CN106696258B - A kind of method of quick 3D printing - Google Patents
A kind of method of quick 3D printing Download PDFInfo
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- CN106696258B CN106696258B CN201611040841.0A CN201611040841A CN106696258B CN 106696258 B CN106696258 B CN 106696258B CN 201611040841 A CN201611040841 A CN 201611040841A CN 106696258 B CN106696258 B CN 106696258B
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- Prior art keywords
- epoxy
- acrylate
- quick
- photosensitive resin
- precursor liquid
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000010146 3D printing Methods 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 230000008961 swelling Effects 0.000 claims abstract description 20
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 11
- -1 functional group Compound Chemical class 0.000 claims description 11
- 239000005357 flat glass Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 229940093476 ethylene glycol Drugs 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- QDHUQRBYCVAWEN-UHFFFAOYSA-N amino prop-2-enoate Chemical class NOC(=O)C=C QDHUQRBYCVAWEN-UHFFFAOYSA-N 0.000 claims 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000010257 thawing Methods 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 description 36
- 206010042674 Swelling Diseases 0.000 description 18
- 239000004925 Acrylic resin Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 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
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VJMJYBVERHZATL-UHFFFAOYSA-N (2,4,6-trimethylbenzoyl)phosphonoyl-(2,4,6-trimethylphenyl)methanone Chemical class CC1=CC(C)=CC(C)=C1C(=O)P(=O)C(=O)C1=C(C)C=C(C)C=C1C VJMJYBVERHZATL-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N ethylene glycol diacrylate Substances C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100036045 Colipase Human genes 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 101000876022 Homo sapiens Colipase Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004870 Styrax Substances 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
- SAIXKCDRRZNGSO-UHFFFAOYSA-N [O].OCC(O)CO Chemical group [O].OCC(O)CO SAIXKCDRRZNGSO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a kind of methods of quick 3D printing, press default two-dimensional pattern using DLP projector and carry out multiple partial projection, exposure curing to photosensitive resin precursor liquid, obtain heterogeneous two-dimensional surface.It obtained heterogeneous two-dimensional surface will be solidified is soaked in the paraffin of thawing and be swollen, take out cooling；Or in photosensitive resin precursor liquid, take out, illumination curing, obtains three-dimensional structure.Not aqueous and volatile solvent in the three-dimensional structure that arbitrary structures in the present invention in swelling process can be fixed up, and obtain, it is practical.
Description
Technical field
The present invention relates to Polymer Processing manufacturing field more particularly to a kind of methods of quick 3D printing.
Background technique
Polymer product with three-dimensional structure is usually to pass through the method for mold moulding to be process.This tradition
Method can only often process some simple three-dimensional structures due to the limitation that mold is processed and the later period demoulds.Moreover, mold is opened
It sends out period length, put into big, low efficiency.
3D printing (increasing material manufacturing) is one kind based on digital model file, carrys out structure by layer-by-layer printing
The forming technique of body has been widely used for the direct manufacture of mold, the model manufacturing of industrial design and some products.3D printing
Technology is a kind of straight forming technology, is not needed using mold.In addition, its advantage most outstanding is can to construct some not advise
Then, complicated three-dimensional structure.But all 3D printing techniques (including fusion sediment FDM, selective Stereo Lithography SLA, number
Word light processing DLP, selective laser sintering SLS etc.) it requires for target object to be sliced, it prints layer by layer, so printing single object
Time needed for body is relatively long.When in particular for higher printing precision, need thickness thinner, the number of plies is more, printing
Time is also just longer.Although the CLPS technology of Carbon company substantially increases the print speed of conventional DLP technology, but it is absolutely
Speed is still relatively slow.
