinyl groups is capable of producing a homopolymer having a glass transition temperature below 25 ℃, and the photo-curable monofunctional hard monomer with vinyl groups is capable of producing a homopolymer having a glass transition temperature above 25 ℃.
In one embodiment, the vinyl-containing photocurable monofunctional soft monomer may be selected from one or more of alkyl (meth) acrylate, alkoxylated (meth) acrylate, cyclic structural (meth) acrylate, urethane-containing (meth) acrylate.
Wherein the alkyl (meth) acrylate may be selected from one or more of isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isostearyl acrylate, isononanyl acrylate, lauric acid acrylate, isodecyl methacrylate, methyl stearyl acrylate, dodecyl methacrylate, isotridecyl methacrylate;
the alkoxylated (methyl) acrylate can be selected from one or more of 2-methoxy-2-methoxy acrylate, ethoxyethoxy ethyl acrylate, methoxy polyethylene glycol monoacrylate and methoxy polyethylene glycol methacrylate;
the (methyl) acrylic ester with a cyclic structure can be selected from one or more of tetrahydrofuran acrylic ester, 4-acryloylmorpholine, acrylic acid-2-phenoxyethyl ester, (2-ethyl-2-methyl-1, 3-dioxypentyl-4-yl) acrylic ester, alkoxylated nonylphenol acrylic ester, cyclotrimethylolpropane methylal acrylic ester and ethylated nonylphenol acrylic ester;
the (meth) acrylate having a urethane group may be selected from one or more of urethane acrylate, ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate, and aliphatic urethane acrylate.
The vinyl-containing photo-curable monofunctional hard monomer may be one or more selected from cycloalkyl (meth) acrylate, heterocyclic (meth) acrylate, benzene ring-containing (meth) acrylate, and acryloylmorpholine.
Wherein the cycloalkyl (meth) acrylate may be selected from one or more of isobornyl acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 3, 5-trimethylcyclohexane acrylate, 3, 5-trimethylcyclohexane methacrylate;
the heterocyclic (meth) acrylate may be selected from one or more of cyclotrimethyolpropane formal acrylate, 3-ethyl-3-epoxypropyl methyl acrylate, and tetrahydrofuran methacrylate;
the (methyl) acrylate with benzene ring structure can be selected from one or more of 2-phenoxyethyl methacrylate and o-phenylphenoxyethyl acrylate.
The photocuring crosslinking agent can enable polymer chains formed by polymerization of the photocuring monomers to be mutually connected to form a net structure, so that the crosslinking density of the 3D object is improved, the mechanical property of the 3D object is improved, and the weight of the photocuring crosslinking agent is 5-40% of the total weight of the composition; specifically, the photo-curing crosslinking agent may be one or two selected from a bifunctional resin and a bifunctional monomer, wherein the bifunctional resin is a polymer containing two (methyl) acryloyloxy groups in a molecular structure, and the bifunctional monomer is a monomer containing two (methyl) acryloyloxy groups in a molecular structure.
Specifically, the difunctional resin is one or more selected from difunctional polyurethane (methyl) acrylate, difunctional polyester (methyl) acrylate, difunctional epoxy (methyl) acrylate and polybutadiene (methyl) acrylate; further, the difunctional resin is one or two of difunctional polyurethane (methyl) acrylic ester and polybutadiene (methyl) acrylic ester, and the polybutadiene structure in the molecular structure of the difunctional polyurethane (methyl) acrylic ester and the polybutadiene structure is beneficial to enhancing the elongation and strength of the 3D object.
The difunctional polyurethane (methyl) acrylate is preferably aliphatic polyurethane (methyl) acrylate which has better flexibility and extensibility, more products are sold at present, and can be 6113, 6217, 6148T-85, 615-100, 6168, 6152B-80, 6148T-80 and the like of Changxing materials industry Co., ltd, CN9021NS, CN964, CN965NS, CN980NS, CN978NS and the like of Saduoma Co., and the like, freon 4256, 4215, 4217, 4230 and the like, EBECRYL8402, EBECRYL270, EBECRYL8411 and the like of Zhang, BR-344, BR-345, BR-374, BR-3042 and the like of Bomar;
the difunctional polyester (meth) acrylate may be CN7001NS, CN2283NS, etc. of the company shama, trust7118, trust7008, trust7110, trust7100, etc. of the company shengyan science and technology, inc, 6343, 6371, 6372, etc. of the company chang materials industry, inc;
The difunctional epoxy (methyl) acrylate can be CN123, CN2003NS and the like of the sand-gama company, 623A-80, 6215-100 and the like of the Changxing materials industry Co., ltd;
polybutadiene (meth) acrylate is an oligomer obtained by incorporating a (meth) acrylate group into polybutadiene, which is capable of forming an elastomer and polyacrylate by UV photocrosslinking, and is liquid at ordinary temperature, and many products are commercially available, such as CN301, CN302, CN307, CN303, ricryl 3801, etc., osaka organic BAC15, BAC45, etc., and BR641, BR643, etc., of bomar corporation.
