CN107641200A - A kind of thiol-ene light-cured resin for 3D printing and preparation method thereof - Google Patents
A kind of thiol-ene light-cured resin for 3D printing and preparation method thereof Download PDFInfo
- Publication number
- CN107641200A CN107641200A CN201710857929.XA CN201710857929A CN107641200A CN 107641200 A CN107641200 A CN 107641200A CN 201710857929 A CN201710857929 A CN 201710857929A CN 107641200 A CN107641200 A CN 107641200A
- Authority
- CN
- China
- Prior art keywords
- printing
- mercaptan
- cured resin
- light
- alkene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 68
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- 238000010146 3D printing Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 title 1
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 26
- 229920006295 polythiol Polymers 0.000 claims abstract description 20
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- -1 mercaptan alkene Chemical class 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract 2
- 229920002554 vinyl polymer Polymers 0.000 claims abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 3
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 2
- 235000015511 Liquidambar orientalis Nutrition 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004870 Styrax Substances 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- UXWSUTBOOHDZIL-UHFFFAOYSA-N bis(1-hydroxycyclohexyl)methanone Chemical class C1CCCCC1(O)C(=O)C1(O)CCCCC1 UXWSUTBOOHDZIL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- SJNWVJGWEJCMEY-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;phthalic acid Chemical compound OCCOCCO.OC(=O)C1=CC=CC=C1C(O)=O SJNWVJGWEJCMEY-UHFFFAOYSA-N 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims 1
- 125000004386 diacrylate group Chemical group 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 claims 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000006276 transfer reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 5
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 2
- RQPNXPWEGVCPCX-UHFFFAOYSA-N 3-sulfanylbutanoic acid Chemical class CC(S)CC(O)=O RQPNXPWEGVCPCX-UHFFFAOYSA-N 0.000 description 2
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical class CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- JLLMOYPIVVKFHY-UHFFFAOYSA-N Benzenethiol, 4,4'-thiobis- Chemical compound C1=CC(S)=CC=C1SC1=CC=C(S)C=C1 JLLMOYPIVVKFHY-UHFFFAOYSA-N 0.000 description 1
- DAXREOFYACZDJD-UHFFFAOYSA-N C(C)C1=CC=2C(C3=CC=CC=C3SC2C(=C1)CC)=O.C1(=CC=CC=C1)[PH2]=O Chemical class C(C)C1=CC=2C(C3=CC=CC=C3SC2C(=C1)CC)=O.C1(=CC=CC=C1)[PH2]=O DAXREOFYACZDJD-UHFFFAOYSA-N 0.000 description 1
- ZEYKSBOVXOVGCG-UHFFFAOYSA-N ClC=1C(=C(C(=C(C1)Cl)Cl)Cl)Cl.C(C(=C)C)(=O)O Chemical compound ClC=1C(=C(C(=C(C1)Cl)Cl)Cl)Cl.C(C(=C)C)(=O)O ZEYKSBOVXOVGCG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-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
- 125000005118 N-alkylcarbamoyl group Chemical group 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZZUPGZLDMTMFL-UHFFFAOYSA-N triazine;trithiole Chemical compound S1SC=CS1.C1=CN=NN=C1 VZZUPGZLDMTMFL-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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Abstract
The present invention relates to 3D printing technique field, and in particular to a kind of mercaptan-alkene light-cured resin for 3D printing and preparation method thereof.The described mercaptan-alkene light-cured resin for 3D printing, is prepared by polythiol, acrylic resin prepolymer, reactive diluent, initiator, ultraviolet absorber, filler and auxiliary agent raw material.Such a 3D printing light-cured resin is in the presence of photo initiator, when printing polymerization forming, chain transfer reaction between double bond and sulfydryl causes polymer volume is shunk to reduce, with without oxygen inhibition, the degree of crosslinking and the speed of reaction can be controlled according to different vinyl monomers, the advantages that the use of a small amount of light trigger.The present invention is reacted by introducing mercaptan alkene clicking chemistry in 3D printing resin, can be reached and be shortened hardening time, is improved the toughness and hardness of 3D printing material, is improved production efficiency, energy rate utilization rate greatly improves.
Description
Technical field
The present invention relates to 3D printing technique field, and in particular to a kind of mercaptan-alkene light-cured resin for 3D printing and
Its preparation method.