Chinese invention patent (105818382 A of CN) discloses a kind of side based on digital light processing building three-dimensional structure
Method, this method passes through digitized projection technology first and prints to obtain the heterogeneous two-dimensional surface accurately controlled, then by this
Two-dimensional surface is immersed in specific solvent and is swollen, and a preset three-dimensional structure can be obtained.The skill that the patent discloses
Art principle is there is the distribution density of substance and gradient inside heterogeneous two-dimensional surface, and different zones are to the molten of homogeneous solvent
Expansibility is different, just will form a stable three-dimensional structure when reaching swelling equilibrium.The patent greatly improves 3D printing
Speed, but there is also some limitations: needing just obtain a stable structure, swelling process until complete swelling balance
In some intermediaries to come in handy can not be fixed up；The solvent used is water or volatile organic solvent, limit
It is made in the application of specific occasion.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of method of quick 3D printing, when swelling without
It need to wait until that complete swelling balances, can retain useful intermediary, and solvent used is aqueous or volatile organic solvent,
The three-dimensional structure for obtaining it has bigger use scope and practical value.
Technical solution provided by the present invention are as follows:
A kind of method of quick 3D printing, includes the following steps:
Step (1): the photosensitive resin precursor liquid comprising monomer and photoinitiator is placed in plane die cavity；
Step (2): using DLP projector press default two-dimensional pattern to photosensitive resin precursor liquid carry out multiple partial projection,
Exposure curing obtains heterogeneous two-dimensional surface；
Step (3): will solidify obtained heterogeneous two-dimensional surface and be soaked in the paraffin of thawing and be swollen, and take out, cooling, i.e.,
It can get three-dimensional structure；
It is swollen, takes out alternatively, heterogeneous two-dimensional surface is soaked in photosensitive resin precursor liquid, illumination curing can obtain
Obtain three-dimensional structure.
Innovative point of the invention is the solvent for using the paraffin of thawing or photosensitive resin precursor liquid to be swollen as two-dimensional surface,
To generate and patent 201610239890.0 entirely different mechanism and effect.
The present invention obtains the heterogeneous two-dimensional surface accurately controlled by digitized projection technology, due to flat in two dimension
The swelling rate of the different zones in face is different, until the two-dimensional surface can be converted into preset three-dimensional structure when swelling equilibrium,
And any one intermediary in swelling process can be fixed.When making solvent using the paraffin of thawing,
As long as any stage of swelling process takes out sample, paraffin is cooling at room temperature, solidifies, under capable of fixing three-dimensional structure
Come；When making solvent using photosensitive resin precursor liquid, after at any time taking out sample, specific absorption wavelength is placed it in
Can also three-dimensional structure be fixed up by sufficiently solidifying under light source.
The committed step of the method for the present invention be using DLP projector to photosensitive resin carry out multiple selective area projection,
Exposure makes different zones have different substance distribution gradients；Determine that resin is complete by the kinetics of polymerization reaction of photosensitive resin
Projection time required for all solidstate pushes away its swellbility required in two-dimensional surface point according to final required three-dimensional structure is counter
Cloth, so that it is determined that the figure of the time and projection that project every time.
In the present invention, DLP projector is connected by G code with computer, launches out specific X-Y scheme to photosensitive tree
Rouge forerunner's liquid level.Photosensitive resin generation polymerization reaction and crosslinking curing at projection.The single projection time is controlled, so that single is thrown
Photosensitive resin polymerization reaction is incomplete under shadow, and crosslinking curing is insufficient, i.e. the conversion ratio of photosensitive resin under this projection and crosslinking
Density is lower.DLP projector carries out reprojection, and the photosensitive resin of (repeat region of multiple projections pattern) is further at projection
Polymerization reaction occurs, monomer conversion is gradually increased with crosslink density.Projection, photocuring operation repeat repeatedly, until poly-
Close fully reacting.The process of multiple projections includes at least two kinds of different graphics (view field of different graphic can be overlapped),
So that finally obtained two-dimensional surface includes at least the region of two kinds of differentiated yields and crosslink density.
In the present invention, photosensitive resin precursor liquid described in step (1) and step (3) includes monomer and photoinitiator.
Monomer contains active function groups, can be under light illumination by photoinitiator initiated polymerization.At least one in monomer
A component includes two or more active function groups, so that polymeric acceptor forms cross-linked structure.