The difunctional monomer is selected from one or more of triethylene glycol dimethacrylate, tricyclodecane amine dimethanol diacrylate, polyethylene glycol (300) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) dimethacrylate, polypropylene glycol (400) diacrylate, 4-ethoxy-bisphenol A diacrylate, polypropylene glycol (750) diacrylate, 1, 12-dodecyl dimethacrylate, (10) ethoxylated bisphenol A dimethacrylate, (30) ethoxylated bisphenol A dimethacrylate, (ethoxylated) 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate and tripropylene glycol diacrylate.
The photoinitiator is a free radical photoinitiator, the weight of which is 0.5-5% of the total weight of the composition, and the free radical photoinitiator can be selected from one or more of benzoin diethyl ether, benzoin alpha, alpha-dimethylbenzoyl ketal, alpha-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone-1, 1-hydroxy-cyclohexylbenzophenone (abbreviated as 184), 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylpropanone-1, [ 2-methyl-1- (4-methylsulfophenyl) -2-morpholinophenone-1 ], [ 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 ], benzoyl formate, 2,4, 6-trimethylphenyl acyl-ethoxy-phenylphosphine oxide, 2,4, 6-trimethylphenyl acyl-diphenylphosphine oxide (abbreviated as 819), bis (2, 4, 6-trimethylphenyl acyl) phenylphosphine oxide, 2,4, 6-trimethylbenzoyl ethylphosphine (abbreviated as 819), 4-p-toluyl ketone-L, and p-tolune.
The catalyst is used for adjusting the reactivity and the reaction rate of the blocked polyurethane prepolymer after deblocking and the compound containing active hydrogen, and the weight of the catalyst is 0.1-3% of the total weight of the composition, and the catalyst can be one or more selected from triethylamine hydrogen, triethylenediamine, dibutyltin dilaurate, stannous octoate, sodium oxide, potassium hydroxide, tributylammonium potassium hydroxide, tetrabutylammonium potassium hydroxide, tri-n-butylphosphine, tetramethylammonium propionate and tetrabutylammonium benzoate.
The filler can effectively reduce shrinkage of the molding layer in the curing process, improve printing precision, and simultaneously improve mechanical properties of the material, wherein the weight of the filler is 0.1-5% of the total weight of the composition, and the filler can be one or more selected from silicon dioxide, carbon black, barium sulfate, aluminum hydroxide, kaolin and talcum powder.
The weight of the auxiliary agent is 0.1-2% of the total weight of the composition, and the auxiliary agent can be one or more selected from polymerization inhibitor, leveling agent, defoaming agent and dispersing agent.
Specifically, the polymerization inhibitor can prevent free radical polymerization reaction and improve the storage stability of the composition, and can be selected from one or more of phenols, quinones and nitrite polymerization inhibitors, such as one or more of hydroquinone, terephthalquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone, 2, 5-di-tertiary butyl hydroquinone and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt (polymerization inhibitor 510).
The leveling agent is used for improving the fluidity of the composition, adjusting the surface tension of the composition to enable the composition to print normally, and the choice of the leveling agent is not particularly limited. The products currently available on the market are BYK333, BYK377, BYK-UV3530, BYK-UV3575, BYK-UV3535, etc. of the Pick company, TEGO wet 500, TEGO wet 270, TEGO Glide 450, TEGO RAD 2010, TEGO RAD 2011, TEGO RAD 2100, TEGO RAD 2200, etc.
The defoamer is used for inhibiting, reducing and eliminating bubbles in the composition, and the selection of the defoamer is not particularly limited in the application. The products currently commercially available are more, such as BYK1798, BYK055, BYK088, BYK020, BYK025, etc. of Pick corporation, TEGO Airex 920, TEGO Airex921, TEGO Airex 986, TEGO Foamex 810, TEGO Foamex N, etc. of Di high corporation, efka 7081, efka7082, etc.
The dispersant is used to improve the dispersion stability of the particulate matter in the composition, and the choice of dispersant is not particularly limited herein. The products currently sold in the market are more, and can be BYK102, BYK106, BYK108, BYK110, BYK111, BYK180, and Di high Dispers 655, dispers675, dispers710, dispers 630, dispers 670 and the like.
