TWI654246B - Biodegradable and light-cured composition for three dimensional printing - Google Patents
Biodegradable and light-cured composition for three dimensional printingInfo
- Publication number
- TWI654246B TWI654246B TW105109677A TW105109677A TWI654246B TW I654246 B TWI654246 B TW I654246B TW 105109677 A TW105109677 A TW 105109677A TW 105109677 A TW105109677 A TW 105109677A TW I654246 B TWI654246 B TW I654246B
- Authority
- TW
- Taiwan
- Prior art keywords
- biodegradable
- photopolymerizable
- dimensional printing
- weight percentage
- inorganic compound
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 238000010146 3D printing Methods 0.000 title abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 18
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 18
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 229920002988 biodegradable polymer Polymers 0.000 abstract description 10
- 239000004621 biodegradable polymer Substances 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 2
- -1 Substituted alkoxy decane Chemical compound 0.000 description 23
- 239000000654 additive Substances 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 12
- 239000006081 fluorescent whitening agent Substances 0.000 description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 7
- WSFJFIDCQBAQQZ-UHFFFAOYSA-N hydroxy(sulfido)phosphanium Chemical compound S[PH2]=O WSFJFIDCQBAQQZ-UHFFFAOYSA-N 0.000 description 6
- 244000028419 Styrax benzoin Species 0.000 description 5
- 235000000126 Styrax benzoin Nutrition 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 description 5
- 229960002130 benzoin Drugs 0.000 description 5
- 235000019382 gum benzoic Nutrition 0.000 description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 5
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229930006711 bornane-2,3-dione Natural products 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 2
- QZOPRMWFYVGPAI-UHFFFAOYSA-N 1-chloroindole Chemical compound C1=CC=C2N(Cl)C=CC2=C1 QZOPRMWFYVGPAI-UHFFFAOYSA-N 0.000 description 2
- BVQVLAIMHVDZEL-UHFFFAOYSA-N 1-phenyl-1,2-propanedione Chemical compound CC(=O)C(=O)C1=CC=CC=C1 BVQVLAIMHVDZEL-UHFFFAOYSA-N 0.000 description 2
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 2
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 2
- VDMLVOIDGSOUTA-UHFFFAOYSA-N 2-(4-methylanilino)ethane-1,1-diol Chemical compound CC1=CC=C(NCC(O)O)C=C1 VDMLVOIDGSOUTA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 2
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OJNNAJJFLWBPRS-UHFFFAOYSA-N phenyl-[(2,4,6-trimethylphenyl)methyl]-[(2,4,6-trimethylphenyl)methylidene]phosphanium Chemical compound CC1=C(C=P(C2=CC=CC=C2)=CC2=C(C=C(C=C2C)C)C)C(=CC(=C1)C)C OJNNAJJFLWBPRS-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- MUQNAPSBHXFMHT-UHFFFAOYSA-N tert-butylhydrazine Chemical compound CC(C)(C)NN MUQNAPSBHXFMHT-UHFFFAOYSA-N 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RMNVDNOYWCSVEX-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(C)=O)=O.C1(=CC=CC=C1)C(C(C)=O)=O Chemical compound C1(=CC=CC=C1)C(C(C)=O)=O.C1(=CC=CC=C1)C(C(C)=O)=O RMNVDNOYWCSVEX-UHFFFAOYSA-N 0.000 description 1
- QUWWDXJGKGOTGR-UHFFFAOYSA-N CC(C[PH2]=O)CC(C)(C)C.COC1=C(C(=O)N)C(=CC=C1)OC.COC1=C(C(=O)N)C(=CC=C1)OC Chemical compound CC(C[PH2]=O)CC(C)(C)C.COC1=C(C(=O)N)C(=CC=C1)OC.COC1=C(C(=O)N)C(=CC=C1)OC QUWWDXJGKGOTGR-UHFFFAOYSA-N 0.000 description 1
- NNOBDPRMXWPAJP-UHFFFAOYSA-N COC1=C(C=C(C(C([PH2]=O)=CC2=C(C=CC=C2OC)OC)C)C(C)(C)C)C(=CC=C1)OC Chemical compound COC1=C(C=C(C(C([PH2]=O)=CC2=C(C=CC=C2OC)OC)C)C(C)(C)C)C(=CC=C1)OC NNOBDPRMXWPAJP-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 101001116774 Homo sapiens Methionine-R-sulfoxide reductase B2, mitochondrial Proteins 0.000 description 1