Background technology
Mercaptan-alkene clicking chemistry vividly describes chemical reaction process that to hit mouse for picture point equally simple, efficient, real
With its feature has：(1) reaction raw materials be readily available, monomer it is applied widely；(2) there is higher thermodynamic driving force, react
Speed is fast；(3) reaction condition is simply gentle, is hardly influenceed by external environment (oxygen and water etc.)；(4) do not need solvent or
The solvent used is easily isolated；(5) yield is high, product regularity is good；(6) product Isolation and purification method is simple.Click chemistry
It can realize that atom connects using a series of high efficient and reliables and selective C-S binding reactions, carry out novel high-performance
And functional polymer modularization prepare, this series of advantages, make its as fastening means organic synthesis, material science, divide
There is wide application in the field such as sub- biology and biotechnology, Polymer Synthesizing.
3D printing is described as overturning the industrial revolution again of traditional manufacture, and 3D printing technique is to utilize computer, will
Three-dimensional stereo model is converted into simple two-dimensional model, controls Composition by computer, finally gives complicated shape
Molding part manufacturing technology.Quick shaping process is existing tens kinds at present, and wherein Introduction To Stereolithography is that occur most
A kind of early rapid shaping technique, using photosensitive resin as material, the characteristic of resin directly affects the performance of product, Production Time
With the final precision of part etc..At present, photosensitive resin is divided into 3 classes：Radical photosensitive resin, cation photosensitive resin and mix type light
Quick resin.Volume contraction can occur in the mechanism of photopolymerization for these traditional photosensitive resins, directly affects product
Performance, the decline for causing the performances such as adhesive force, hardness, extend Production Time, have impact on the precision of product, make oxygen inhibition tight
Weight.
For technical problem present in prior art, there is provided a kind of photosensitive resin material of new performance is urgently to be resolved hurrily
The problem of.
The content of the invention
In order to solve problems of the prior art, the invention provides a kind of new light for 3D printing technique
Quick resin：Mercaptan-alkene photosensitive resin, the described mercaptan-alkene light-cured resin available for 3D printing, by polythiol, propylene
Acid resin prepolymer, reactive diluent, initiator, ultraviolet absorber, filler and auxiliary agent raw material are prepared.
In preferred embodiments, described mercaptan-alkene light-cured resin is prepared according to following proportioning：
The mercaptan-alkene light-cured resin of the present invention includes at least one polythiol.Polythiol is that one kind at least contains two
The organic molecule of sulfydryl, there is general formula R-(S-H)n1, wherein R is the organic moiety for having chemical valence n1, and n1 is at least 2.
Polythiol can be polymerize or be crosslinked with acrylate by light radiation in the presence of initiator.Polythiol can
With including 2 or more sulfydryls.
The illustrative example in molecule with the polythiol of 2 or more sulfydryls is represented by following formula (1) (2) (3) (4)：
Compound containing 2 or more sulfydryls in molecule is：1,2- dithioglycol, 1,3- dimercaptopropane, 1,8- is pungent
Two mercaptan, 2,3- succinimide mercaptans, the mercaptan of 1,9- nonyl two, 2,2'- (1,2- second diyl dioxygen generation) double ethyl mercaptans, four (3- sulfydryls third
Acid) pentaerythritol ester, sulfydryl silicone oil, a dimercaptobenzene, Isosorbide-5-Nitrae-benzene dimethanethiol, 4- methyl isophthalic acids, 2- thioresorcins, 4,4 '-sulphur
Generation double benzenethiols, 2,4,6- tri-thiol triazines, four (3- mercaptobutyric acids) pentaerythritol esters.This compound can be used alone or
Two or more are applied in combination.
The degree of functionality of polythiol, the type and quantity of R group, the degree of cross linking, hardness, pliability of material can be adjusted.
Such as when preparing high rigidity, high rigidity material, preferably R group is aryl, alkyl, N- alkyl-carbamoyls.
Preferable polythiol includes, a dimercaptobenzene, Isosorbide-5-Nitrae-benzene dimethanethiol, and 4,4 '-thiobis-benzenethiol, 4- methyl isophthalic acids, the mercaptos of 2- bis-
Base benzene, 2,4,6- tri-thiol triazines etc..