When the composition does not contain a colorant, scattering easily occurs during molding, so that the boundary of a 3D object is blurred, and the molding precision is low, therefore, the composition comprises 0.05-2% of colorant by weight, the colorant can be pigment or dye, the pigment is preferably pigment in the application, and the pigment can be specifically selected from C.I.pigment White 6, C.I.pigment Red3, C.I.pigment Red 5, C.I.pigment Red 7, C.I.pigment Red9, C.I.pigment Red 12, C.I.pigment Red 13, C.I.pigment Red 21, C.I.pigment Red31, C.I.pigment Red49:1, C.I.pigment Red 58:1 and C.I.pigment Red 175; c.i. pigment Yellow 63, c.i. pigment Yellow 3, c.i. pigment Yellow 12, c.i. pigment Yellow 16, c.i. pigment Yellow 83; one or more of C.I.pigment Blue 1, C.I.pigment Blue 10, C.I.pigment Blue B, phthalocyanine Blue BX, phthalocyanine Blue BS, C.I.pigment Blue 61:1.
The preparation method of the composition for 3D printing provided by the application comprises the following steps: firstly, placing a reaction kettle in a yellow light environment, proportionally adding a closed polyurethane prepolymer, a photo-curing monomer and a photo-curing crosslinking agent into the reaction kettle, and uniformly stirring to obtain a first mixture, wherein the viscosity of the closed polyurethane prepolymer is higher at room temperature and is reduced along with the increase of the temperature, so that the temperature in the reaction kettle is increased to 40-50 ℃ to be beneficial to the mixing of the components; then adding the auxiliary agent, the photoinitiator and the colorant according to the formula proportion, stirring uniformly to obtain a second mixture, cooling the mixture to room temperature and preserving the mixture in a dark place. Before 3D printing operation, adding the active hydrogen-containing compound and the catalyst into the second mixture according to a proportion, and stirring uniformly at room temperature to obtain the composition for 3D printing.
The 3D printing composition can stably exist under the light-shielding condition, and the higher stability is beneficial to long-time transportation and storage. In the 3D printing process, a photocuring system consisting of a photocuring monomer, a photocuring crosslinking agent and a photoinitiator can generate a photocuring reaction to form a high-precision 3D object molding frame with certain mechanical properties, and as the temperature of the molding frame rises, a closed polyurethane prepolymer dispersed in the molding frame generates an deblocking reaction to generate a polyurethane prepolymer with isocyanate groups and nano materials and a compound containing the closed groups, the exposed isocyanate groups of the polyurethane prepolymer can generate a thermal polymerization reaction with the compound containing active hydrogen to generate polyurethane, and the nano materials in the polyurethane are matched to endow the 3D object with excellent mechanical properties, in particular to the tensile strength, the elongation at break and the tearing strength of the 3D object, and the compound with the closed groups can be grafted onto the photocuring crosslinking network, so that the influence of the existence of the sealing agent on the molding precision of the 3D object is avoided.
A second aspect of the present application provides a 3D printing method using the composition for 3D printing provided in the first aspect of the present application, comprising the steps of:
acquiring layer printing data of a 3D object to be printed;
filling an area to be printed with the composition for 3D printing described above;
providing energy to the area to be printed according to the layer printing data, and solidifying to form a slice layer;
and printing layer by layer according to the layer printing data to obtain the 3D object.
The application provides a 3D printing method, which comprises the steps of firstly obtaining a digital model of a 3D object to be printed, slicing and layering the digital model, and carrying out data processing and conversion on each slicing layer to obtain layer printing data; and then filling the region to be printed with the composition provided in the first aspect of the application, providing energy to solidify the region to form a slice layer, repeating the steps, and sequentially layering according to the layer printing data to obtain the 3D object.
In a specific implementation manner, fig. 1 is a schematic flow chart of a 3D printing method according to an embodiment of the present application, as shown in fig. 1, where the method specifically includes the following steps:
step 1, acquiring layer printing data of a 3D object to be printed;
the layer print data is data representing a cross section of the 3D object, the method for obtaining the layer print data is not limited, any method for obtaining the layer print data in the 3D object printing process in the field can be adopted, for example, before the 3D object is printed, model data of the 3D object needs to be obtained, data format conversion is carried out on the model data, such as conversion into a format which can be identified by slicing software, such as STL format, PLY format, WRL format, and the like, slicing and layering processing is carried out on the model by using the slicing software, so that data representing the cross section layer of the object is also called layer print data; the layer print data includes information representing the shape of the object, and/or information representing the color of the object.
Step 2, filling an area to be printed with the composition for 3D printing;
the composition provided by the first aspect of the application is filled in the area to be printed, and before filling, the composition can be subjected to heating treatment according to requirements, wherein the heating temperature is not higher than the deblocking temperature of the closed polyurethane prepolymer.