Preferably, the monomer of photosensitive resin precursor liquid described in step (1) and step (3) be acrylate monomer or
Epoxy monomer；
In the acrylate monomer, at least containing there are two acrylate-based functional groups；
In the epoxy monomer, at least containing there are two epoxy-functionals.
In the acrylate monomer, including at least a kind of compound acrylate-based containing two or more；It is described
Epoxy monomer in, including at least a kind of compound containing two or more epoxy-functional.
The active function groups of the acrylate monomer are acrylate-based, photoinitiator initiation monomer progress free radical
Polymerization reaction.The active function groups of the epoxy monomer be epoxy-functional, photoinitiator cause epoxy monomer carry out sun from
Sub- polymerization reaction.
Preferably, the acrylate monomer be selected from polyethyleneglycol diacrylate, ethyleneglycol dimethyacrylate,
One of epoxy acrylic resin, polyurethane acrylic resin, polyester acrylate resin and amino acrylic resin are a variety of；
The epoxy monomer is one or more of bisphenol-A epoxy, Bisphenol F epoxy, alicyclic epoxy.
Cited acrylate monomer and epoxy monomer contains two or more active function groups, itself can occur
Crosslinking.Wherein, epoxy acrylic resin, polyurethane acrylic resin, polyester acrylate resin and amino acrylic resin are pre-
Polymers.
Further preferably, the acrylate monomer is selected from polyethyleneglycol diacrylate and/or methacrylate second
Diol ester.
For the mechanical property of resin after adjusting photosensitive resin precursor liquid viscosity and crosslinking curing, above-mentioned acrylate monomer
In, it also include (methyl) acrylate of mono acrylic ester base functional group.
It include an acrylate-based functional group in described (methyl) acrylate, preferably, (methyl)
The structural formula of acrylate is as shown in Equation 1:
Wherein, R1For methyl or hydrogen, R2For the alkyl of 1-20 carbon atom.
Further preferably, (methyl) acrylate is preferably methyl methacrylate, methyl acrylate, methacrylic acid second
Ester, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-ethyl hexyl acrylate, methacrylic acid
Certain herbaceous plants with big flowers ester, acrylic acid certain herbaceous plants with big flowers ester, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, isobomyl acrylate
One of ester, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate and hydroxypropyl acrylate are more
Kind.
(methyl) acrylate of the acrylate-based functional group accounts for the 60-95% of acrylate monomer weight.It can
Think that the acrylate of single active function groups accounts for the 60-95% of the heavy amount of acrylate monomer.
Further preferably, (methyl) acrylate of the acrylate-based functional group accounts for acrylate monomer weight
80-90%.
Further preferably, the epoxy monomer is selected from novolac epoxy resin, diglycidyl ethers of bisphenol-A, two ring of Bisphenol F
It is oxygen glycerin ether, four Synthesis of Oligo Ethylene Glycol of pentaerythrite, tetrabromobisphenol A diglycidyl ether, 1,6- hexylene glycol diglycidyl ether, double
Phenol A polyethylene glycol diglycidyl ether, epoxidation polyunsaturated fatty acid and epoxidized vegetable oil it is one or more.
In above-mentioned epoxy monomer, the epoxy active diluent for further including mono-epoxy-functional (includes one epoxy functionalized
Group).The epoxy active diluent is the low molecular compound of a kind of one epoxy group of band.Preferably, the epoxy
Reactive diluent is one of butyl glycidyl ether, phenyl glycidyl ether, acrylic glycidol ether or a variety of.
The epoxy active diluent accounts for the 60-95% of epoxy monomer weight.It is believed that the epoxy of single active function groups
Compound accounts for the 60-95% of the heavy amount of epoxy monomer.
Further preferably, epoxy active diluent accounts for the 80-90% of epoxy monomer weight.
In step (1), selected according to the difference of polymerization reaction type (Raolical polymerizable, cationic polymerization)
Adaptable photoinitiator.
The photoinitiator that the acrylate monomer uses is free radical photo-initiation；What the epoxy monomer monomer used
Photoinitiator is cation light initiator；Photoinitiator mass fraction shared in photosensitive resin precursor liquid is 0.1-
5%.