When preparing high flexibility, high-toughness material, preferably R group is polyether-based, alkoxy, straight chained alkyl, siloxy group.It is excellent
The polythiol of choosing includes, 1,2- dithioglycol, 1,3- dimercaptopropane, 1,8- pungent two mercaptan, 2,3- succinimide mercaptans, the sulphur of 1,9- nonyl two
Alcohol, 2,2'- (1,2- second diyl dioxygen generation) double ethyl mercaptans, four (3- mercaptopropionic acids) pentaerythritol esters, sulfydryl silicone oil, four (3- mercaptos
Base butyric acid) pentaerythritol ester etc..
Mercaptan-alkene photosensitive resin preferably includes at least one polythiol, relative to the gross weight of composition, about 5-30 weight
Part, the more preferably from about polythiol of 10-20 parts by weight.
The mercaptan-alkene light-cured resin of the present invention includes at least one acrylic resin oligomer.Mercaptan-alkene photocuring tree
Acrylic resin prepolymer in fat constitutes the main component of light-cured resin system, and its performance largely determines
The main performance of material after solidification.In general, prepolymer molecular weight is big, and volume contraction is small during solidification, and curing rate is also fast, but
Molecular weight is big, and viscosity rise is, it is necessary to which more monomers dilute, and the viscosity height of system can also influence the shaping of 3D printing technique
Precision and forming efficiency.Therefore, the selection of prepolymer and its content is particularly important.In the mercaptan-alkene photosensitive resin of the present invention
Acrylic resin oligomer, including epoxy acrylic resin, polyester acrylate resin, polyurethane acrylic resin, unsaturation are poly-
Ester, the one or more in organic silicon acrylic ester prepolymer and polyoxyalkylene acrylate resin.
In the present invention, when preparing high rigidity, high rigidity material, preferred epoxy acrylic resin, polyester acrylate resin
And unsaturated polyester (UP).When preparing high flexibility, high-toughness material, preferred polyurethane acrylic resin, silicone modified acrylic resin and
Polyoxyalkylene acrylate resin.
Mercaptan-alkene photosensitive resin preferably includes at least one acrylic resin oligomer, relative to the gross weight of composition, about
10-60 parts by weight, more preferably from about 20-50 parts by weight.
The mercaptan-alkene light-cured resin of the present invention includes at least one reactive diluent.Preferably, the reactive diluent
For hydroxy-ethyl acrylate, hydroxyethyl methacrylate, caprolactone, isodecyl acrylate, polyethylene glycol monoacrylate,
2- phenoxyethyl methacrylates, 1,6- hexanediyl esters, propylene glycol diacrylate, bicyclopentadiene
(methyl) acrylate, triethylene glycol diacrylate, the third oxidation neopentylglycol diacrylate, (methyl) acrylic acid pentachlorobenzene
Base ester, trimethylolpropane trimethacrylate and pentaerythritol triacrylate, dipentaerythritol tetraacrylate, EO- modifications
Bisphenol-A two (methyl) acrylate, PO- modification bisphenol-A two (methyl) acrylate in one or more, relative to group
The gross weight of compound, more preferably from about about 5-40 parts by weight, 10-35 parts by weight.
The initiator that the mercaptan-alkene light-cured resin of the present invention includes includes styrax dimethyl ether (DMAP), 2- hydroxyls
Base -2- methyl isophthalic acids-phenyl -1- acetone, 1- hydroxy-cyclohexyl ketones, 2,4,6- trimethylbenzoy-dipheny phosphine oxides are double
(2,4,6 ,-trimethylbenzoyl) phenyl phosphine oxide 2,4- diethyl thioxanthones, benzophenone, 2- methyl isophthalic acids-(4- first mercaptos
Base phenyl) one or more in -2- morpholines acetone -1 and 4- benzoyls -4 '-dimethyl diphenyl sulfide.Relative to composition
Gross weight, about 0.1~10 parts by weight, more preferably from about 0.5~6 parts by weight.
The mercaptan-alkene photosensitive resin of the present invention includes at least one ultraviolet absorber.Can by the dosage of ultraviolet absorber
To adjust the curing depth of 3D photosensitive resins, so as to adjust the precision of resin cured material.Described ultraviolet absorber includes 2-
The just new epoxide benzophenone of hydroxyl -4, ESCALOL 567,2- hydroxyl -4- methoxyl group -5- sulfonic acid benzophenone,
One in 2- (2 '-hydroxyl -5 '-t-octyl phenyl) BTAs and double (2,2,6,6- pentamethyl -4- piperidyls) sebacates
Kind is several.Relative to the gross weight of composition, more preferably from about about 0.01-1 parts by weight, 0.1-0.5 parts by weight.