Step 3, providing energy to the region to be printed according to the layer printing data, and solidifying to form a slice layer;
according to the layer printing data, energy is provided to the area to be printed, so that the composition in the area to be printed is solidified to form a slice layer, the solidification refers to that the area to be printed is irradiated with energy by using a radiation source, so that a photo-curing system in the area to be printed is subjected to photo-curing reaction to be in a solidification or semi-solidification state, and the radiation source can be one or more of UV light, electromagnetic radiation and infrared rays.
In the curing process, the temperature of the reaction system tends to rise, and a very small part of the closed polyurethane prepolymer reaches the deblocking temperature, so that the deblocking is carried out to generate the polyurethane prepolymer with isocyanate groups for thermal polymerization reaction, thereby improving the mechanical properties of the 3D object.
And 4, printing layer by layer according to the layer printing data to obtain the 3D object.
And (3) after forming a slice layer according to the step (2-3), repeatedly executing the steps, namely continuously forming an area to be printed on the surface of the previous slice layer, solidifying the area to be printed to form a new slice layer, sequentially superposing a plurality of slice layers, and heating the whole of a plurality of sequentially superposed slice layers obtained after layer-by-layer printing to obtain the final 3D object.
Specifically, the heating is performed by adopting a gradient heating mode, and the method specifically comprises four stages: the gradient heating comprises four stages, wherein the temperature of the first stage is 50-70 ℃ and the time is 1-3h; the temperature of the second stage is increased to 70-90 ℃ for 2-4h; the temperature in the third stage is increased to 90-110 ℃ for 1-3h; the temperature in the fourth stage is increased to 110-130 ℃ for 2-4h; in the heating process, the deblocking of the closed polyurethane prepolymer and the thermal polymerization reaction are facilitated, and the mechanical properties of the 3D object, in particular the tensile strength, the elastic modulus, the elongation at break and the tearing strength, are improved.
It should be noted that the temperature during the heating process should not be too high, as long as the deblocking reaction of the blocked polyurethane prepolymer can be initiated, otherwise, the 3D object is aged due to the too high temperature.
In summary, according to the 3D printing method provided by the present application, the composition for 3D printing is used to help to improve the molding precision and mechanical properties of a 3D object, in particular, the tensile strength, elongation at break and tear strength of the 3D object.
A third aspect of the present application provides an apparatus for performing any of the above 3D printing methods, comprising a build platform, a material container, an energy generator, and a forming surface, wherein:
the material container is used for containing the composition provided by the first aspect of the application;
the molding surface is positioned at the bottom of the material container, and the molding surface and the construction platform are used for determining a molding area of the 3D object;
the energy generator is configured to provide energy to the composition of the molding surface to cure to form the sliced layer based on the layer print data.
In a specific embodiment, fig. 2 is a schematic structural diagram of a 3D printing device provided in an embodiment of the present application, as shown in fig. 2, which includes a build platform 1, a material container 2, an energy generator 3, and a molding surface 5, where the material container 2 is used to hold a composition 4 provided in the first aspect of the present application, a molding surface 5 is provided at a bottom of the material container 2, and the build platform 1 and the molding surface 5 are used to determine a molding area of a 3D object 6; an energy generator 3 is located below the material container 2 for providing energy to the composition of the forming surface to cure to form a sliced layer in accordance with the layer print data.
The specific process of implementing 3D printing using the 3D printing apparatus may be: first, the 3D printing composition 4 is placed in the material container 2, and then, the energy generator 3 irradiates the molding surface 5 according to the layer printing data to cure the composition to form sliced layers, and after each sliced layer is formed, the build platform 1 is raised by a certain distance in the height direction, and after the sliced layers are stacked layer by layer in the height direction, the 3D object 6 is formed.
In one embodiment, the energy generator 3 is one or more of a UV LED lamp, a mercury lamp, a metal halogen lamp, an electrodeless lamp, a xenon lamp.
In addition, the device provided by the application further comprises a heater (not shown in the figure), and the heating component is used for heating a plurality of slice layers which are sequentially stacked to obtain the 3D object 6.
In one embodiment, the heater is selected from one or more of an infrared lamp, a microwave oven, a heating oven, an oven, a high temperature vacuum oven.
The apparatus provided by the present application further comprises a lifter (not shown in the figures) for adjusting the relative distance between the build platform 1 and the forming surface 5 to form a number of sequentially stacked sliced layers.
The device provided by the application further comprises a controller (not shown in the figures) for controlling the operation of one or more of the components of the energy generator 3, the heater and the lifter.
For example, the controller may control the radiation range, radiation intensity and radiation time of the area to be printed by the energy generator 3, control the relative distance of the build platform 1 and the forming surface 5 in the Z-direction, and control the temperature and heating time of the heater.
The 3D printing device is used for implementing the 3D printing method and can obtain the 3D object with high molding accuracy and high mechanical strength.