- 102100024862 Methionine-R-sulfoxide reductase B2, mitochondrial Human genes 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 101100099821 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cbs-1 gene Proteins 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本發明揭露一種用於三維列印之生物可分解的光聚合組合物，主要包括有以下重量百分比含量的材料：70~90%的一光聚合樹脂及重量百分比大於0且上限為20%的一無機化合物，其中，所述之光聚合樹脂為具有丙烯酸酯官能基之可光聚合的生物可分解聚合物，又，無機化合物可再與一矽烷交聯劑進行矽烷化反應，本發明之光聚合組合物因使用小分子量之光聚合樹脂，其於室溫下為液體狀態，有利於作為三維列印時所需的光固化材料。 The invention discloses a biodegradable photopolymerizable composition for three-dimensional printing, which mainly comprises a material having the following content by weight: 70-90% of a photopolymer resin and a weight percentage greater than 0 and an upper limit of 20% An inorganic compound, wherein the photopolymerizable resin is a photopolymerizable biodegradable polymer having an acrylate functional group, and further, the inorganic compound can be further subjected to a decane reaction with a monodecane crosslinking agent, and the photopolymerization of the present invention The composition is a liquid state at room temperature due to the use of a small molecular weight photopolymerizable resin, which is advantageous as a photocurable material required for three-dimensional printing.
Description
一種以具有丙烯酸酯官能基之可光聚合的生物可分解聚合物作為主體材料的用於三維列印之生物可分解的光聚合組合物。 A biodegradable photopolymerizable composition for three-dimensional printing using a photopolymerizable biodegradable polymer having an acrylate functional group as a host material.
三維列印(3D-Printing)技術為一種快速成型(Rapid Prototyping)技術，其技術種類相當多元，包括如熔融沉積成型技術(Fused Deposition Modeling，FDM)、分層實體製造技術(Laminated Object Manufacturing，LOM)與立體光固化成型技術(Stereolithography，SLA)等，其中，立體光固化成型技術的技術原理是用特定波長與強度的“光”聚焦到“光固化材料”的表面，從而完成單層材料的圖形化，因其具有成型速度較快的優點，故而被廣泛使用，又，在講求環保觀念的現代，生物可分解聚合物(Biodegradable polymer，或稱生物降解聚合物)常被用來做為光固化材料的材料，如中國發明專利公告案第CN103923470B號「一種用於3d打印的生物可降解材料」，便揭露一種包括由20~45%的丙烯酸食品膠衍生物、10~40%的丙烯酸松香衍生物、 5~10%的月桂酸丙烯酸酯、5~15%的超細碳酸鈣、1-8%的乙烯基矽烷交聯劑、20-50%的羥基丙烯酸酯以及1~5%的光引髮劑所組成之用於3d打印的生物可降解材料，其材料的光降解率最高可達到95%，亦可參閱以下其他專利前案：(1)中華民國發明專利公告案第I480293B號「光硬化性樹脂及光硬化性樹脂組成物」；(2)中國發明專利公開案第CN103665802A號「一種用於3d打印的聚乳酸材料及其製備方法」；(3)中國發明專利公開案第CN103980682A號「一種用於3d打印的聚己內酯材料及其製備方法」。 3D-Printing technology is a Rapid Prototyping technology with a wide variety of technologies, including Fused Deposition Modeling (FDM) and Laminated Object Manufacturing (LOM). And Stereolithography (SLA), etc., in which the technical principle of stereoscopic curing technology is to focus on the surface of the "photocurable material" with "light" of specific wavelength and intensity, thereby completing the single layer material. Graphical, because it has the advantage of faster forming speed, it is widely used, and in modern, biodegradable polymer (biodegradable polymer) is often used as light. The material of the solidified material, such as the Chinese Patent Publication No. CN103923470B "a biodegradable material for 3d printing", discloses a rosin containing 10 to 45% of acrylic acid, 10 to 40% of acrylic rosin. derivative, 5~10% lauric acid acrylate, 5~15% ultrafine calcium carbonate, 1-8% vinyl decane crosslinker, 20-50% hydroxy acrylate and 1~5% photoinitiator The biodegradable material composed of 3d printing has a photodegradation rate of up to 95%. Please refer to the following other patents: (1) Republic of China Invention Patent Notice No. I480293B "Photocuring "Resin and photocurable resin composition"; (2) Chinese Patent Publication No. CN103665802A "a polylactic acid material for 3d printing and a preparation method thereof"; (3) Chinese Invention Patent Publication No. CN103980682A "A kind of Polycaprolactone material for 3d printing and its preparation method".