The filler that includes of mercaptan-alkene light-cured resin of the present invention, preferably includes calcium carbonate superfine powder, superfine silicon dioxide,
One or more in talcum powder and nano core shell rubber.Relative to the gross weight of composition, about 0.5~8 parts by weight, more preferably
About 1~5 parts by weight.
The auxiliary agent that the mercaptan-alkene light-cured resin of the present invention includes preferably includes coupling agent, polymerization inhibitor, levelling agent, defoaming
One or more in agent, fluorescent whitening agent, wetting dispersing agent or pigment, the coupling agent are preferably KH-560 or KH-570.
Pigment includes inorganic pigment and organic pigment, and wherein inorganic pigment is one kind in titanium white, lithopone, lead chromate yellow, barba hispanica；It is organic
Pigment is one kind in pigment scarlet powder, azophosphine, phthalocyanine blue, quinacridone.The auxiliary agent is preferably 0.1~3 parts by weight, more preferably
For 0.2~4 parts by weight.
The present invention introduces new mechanism of polymerization in 3D printing photosensitive resin：Mercaptan-alkene clicking chemistry, reaction speed is fast,
Without oxygen inhibition, solvent-free, the degree of cross linking, hardness, pliability of material can be adjusted by different degrees of functionality, substituent R.
Accordingly, the present invention also provides a kind of preparation method of the mercaptan-alkene light-cured resin available for 3D printing, including
Following steps：By the polythiol described in above-mentioned technical proposal, acrylic ester prepolymer, reactive diluent, initiator, UV absorption
Agent, filler and auxiliary agent mixing, stir 30~120 minutes at 20~60 DEG C, obtain mercaptan-alkene photocuring 3D printing material.Its
In, whipping temp is preferably 30~50 DEG C, more preferably 30~40 DEG C；Mixing time is preferably 40~100 minutes, more preferably
For 50~90 minutes.
Mercaptan-alkene light-cured resin available for 3D printing prepared by the present invention, mercaptan-alkene clicking chemistry is reacted and introduced
In the printing of 3D photocurings, mercaptan-alkene clicking chemistry reacts simple and effective, course of reaction does not produce accessory substance or accessory substance is harmless,
It is easy to apply, can be rapidly performed by room temperature, and the accurate control to reaction can be realized to the selection of exposure area and time,
Apply it to 3D photocurings printing field, there is provided a kind of new 3D photocuring reaction modes, and polythiol and third can be passed through
The selection of the species of olefin(e) acid ester and proportioning control the hardness of material, intensity, toughness.
For a further understanding of the present invention, technical scheme provided by the invention is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
Embodiment
The raw material that the embodiment of the present invention uses is purchased in market.
Embodiment 1
A kind of mercaptan-alkene light-cured resin that can be applied to 3D printing, wherein each component mass percent are respectively：1,4-
Benzene dimethanethiol 13%, four (3- mercaptopropionic acids) pentaerythritol esters 12%, epoxy acrylate 15%, polyester acrylate
21%, bicyclopentadiene (methyl) acrylate 20%, hydroxy-ethyl acrylate 10%, dimethoxybenzoin 3%, nanometer titanium dioxide
Silicon 5%, ESCALOL 567 0.1%, defoamer 0.2%, wetting dispersing agent 0.3%, levelling agent 0.2%,
KH-560 coupling agents 0.2%.25 DEG C of whipping temp, mixing time 90min.
Embodiment 2
A kind of mercaptan-alkene light-cured resin that can be applied to 3D printing, wherein each component mass percent are respectively：Sulfydryl
Silicone oil 20%, four (3- mercaptobutyric acids) pentaerythritol esters 6%, polyoxyalkylene acrylate resin 15%, polyurethane acrylic resin 15%,
1,6- hexanediyl ester 30%, dimethoxybenzoin 5%, nano core shell rubber 8%, 2- hydroxyl -4- methoxyl group hexichol
Ketone 0.1%, defoamer 0.3%, wetting dispersing agent 0.3%, levelling agent 0.3%.30 DEG C of whipping temp, mixing time 60min.