Free radical photo-initiation is selected from benzoin and derivative, benzil class, alkylbenzene ketone, acyl group neighbour oxide, two
Benzophenone class and thioxanthones it is one or more；Cation light initiator be selected from diaryl iodonium salt, triaryl salt compounded of iodine,
One or more of alkyl salt compounded of iodine, isopropylbenzene cyclopentadienyl iron hexafluorophosphate.
Further preferably, free radical photo-initiation is selected from styrax, benzoin dimethylether, diphenylethan, dimethoxy
Phenyl acetophenone, hydroxyalkyl phenones, aroyl phosphorous oxides, benzophenone, 2,4-DihydroxyBenzophenone and thio propoxyl group
One of thioxanthone is a variety of.
Preferably, initiator mass fraction shared in photosensitive resin precursor liquid is 0.2-1%.
In the present invention, be used to be swollen heterogeneous two-dimensional surface described in step (3) is the paraffin melted or photosensitive tree
Rouge precursor liquid.
Preferably, the temperature of the paraffin of thawing described in step (3) is 45-65 DEG C.
Melting point of paraffin wax is different according to trade mark difference, need to only be heated to fusing point in 45-65 DEG C of range, use
Above melt can be used.
Photosensitive resin precursor liquid can directly be selected from the formula in step (1), can also separately prepare.
Preferably, the plane die cavity is formed by two parallel sheet glass by the way that gasket is closely sealed, between two sheet glass
Spacing be 0.5-5mm.
The thickness of plane mould will affect projection, curing efficiency.Preferably, the plane die cavity is by parallel two panels
Glass is formed by the way that gasket is closely sealed, and the spacing between two sheet glass is 0.5-5mm.
Spacing between glass it is also contemplated that photosensitive resin precursor liquid plane mould filling thickness.
In step (2), using DLP projector in step (1) photosensitive resin precursor liquid carry out partial projection, exposure,
Solidification, the pattern of projection are transmitted to DLP projector by the CAD model of CAD；Step (2) circulation carries out at least two
Secondary, the pattern projected every time is different.
The method of digitized projection technology building three-dimensional structure proposed by the present invention, final three-dimensional structure are flat by two dimension
What the different conversion ratio of face different zones and crosslink density determined.Its conversion ratio of the region exposed repeatedly by multiple projections and crosslinking
Density is higher, on the contrary then low.So key of the invention is that photosensitive resin is fully cured to the required time to be divided into several segments,
The different region of projection in every time.
The DLP projector of DLP projector commodity in use in the present invention.
Preferably, the optical source wavelength of DLP projector described in step (2) is 200-700nm.
Preferably, the DLP projector single projection time described in step (2) is 0.5-5s.
In the power and the photosensitive resin precursor liquid coordinated, polymerization reaction efficiency is improved, shortens 3D structure structure
Build the time.
The light source in the light source displacement DLP projector of the ultraviolet band less than 400nm can also be used in DLP projector.
Compared with prior art, the beneficial effects of the present invention are embodied in:
(1) method of quick 3D printing provided by the present invention is carried out using the paraffin or photosensitive resin precursor liquid of thawing
When swelling, the arbitrary structures in swelling process can be all fixed up.
(2) method of quick 3D printing provided by the present invention, not aqueous and volatile solvent in obtained three-dimensional structure,
It is practical.
Detailed description of the invention
Fig. 1 is digitized projection equipment and schematic device；
Fig. 2 is gained three-dimensional structure pictorial diagram after 1 two-dimensional surface of embodiment and swelling；
Fig. 3 is gained three-dimensional structure pictorial diagram after 2 two-dimensional surface of embodiment and swelling；
Fig. 4 is gained three-dimensional structure pictorial diagram after 3 two-dimensional surface of embodiment and swelling.
Specific embodiment
The present invention will be further described with reference to embodiments, but the scope of protection of present invention is not limited to reality
Apply the range of example expression.