惟，細究上述諸多前案所揭露之用於三維列印的組合物，可發現其仍皆不利使用於三維列印的漿料之中，如多為大分子量之生物可分解聚合物，如要混合成三維列印用之漿料材料，仍必須與其他單體或是寡聚物材料進行混合才行，是以，亟需開發一種包括有小分子量聚合物的三維列印材料。 However, the compositions disclosed in the above-mentioned various previous examples for three-dimensional printing can be found to be disadvantageously used in three-dimensional printing pastes, such as biodegradable polymers of large molecular weight. The slurry material mixed into the three-dimensional printing must still be mixed with other monomer or oligomer materials, so that it is urgent to develop a three-dimensional printing material including a small molecular weight polymer.
有鑑於上述的問題，本發明人係依據多年來從事相關行業的經驗，針對現有的三維列印材料進行研究及分析，期能研發出較佳的三維列印材料；緣此，本發明之主要目的在於提供一種以具有丙烯酸酯官能基之可光聚合的 生物可分解聚合物，及未矽烷化或矽烷化的無機化合物作為主體材料，以利進行光聚合反應的用於三維列印之生物可分解的光聚合組合物。 In view of the above problems, the present inventors have researched and analyzed existing three-dimensional printing materials based on years of experience in related industries, and are able to develop better three-dimensional printing materials; thus, the main features of the present invention The object is to provide a photopolymerizable polymer having an acrylate functional group. A biodegradable polymer, and an unalkylated or decylated inorganic compound is used as a host material to facilitate photopolymerization of a biodegradable photopolymerizable composition for three-dimensional printing.
為達上述之目的，本發明之用於三維列印之生物可分解的光聚合組合物主要由重量百分比為70~90%的一光聚合樹脂、重量百分比大於0且上限為20%的一無機化合物。 For the above purposes, the biodegradable photopolymerizable composition for three-dimensional printing of the present invention is mainly composed of a photopolymerizable resin having a weight percentage of 70 to 90%, an inorganic component having a weight percentage greater than 0 and an upper limit of 20%. Compound.
其中，所述之光聚合樹脂為一種具有丙烯酸酯官能基的可光聚合的生物可分解聚合物。 Wherein the photopolymerizable resin is a photopolymerizable biodegradable polymer having an acrylate functional group.
其中，所述之無機化合物為羥基磷灰石(Hydroxyapatite，HA)、玻璃粉末如二氧化矽(SiO2)或二氧化鋯(ZrO2)、三氧礦化物(Mineral Trioxide Triaggrigate，MTA)，然不以此為限。 Wherein, the inorganic compound is hydroxyapatite (HA), glass powder such as cerium oxide (SiO 2 ) or zirconium dioxide (ZrO 2 ), and mineral trioxide triaggrim (MTA). Not limited to this.
其中，所述之無機化合物可再與一矽烷交聯劑進行矽烷化反應(Silanization)藉以作表面修飾，又，所述之矽烷交聯劑為矽烷之Si-H鍵的氫原子被烷氧基取代的烷氧基矽烷，如單烷氧基矽烷交聯劑(Monoalkoxysilane)、雙烷氧基矽烷交聯劑(Diaikoxysilane)或三烷氧基矽烷交聯劑(Monoalkoxysilane)，然不以此為限。 Wherein, the inorganic compound can be further subjected to a cerium grouping reaction by silanization, and the hydrogen atom of the Si-H bond of the decane cross-linking agent is alkoxy. Substituted alkoxy decane, such as Monoalkoxysilane, Diaikoxysilane or Monoalkoxysilane, but not limited thereto .
承上，本發明之用於三維列印之生物可分解的光聚合組合物除主要包括有重量百分比為70~90%的一光聚合樹脂、重量百分比大於0且上限為20%的一無機化合物外，可再包括有其他至少一種的添加劑。 The biodegradable photopolymerizable composition for three-dimensional printing of the present invention comprises, in addition to a photopolymerizable resin having a weight percentage of 70 to 90%, an inorganic compound having a weight percentage greater than 0 and an upper limit of 20%. In addition, there may be further included at least one other additive.