The following details are made in connection with specific examples, and the compositions for 3D printing provided in examples 1 to 6 and comparative examples 1 to 6 are shown in tables 1 to 4, and the structures and preparation methods of the blocked polyurethane prepolymers a to F provided in examples 1 to 6 and the blocked polyurethane prepolymers G to H, J and the polyurethane prepolymer I provided in comparative examples 1 to 6 are as follows:
the blocked polyurethane prepolymer A has a structure shown in a formula 1, wherein R is 1 Is a carbon nanotube with an outer diameter of 13nm and an aspect ratio of 100, R 2 And R is 3 Ethers of molecular weight 4000R 4 And R is 5 Are arylene groups having 7 carbon groups +.>R 6 And R is 7 All have the structure shown in formula 2.
The preparation method of the closed polyurethane prepolymer A comprises the following steps: firstly, 50g of carbon nano tubes are treated for 6 hours under the condition of strong acid, then the treated carbon nano tubes are dispersed in an organic solvent, thionyl chloride is added, and the reaction is carried out for 8 hours at 50 ℃ to obtain the carbon nano tubes containing acyl chloride functional groups; then, the carbon nanotubes containing the acid chloride functional group were reacted with a polyether polyol (Arcol PPG-4000, kogyo Co.) at 70℃for 12 hours, and the molar ratio of the two was controlled to be 2.1:1, obtaining polyol containing carbon nano tubes; then, the polyol containing carbon nano tubes is reacted with toluene diisocyanate, and the molar ratio of isocyanate to polyol is 2.1:1, finally, a molar ratio to isocyanate groups of 1.1:1 to give a blocked polyurethane prepolymer A.
The present example provides a method for preparing a composition for 3D printing as follows: placing the reaction kettle in a yellow light environment, proportionally adding the closed polyurethane prepolymer A, the photo-curing monomer and the photo-curing crosslinking agent into the reaction kettle according to the formula proportion, heating to 45 ℃, and stirring for 30min until the mixture is uniformly mixed to obtain a first mixture; and then adding the auxiliary agent, the initiator and the colorant according to the formula proportion, stirring for more than 50min until the mixture is uniformly mixed, obtaining a second mixture, cooling to 25 ℃ and preserving in dark. Before 3D printing operation, adding the active hydrogen-containing compound and the catalyst into the second mixture according to the proportion, and stirring for more than 20 minutes at room temperature until the mixture is uniformly mixed to obtain the composition for 3D printing.
The blocked polyurethane prepolymer B has a structure shown in a formula 1, wherein R 1 Is carbon nanofiber with an outer diameter of 40nm and an aspect ratio of 50, R 2 And R is 3 Are all caprolactoneR 4 And R is 5 Are all 9 carbon-based cycloalkanylidene +.>R 6 And R is 7 All have the structure shown in formula 2.
The blocked polyurethane prepolymer C has a structure shown in a formula 1, wherein R 1 Is a carbon nanotube with an outer diameter of 60nm and an aspect ratio of 1800, R 2 And R is 3 Are all caprolactoneR 4 And R is 5 Are arylene groups having 13 carbon groups +. >R 6 And R is 7 Has a structure shown in formula 3.
The blocked polyurethane prepolymer D has a structure shown in a formula 1, wherein R is 1 Is carbon nanofiber with an outer diameter of 80nm and an aspect ratio of 450, R 2 And R is 3 Are all carbonatesR 4 And R is 5 Are all cycloalkane subunits having 9 carbon groupsR 6 And R is 7 All have the structure shown in formula 3.
The blocked polyurethane prepolymer E has a structure shown in a formula 1, wherein R 1 Is boron nanofiber with an outer diameter of 50nm and an aspect ratio of 200, R 2 And R is 3 Are all caprolactoneR 4 And R is 5 Are arylene groups having 7 carbon atoms +.>R 6 And R is 7 All have the structure shown in formula 2.
The blocked polyurethane prepolymer F has a structure shown in formula 1, wherein R 1 Is boron nanofiber with an outer diameter of 50nm and an aspect ratio of 800, R 2 And R is 3 Are all carbonatesR 4 And R is 5 Arylene groups each having 13 carbon groupsR 6 And R is 7 Has a structure shown in formula 3.
The closed polyurethane prepolymer G is a closed polyurethane prepolymer which does not contain nano materials.
The preparation method of the closed polyurethane prepolymer G comprises the following steps: toluene diisocyanate was reacted with a polyether polyol having a molecular weight of 4000 (Col Arcol PPG-4000) and the molar ratio of isocyanate to polyol was controlled to 2.1:1, controlling the reaction temperature to be 50 ℃, reacting for 4 hours, and then adding a catalyst with the mole ratio of isocyanate groups of 1.1:1, and carrying out end-capping reaction for 4 hours at 50 ℃ to obtain a closed polyurethane prepolymer G.