As shown in Figure 1, digitized projection equipment and device that the present invention uses include computer 1,2 peace of DLP projector
Face mould tool；Plane mould includes two sheet glass 3 and gasket 4, and two sheet glass 3 enclose (closely sealed) into plane die cavity by gasket 4, put down
Face mould is intracavitary to be filled with photosensitive resin precursor liquid 5.
DLP projector 2 is connected by G code with computer 1, the pattern of projection by 1 Computer Aided Design of computer CAD model
It is transmitted to DLP projector 2；It is repeatedly projected to 5 surface of photosensitive resin precursor liquid by 2 part of DLP projector, is carried out local, more
Secondary solidification.After the completion of solidification, paraffin or photosensitive tree of the obtained photosensitive resin (heterogeneous two-dimensional surface) in thawing will be solidified
It is swollen in rouge precursor liquid, obtains three-dimensional structure.
Embodiment 1
Photosensitive resin precursor liquid raw material:
Lauryl acid esters (HLA): Sigma-Aldrich company；
Ethylene glycol diacrylate methyl esters (EGDMA), Sigma-Aldrich company；
Bis- (2,4,6- trimethylbenzoyl) phosphine oxides (Irgacure 819) of phenyl: Sigma-Aldrich company；
By monomer, (mass fraction HLA:EGDMA=1:0.01, Irgacure 819 are in photosensitive resin forerunner by a certain percentage
Shared mass fraction is 0.5% in liquid.) be uniformly mixed, precursor liquid is being introduced into the plane that two sheet glass are constituted with syringe
Among mold (thickness 1mm), then the sample of preparation is placed in below projector lens at 15cm.
Circulation projection, exposure and solidification: DLP projection are carried out using digitized projection equipment and device figure illustrated in Figure 1
The wave band that instrument light source issues is 400-700nm, and the single projection time is 2s, and each projecting figure is accumulated as following two-dimensional surface and shows
It is intended to (see Fig. 2 (a)), color is deeper, and the more i.e. light application times of representative projection number are longer.
Swelling: the two-dimensional surface film (shown in such as Fig. 2 (b)) after projection is solidified is transferred in the paraffin of thawing, temperature 70
DEG C, make its swelling, is taken out in swelling process, it is cooling, it obtains shown in stable three-dimensional structure such as Fig. 2 (c)；Thawing is placed it in again
Paraffin in continue to be swollen, shown in final stable three-dimensional structure such as Fig. 2 (d).
Embodiment 2
Photosensitive resin precursor liquid raw material:
Hydroxy-ethyl acrylate (HEA): Sigma-Aldrich company；
Ethylene glycol diacrylate methyl esters (EGDMA): Sigma-Aldrich company；
Bis- (2,4,6- trimethylbenzoyl) phosphine oxides (Irgacure 819) of phenyl: Sigma-Aldrich company；
Monomer is mixed by a certain percentage (mass fraction HEA:EGDMA:Irgacure 819=1:0.2:0.005)
It is even, precursor liquid is being introduced among the plane mould (thickness 1mm) that two sheet glass are constituted with syringe, then by the sample of preparation
It is placed in below projector lens at 15cm.
Shown in two-dimensional surface schematic diagram such as Fig. 3 (a) of projection exposure, shown in obtained two-dimensional surface such as Fig. 3 (b), by it
Be placed in the precursor liquid in this example and be swollen, be deformed into shown in three-dimensional structure such as Fig. 3 (c), take out, be placed in ultra-violet curing case make it is molten
The swollen precursor liquid entered is fully cured, and three-dimensional structure is stablized.
Embodiment 3
Photosensitive resin precursor liquid raw material:
Polyglycols 2-glycidyl ether resin (DER732): Sigma-Aldrich company；
Ethyl acetate (EA): Sinopharm Chemical Reagent Co., Ltd.；
4- isobutyl phenenyl -4- aminomethyl phenyl iodine hexafluorophosphate (Irgacure 250): You Yang Science and Technology Ltd.；
Monomer is mixed by a certain percentage (mass fraction DER732:EGDMA:Irgacure 819=1:0.01:0.005)
Uniformly, precursor liquid is being introduced among the plane mould (thickness 1mm) that two sheet glass are constituted with syringe, then by the sample of preparation
Product are placed in below projector lens at 15cm.