Embodiment 3
A kind of mercaptan-alkene light-cured resin that can be applied to 3D printing, wherein each component mass percent are respectively：4,
The tri-thiol triazine 12.85% of 4 '-thiobis-benzenethiol 10%, 2,4,6-, polyester acrylate 20%, epoxy acrylate
15%, dipentaerythritol tetraacrylate 15%, 2- phenoxyethyl methacrylates 20%, 2- hydroxy-2-methyls -1-
Phenyl -1- acetone 4%, calcium carbonate superfine powder 2%, 2- hydroxyl -4- methoxyl group -5- sulfonic acid benzophenone 0.2%, defoamer 0.3%, profit
Hygroscopic water powder 0.3%, levelling agent 0.3%, fluorescent whitening agent 0.05%.40 DEG C of whipping temp, mixing time 90min.
Embodiment 4
A kind of mercaptan-alkene light-cured resin that can be applied to 3D printing, wherein each component mass percent are respectively：Four
(3- mercaptopropionic acids) pentaerythritol ester 20%, urethane acrylate 8%, epoxy acrylate 10%, polyester acrylate
20%, triethylene glycol diacrylate 15.7%, dipentaerythritol tetraacrylate 18%, 4- benzoyls -4 '-methyl two
Aralkyl sulfid 1%, dimethoxybenzoin 3%, nano silicon 3%, ESCALOL 567 0.2%, disappear
Infusion 0.3%, wetting dispersing agent 0.3%, levelling agent 0.3%, titanium white 0.2%.30 DEG C of whipping temp, mixing time 100min.
Table 1 below is the method according to embodiment 1, changes the mercaptan-alkene light-cured resin that each group distribution ratio obtains：
The performance of 1-9 of the embodiment of the present invention light-cured resins prepared is detected respectively, as a result as shown in table 2.
Mercaptan-alkene 3D printing light-cured resin performance test results prepared by the embodiment 1-9 of table 2
The result of the test provided from upper table can be seen that：
The product that the mercaptan-alkene light-cured resin that embodiment 1 obtains is prepared, there is the characteristics of high intensity, high rigidity.
The product that the mercaptan-alkene light-cured resin that embodiment 2 obtains is prepared, have high tenacity, low viscosity, high flexibility,
The characteristics of soft sense of touch, high impact.
The product that the mercaptan-alkene light-cured resin that embodiment 3 obtains is prepared, there is high rigidity, high intensity, excellent tough
The characteristics of property and impact strength, combination property is preferable.
The product that the mercaptan-alkene light-cured resin that embodiment 4 obtains is prepared, there is high tenacity, HI high impact, excellent hard
The characteristics of degree and impact strength.
The mercaptan-alkene light-cured resin that embodiment 5 obtains, because epoxy acrylic resin content is higher, resin viscosity compared with
Greatly.By the standby product of the resin-made, there is the characteristics of intensity is high, hardness is high, there is acceptable impact strength, but and embodiment
1-4 is compared to less better.
The mercaptan-alkene light-cured resin that embodiment 6 obtains, the reactive diluent containing higher proportion, the viscosity of resin compared with
It is low, but the higher intensity for causing material of monomer ratio substantially reduces.Simultaneously as the content of ultraviolet absorber is higher, the resin
The hardness of the product of preparation has declined.
The mercaptan-alkene light-cured resin that embodiment 7 obtains, the ratio of polythiol is higher, beyond preferred scope, the resin-made
The standby product degree of cross linking is higher, and polymer contains more ester linkage group, has high rigidity, high intensity, but toughness and impact
Intensity is relatively low.
The mercaptan-alkene light-cured resin that embodiment 8 obtains, the ratio of polythiol is relatively low, less than preferred scope, the resin-made
The standby product degree of cross linking is relatively low, and intensity, the hardness of material are relatively low.
The mercaptan-alkene light-cured resin that embodiment 9 obtains, the ratio of acrylic resin oligomer is higher, beyond preferred model
Enclose, the viscosity of the resin is higher, is unfavorable for printing shaping, has large effect for the precision of resin cured matter.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
- A kind of 1. mercaptan-alkene light-cured resin for 3D printing, it is characterised in that by polythiol, acrylic resin prepolymer, Reactive diluent, initiator, ultraviolet absorber, filler and auxiliary agent raw material are prepared.