The blocked polyurethane prepolymer H has a structure shown in a formula 1, wherein R is 1 Is a carbon nanotube with an outer diameter of 25nm and an aspect ratio of 1800, R 2 And R is 3 Are all caprolactoneR 4 And R is 5 Arylene groups each having 13 carbon groupsR 6 And R is 7 Are butanone oxime.
Polyurethane prepolymer I was an unblocked polyurethane prepolymer prepared in the same manner as the polyurethane prepolymer of example 1, but without blocking with a blocking agent.
The blocked polyurethane prepolymer J was a phenol blocked polyurethane prepolymer prepared in the same manner as the blocked polyurethane prepolymer A of example 1, but was blocked with phenol.
TABLE 1
TABLE 2
TABLE 3 Table 3
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TABLE 4 Table 4
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Example 7
The embodiment provides a 3D printing method, which specifically includes the following steps:
step 1, filling the printing area with the 3D printing composition provided in examples 1 to 6 and comparative examples 1 to 6, respectively;
step 2, providing energy to the printing area according to the layer printing data so as to at least partially solidify and form a slice layer;
and step 3, repeatedly executing the steps to obtain a plurality of sequentially laminated slice layers, and heating the sequentially laminated slice layers to form the 3D object.
Example 8
The present embodiment provides a 3D printing apparatus for implementing the printing method described above, as shown in fig. 2, including a build platform 1, a material container 2, an energy generator 3, a molding surface 5, a lifter, a controller, and a heater (not shown in the drawing).
The material container 2 is used for containing the composition for 3D printing provided in the foregoing examples or comparative examples;
the controller controls the energy generator 3 to supply energy to at least partially cure the print area in accordance with the layer print data, thereby forming a sliced layer. Layer print data is data characterizing a cross-section of a three-dimensional object, including information representing the shape of the object, and/or information representing the color of the object.
After forming at least one sliced layer, the controller controls the lifter to change the relative distance between the build platform 1 and the forming surface 5 in the Z direction; in this embodiment, the controller controls the lifting mechanism to drive the build platform 1 to move upwards by a layer thickness distance every time a slice layer is formed.
Subsequently, the controller fills the printing area with the material composition on the previous layer according to the layer print data and controls the energy generator 3 to provide energy to the printing area according to the layer print data to at least partially cure to form a new sliced layer; the steps are repeatedly executed, and a plurality of slice layers which are sequentially stacked are formed one by one.
And heating a plurality of sequentially laminated slice layers, and controlling the heating temperature of the heating component to be higher than the deblocking temperature in the closed polyurethane prepolymer to obtain the 3D object 6.
The following performance tests were conducted using the 3D printing compositions provided in examples 1 to 6 and comparative examples 1 to 6, and the specific results are shown in table 5.
1. Viscosity detection
The viscosity of the 3D printing composition was tested using a DV-I digital viscometer.
2. Accuracy of molding
The molding accuracy test is mainly reflected by volume shrinkage, and the test method comprises the following steps:
the density ρ of the composition before curing and its density ρ after complete curing were measured at 25 ℃ using a pycnometer method with water as reference, and the volume shrinkage was calculated according to the formula volume shrinkage (%) = (ρ1- ρ2)/ρ2 x 100%.
3. Shore hardness of
The 3D printing composition is applied to a DLP printer, and tested materials with required size specifications in GB/T2411-2008 (hardness of Shore hardness) is printed by using a durometer to measure plastics and hard rubber, and the Shore hardness is tested according to the standard.
4. Tensile Strength, elastic modulus, elongation at break
The 3D printing composition is applied to a DLP printer to print GB/T1040-2006, determination of Plastic tensile Property part 1: the test materials with the required size specifications in general rule are dumbbell-shaped, wherein the length is 155mm, the width at two ends is 20mm, the thickness is 4mm, the width at the middle is 10mm, the length of the narrow parallel part is 80mm, the radius is 60mm, and the test materials are prepared according to the section 1 of the measurement of the tensile properties of plastics in GB/T1040-2006: general rule "test tensile strength, modulus of elasticity, elongation at break of the test material. The test material (tensile test sample strip) is printed with two different placing positions, wherein the first surface with the width of 10mm is along the Z-axis direction and corresponds to sample strip 1; the second is that the surface with the length of more than or equal to 150mm is along the Z circumferential direction and corresponds to the spline 2. The printing and placing positions of other test sample strips are the first type, and the test sample strip numbers are not distinguished.
5. Flexural Strength and flexural modulus
The 3D printing composition was applied to a DLP printer, and test materials of the required dimensional specifications in GB/T9341-2008 "determination of plastic bending properties" were printed and tested for bending strength and flexural modulus according to this standard, with the bars being 80mm long, 10mm wide and 4mm thick.