Shown in two-dimensional surface schematic diagram such as Fig. 4 (a) of projection exposure, obtained two-dimensional surface places it in photosensitive resin
In precursor liquid (HEA:EGDMA:Irgacure 819=1:0.1:0.01), it is deformed into shown in three-dimensional structure such as Fig. 4 (b), takes out,
The precursor liquid that being placed in ultra-violet curing case makes swelling enter is fully cured, and three-dimensional structure is stablized.
Claims (8)
1. a kind of method of quick 3D printing, which comprises the steps of:
Step (1): the photosensitive resin precursor liquid comprising light reaction compound and photoinitiator is placed in plane die cavity；
Step (2): default two-dimensional pattern is pressed using DLP projector, multiple partial projection, exposure are carried out to photosensitive resin precursor liquid
Solidification, obtains heterogeneous two-dimensional surface；
Step (3): heterogeneous two-dimensional surface being soaked in photosensitive resin precursor liquid and is swollen, and is taken out any one in swelling process
A intermediary, illumination curing can be obtained three-dimensional structure.
2. the method for quick 3D printing according to claim 1, which is characterized in that described in step (1) and step (3)
The light reaction compound of photosensitive resin precursor liquid is for the compound containing acrylate-based functional group or containing epoxy-functional
Compound；
In the compound containing acrylate-based functional group, at least containing there are two acrylate-based functional groups；
In the compound containing epoxy-functional, at least containing there are two epoxy-functionals.
3. the method for quick 3D printing according to claim 2, which is characterized in that described containing acrylate-based functional group
Compound is selected from polyethyleneglycol diacrylate, ethyleneglycol dimethyacrylate, epoxy acrylate, polyurethane acroleic acid
One of ester, polyester acrylate and amino acrylates are a variety of；
The compound containing epoxy-functional is one or more of bisphenol-A epoxy, Bisphenol F epoxy and alicyclic epoxy.
4. the method for quick 3D printing according to claim 2, which is characterized in that described containing acrylate-based functional group
It also include (methyl) acrylate of mono acrylic ester base functional group in compound；
It also include the epoxy active diluent of mono-epoxy-functional in the compound containing epoxy-functional.
5. the method for quick 3D printing according to claim 2, which is characterized in that described containing acrylate-based functional group
The photoinitiator that compound uses is free radical photo-initiation；The photoinitiator that the compound containing epoxy-functional uses for
Cation light initiator；Photoinitiator mass fraction shared in photosensitive resin precursor liquid is 0.1-5%.
6. the method for quick 3D printing according to claim 1, which is characterized in that DLP projector described in step (2)
Optical source wavelength is 200-700nm.
7. the method for quick 3D printing according to claim 1, which is characterized in that the plane die cavity is by parallel two
Sheet glass is formed by the way that gasket is closely sealed, and the spacing between two sheet glass is 0.5-5mm.
8. the method for quick 3D printing according to claim 1, which is characterized in that DLP projector list described in step (2)
Secondary projection time is 0.5-5s.
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| CN108786482A (en) * | 2018-06-05 | 2018-11-13 | 福州大学 | A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique |
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| CN204936221U (en) * | 2015-09-10 | 2016-01-06 | 杜晖 | A kind of photosensitive resin 3D printer that is light source with LED array battle array |
| CN105818382A (en) * | 2016-04-15 | 2016-08-03 | 浙江大学 | Method for constructing three-dimensional structure based on digital light processing |
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| KR101647799B1 (en) * | 2015-04-29 | 2016-08-11 | 주식회사 메이커스에스아이 | Cartridge for digital light processing type 3d printer |
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| CN204936221U (en) * | 2015-09-10 | 2016-01-06 | 杜晖 | A kind of photosensitive resin 3D printer that is light source with LED array battle array |
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