- 2. a kind of mercaptan-alkene light-cured resin for 3D printing, it is characterised in that by polythiol 5-30 parts, acrylic resin Prepolymer 10-60 parts, reactive diluent 5-40 parts, initiator 0.1-10 parts, ultraviolet absorber 0.01-1 parts, filler 0.5-8 weights Part is measured, auxiliary agent 0.1-5 parts are prepared.
- 3. the mercaptan-alkene light-cured resin according to claim 1 or 2 for 3D printing, it is characterised in that：Described is more Mercaptan has general formula R-(S-H)n1, wherein R is the organic moiety for having chemical valence n, and n1 is at least 2；Described acrylic resin Prepolymer is epoxy acrylic resin, polyurethane acrylic resin, one in polyester acrylate resin and polyoxyalkylene acrylate resin Kind is a variety of.
- 4. the mercaptan-alkene light-cured resin for 3D printing described in claim 3, it is characterised in that：Described polythiol, its Middle R is that there is 1-30 carbon atom and optional 1-4 chains oxygen, the aliphatic of nitrogen or sulfur heteroatom, alicyclic, fragrant or alkyl to take The aryl moieties or siloxy group in generation.
- 5. the mercaptan-alkene light-cured resin according to claim 1 or 2 for 3D printing, it is characterised in that：Described work Property diluent is isobornyl acrylate, propylene N-butyl, 1,6- hexanediyl ester, polyethyleneglycol diacrylate, Cyclohexyl acrylate, trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, neck phthalic acid diethylene glycol two Acrylate, bisphenol-A diethylene glycol diacrylate, propoxylation trimethylolpropane trimethacrylate, pentaerythrite 3 third One or more in olefin(e) acid ester, tetrahydrofuran acrylate, the third oxidation neopentylglycol diacrylate or vinyl silicone oil.
- 6. the mercaptan-alkene light-cured resin according to claim 1 or 2 for 3D printing, it is characterised in that：Described draws Hair agent is styrax dimethyl ether (DMAP), 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl ketones, 2,4, 6- trimethylbenzoy-diphenies phosphine oxide and double (2,4,6 ,-trimethylbenzoyl) phenyl phosphine oxide 2,4- diethyl One or more in thioxanthone.
- 7. the mercaptan-alkene light-cured resin according to claim 1 or 2 for 3D printing, it is characterised in that：Described purple Outer absorbent includes the just new epoxide benzophenone of 2- hydroxyls -4, ESCALOL 567, and 2- hydroxyl -4- methoxyl groups - 5- sulfonic acid benzophenone, 2- (2 '-hydroxyl -5 '-t-octyl phenyl) BTAs and double (2,2,6,6- pentamethyl -4- piperidyls) last of the ten Heavenly stems One or more in two acid esters.
- 8. the mercaptan-alkene light-cured resin according to claim 1 or 2 for 3D printing, it is characterised in that：Described fills out Material includes calcium carbonate superfine powder, superfine silicon dioxide, the one or more in talcum powder and nano core shell rubber.
- 9. the mercaptan-alkene light-cured resin according to claim 1 for 3D printing, it is characterised in that：Described auxiliary agent Including the one or more in coupling agent, fluorescent whitening agent, levelling agent, defoamer, wetting dispersing agent and pigment.
- 10. the preparation method of a kind of mercaptan-alkene light-cured resin for 3D printing, it is characterised in that including step：By the polythiol described in claim 1,2,4-9 any claims, acrylic resin prepolymer, reactive diluent, draw Hair agent, ultraviolet absorber, filler, auxiliary agent are mixed in mass ratio, and high-speed stirred 30-120 minutes, are used at 20-50 DEG C The mercaptan-alkene light-cured resin of 3D printing.
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| CN108822261A (en) * | 2018-07-16 | 2018-11-16 | 河源然生新材料有限公司 | A kind of UV photocuring light-sensitive material for DLP rapid shaping desktop grade equipment |
| CN109111554A (en) * | 2018-07-25 | 2019-01-01 | 浩力森涂料（上海）有限公司 | A kind of wear-resistant vinyl silicone oil modified acrylic acid emulsion and preparation method thereof |
| CN109369857A (en) * | 2018-10-31 | 2019-02-22 | 深圳市诺瓦机器人技术有限公司 | A kind of photocuring toughened resin material and preparation method thereof |
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| CN107641200B (en) | 2020-12-15 |
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