6. Impact Strength
The 3D printing composition is applied to a DLP printer, and a tested material with the size specification required by GB/T1843-2008 "determination of impact Strength of Plastic cantilever beam" is printed and the impact strength is tested according to the standard, wherein a spline is 80mm long, 10mm wide, 4mm thick, and the residual width after notch is 8mm.
7. Dimensional stability test
Applying the 3D printing composition to a DLP printer, and printing squares with the length, width and height of 10mm, 10mm and 10mm respectively; after printing, performing heat treatment, wherein the heating temperature in the first stage is 90 ℃ for 2 hours, the heating temperature in the second stage is 110 ℃ for 3 hours, and the heating temperature in the third stage is 140 ℃ for 4 hours; naturally cooling to 25 ℃, measuring the length, width and height of the square block after heat treatment, wherein the measured length, width and height are all 10+/-0.1 mm, namely the dimensional stability is good, and if the measured length, width and height pass the test, otherwise, the measured length, width and height do not pass the test.
TABLE 5
From table 5, it can be seen that: the 3D object printed by the composition for 3D printing provided in examples 1-6 has high molding accuracy and good mechanical properties (tensile strength, elastic modulus, elongation at break, bending strength, bending modulus, impact strength). The 3D printed object formed without the polyurethane prepolymer grafted with the nanomaterial in comparative example 1 is inferior in tensile strength, elastic modulus, flexural strength, flexural modulus; in comparative example 2, carbon nanotubes were added as a filler to a 3D printing material for molding, and although the mechanical properties were improved relative to comparative example 1, the mechanical properties were inferior to examples 1 to 6 because of poor compatibility and interfacial interaction of carbon nanotubes with polyurethane, and the amount of carbon nanotubes added was limited; in comparative example 4, an unblocked polyurethane prepolymer was used, and a 3D object could not be formed due to unstable storage and printing process of a 3D printing material caused by the presence of free isocyanate groups; while the ketoxime end-capping agent is adopted for end capping in the comparative example 3, and the phenol end-capping agent is adopted for end capping in the comparative example 5, compared with the end-capping agents provided by the invention, the ketoxime small molecule end-capping agent and the phenol small molecule end-capping agent are easy to cause low molding precision of the 3D object and poor mechanical property; the content of the blocked polyurethane prepolymer F used in comparative example 6 was low, the effect of heat curing chain extension was hardly exhibited, and the elongation at break and impact strength were low, although the tensile strength and elastic modulus were improved to some extent, and the mechanical properties were inferior to those of example 6.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (22)
1. The composition for 3D printing is characterized by comprising, by weight, 20-60% of a closed polyurethane prepolymer, 5-20% of an active hydrogen-containing compound, 5-40% of a photo-curing monomer, 5-40% of a photo-curing crosslinking agent, 0.5-5% of a photo-initiator, 0.1-3% of a catalyst, 0.1-5% of a filler, 0.1-2% of an auxiliary agent and 0.05-2% of a colorant;
the blocked polyurethane prepolymer has a structure shown in formula 1:
in formula 1, R 1 One selected from carbon nanotubes, carbon nanofibers and boron nanofibers; r is R 2 And R is 3 Independently selected from one of ethers and esters; r is R 4 And R is 5 Independently selected from one of C1-C18 alkylene, C5-C18 alicyclic, C6-C18 arylene, C6-C20 arylalkylene and C6-C20 alkylarylene with straight chain or branched chain; r is R 6 And R is 7 Is N-methacryloyloxyethyl-tert-butylamino;
the N-methacryloyloxyethyl-tert-butylamino group has a structure represented by formula 2:
the deblocking temperature of the blocked polyurethane prepolymer is at least 20 ℃ higher than the printing temperature of the 3D printing composition.
2. The composition for 3D printing according to claim 1, wherein the esters are one selected from carbonates and caprolactones.
3. The 3D printing composition according to claim 1, wherein R 2 And/or R 3 Has a molecular weight of 500-5000.
4. The composition for 3D printing according to claim 1, wherein the carbon nanotubes have an outer diameter of 1 to 50nm and an aspect ratio of 20 to 2000;
and/or the outer diameter of the carbon nanofiber is 20-200nm, and the length-diameter ratio of the carbon nanofiber is 50-500;
and/or the external diameter of the boron nanofiber is 10-100nm, and the length-diameter ratio of the boron nanofiber is 100-1000.
5. The composition for 3D printing of claim 1, wherein the carbon nanotubes are one of single-walled carbon nanotubes and multi-walled carbon nanotubes.
6. The 3D printing composition according to any one of claims 1 to 5, wherein the deblocking temperature of the blocked polyurethane prepolymer is 40 to 200 ℃.
7. The composition for 3D printing according to any one of claims 1 to 5, wherein the active hydrogen-containing compound is selected from one or more of a polyhydric alcohol, a polyamine, a polyalcohol amine, a liquid unsaturated polyester resin, a liquid epoxy resin, a liquid phenolic resin, an active hydrogen-containing liquid silicone resin, and a liquid rubber having an active hydrogen-containing terminal group.
8. The composition for 3D printing according to any one of claims 1 to 5, wherein the photo-curable monomer is one or both selected from a photo-curable monofunctional soft monomer with vinyl group and a photo-curable monofunctional hard monomer with vinyl group.
9. The 3D printing composition of claim 8, wherein the vinyl-containing photo-curable monofunctional soft monomer is capable of producing a homopolymer having a glass transition temperature below 25 ℃, and wherein the vinyl-containing photo-curable monofunctional hard monomer is capable of producing a homopolymer having a glass transition temperature above 25 ℃.
10. The composition for 3D printing according to claim 9, wherein the photo-curable monofunctional soft monomer having a vinyl group is selected from one or more of alkyl (meth) acrylate, alkoxylated (meth) acrylate, cyclic (meth) acrylate, urethane group-containing (meth) acrylate.
11. The composition for 3D printing according to claim 9, wherein the vinyl group-containing photo-curable monofunctional hard monomer is one or more selected from cycloalkyl (meth) acrylate, heterocyclic (meth) acrylate, benzene ring-containing (meth) acrylate, and acryloylmorpholine.
12. The composition for 3D printing according to any one of claims 1 to 5, wherein the photo-curable cross-linking agent is one or two selected from a bifunctional resin, a bifunctional monomer, and the bifunctional resin is a polymer having two (meth) acryloyloxy groups in a molecular structure, and the bifunctional monomer is a monomer having two (meth) acryloyloxy groups in a molecular structure.
13. The composition for 3D printing according to claim 12, wherein the difunctional resin is selected from one or more of difunctional polyurethane (meth) acrylate, difunctional polyester (meth) acrylate, difunctional epoxy (meth) acrylate, polybutadiene (meth) acrylate.
14. The 3D printing composition of claim 12, wherein the difunctional monomer is selected from one or more of triethylene glycol dimethacrylate, tricyclodecane amine dimethanol diacrylate, polyethylene glycol (300) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) dimethacrylate, polypropylene glycol (400) diacrylate, 4-ethoxy-bisphenol a diacrylate, polypropylene glycol (750) diacrylate, 1, 12-dodecyl dimethacrylate, (10) ethoxylated bisphenol a dimethacrylate, (30) ethoxylated bisphenol a dimethacrylate, (ethoxylated) 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate.
15. The 3D printing composition of any of claims 1-5, wherein the photoinitiator is a free radical photoinitiator.
16. The 3D printing composition of any of claims 1-5, wherein the catalyst is selected from one or more of triethylenediamine, dibutyltin dilaurate, stannous octoate, sodium oxide, potassium hydroxide, tributylammonium potassium hydroxide, tetrabutylammonium potassium hydroxide, tri-n-butylphosphine, tetramethylammonium propionate, tetrabutylammonium benzoate.
17. The 3D printing composition according to any one of claims 1-5, wherein the filler is selected from one or more of silica, carbon black, barium sulfate, aluminum hydroxide, kaolin, talc.
18. The composition for 3D printing according to any one of claims 1 to 5, wherein the auxiliary agent is selected from one or more of polymerization inhibitors, leveling agents, antifoaming agents, dispersing agents.
19. A 3D printing method, comprising the steps of:
filling an area to be printed with the composition for 3D printing of any one of claims 1 to 18;
providing energy to the area to be printed according to the layer printing data, and solidifying to form a slice layer;
And repeatedly executing the steps to obtain a plurality of sequentially laminated slice layers to form the 3D object.
20. The 3D printing method as defined in claim 19 wherein the method further comprises: and heating a plurality of sequentially laminated slice layers to obtain the 3D object.
21. The 3D printing method as defined in claim 20 wherein the heating is performed by means of gradient heating.
22. The 3D printing method as defined in claim 21 wherein the gradient heating includes four stages, wherein the temperature of the first stage is 50-70 ℃ for 1-3 hours; the temperature of the second stage is increased to 70-90 ℃ for 2-4h; the temperature in the third stage is increased to 90-110 ℃ for 1-3h; and the temperature in the fourth stage is increased to 110-130 ℃ for 2-4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210886181.7A CN115043987B (en) | 2022-07-26 | 2022-07-26 | Composition for 3D printing, printing method and device |
Applications Claiming Priority (1)
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