其中，所述之添加劑為光引發劑(Phtoinitiator)、螢光增白劑或顏色添加劑之其中一種或組合。 Wherein, the additive is one or a combination of a photoinitiator, a fluorescent whitening agent or a color additive.
其中，所述之光引發劑為苯偶姻化合物、苯乙酮化合物、蒽醌化合物、噻噸酮化合物、縮酮化合物、二苯基酮化合物或醯基膦氧化物，然不以此為限，具體而言，苯偶姻化合物包括如苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚；苯乙酮化合物包括如苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮；蒽醌化合物包括如2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌；噻噸酮化合物包括如2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙基噻噸酮；縮酮化合物包括如苯乙酮二甲基縮酮、芐基二甲基縮酮；二苯基酮化合物包括如二苯基酮、4-苯甲醯基二苯硫醚、4-苯甲醯基-4'-甲基二苯硫醚、4-苯甲醯基-4'-乙基二苯硫醚、4-苯甲醯基-4'-丙基二苯硫醚；醯基膦氧化物包括如2,4,6-三甲基苯甲醯基二苯膦氧化物(簡稱TPO)、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基膦氧化物，於較佳實施例下，本發明之光引發劑係為醯基膦氧化物的2,4,6-三甲基苯甲醯基二苯膦氧化物。 Wherein, the photoinitiator is a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a diphenylketone compound or a mercaptophosphine oxide, but not limited thereto Specifically, the benzoin compound includes, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone compounds include, for example, acetophenone, 2,2-dimethoxy 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; anthracene compounds including, for example, 2-methylindole, 2 -ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole; thioxanthone compounds including, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 - chlorothioxanthone, 2,4-diisopropylthioxanthone; ketal compounds including, for example, acetophenone dimethyl ketal, benzyl dimethyl ketal; diphenyl ketone compounds including, for example, diphenyl Ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylidene-4'-ethyldiphenyl sulfide, 4-benzene Mercapto-4'-propyldiphenyl sulfide; mercaptophosphine oxides include, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide ( Abbreviated as TPO), bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-tri Methyl amylphosphine oxide. In a preferred embodiment, the photoinitiator of the present invention is 2,4,6-trimethylbenzimidyl diphenylphosphine oxide which is a mercaptophosphine oxide.
其中，所述之光引發劑亦可為樟腦酮(Camphorquinone，CQ)、1-苯基-1,2-丙二酮(1-phenyl 1,2-propanedione，PPD)、4-二甲氨基苯甲酸乙酯 (Ethyl-4-4dimethylaminobenzoate，EDAB或EDMAB)、二羥乙基-對甲基苯胺(Dihydroxyethyl-p-toluidine)或甲基丙烯酸二甲氨基乙酯(2-(Dimethylamino)ethyl methacrylate)。 The photoinitiator may also be Camphorquinone (CQ), 1-phenyl 1,2-propanedione (PPD), 4-dimethylaminobenzene. Ethyl formate (Ethyl-4-4dimethylaminobenzoate, EDAB or EDMAB), Dihydroxyethyl-p-toluidine or 2-(Dimethylamino)ethyl methacrylate.
其中，所述之螢光增白劑用以吸收紫外光並將其轉換為其他波長的光，其可為產品名稱為DOUBLE 127、DOUBLE CBS-1、DOUBLE KCB、DOUBLE KSN、DOUBLE OB、DOUBLE OB-1、DOUBLE OB-80、DOUBLE OB-90或螢光增白劑28(Fluorescent brightener 28)之其中一種，然不以此為限。於較佳實施例下，本發明之螢光增白劑係為產品名稱DOUBLETEX OB。 Wherein, the fluorescent whitening agent is used to absorb ultraviolet light and convert it into light of other wavelengths, which may be product names DOUBLE 127, DOUBLE CBS-1, DOUBLE KCB, DOUBLE KSN, DOUBLE OB, DOUBLE OB -1, DOUBLE OB-80, DOUBLE OB-90 or Fluorescent brightener 28, but not limited to this. In the preferred embodiment, the fluorescent whitening agent of the present invention is the product name DOUBLETEX OB.
其中，所述之顏色添加劑用以改變材料的顏色，如可為氧化鈦、氧化鐵或色膏，然不以此為限。 Wherein, the color additive is used to change the color of the material, such as titanium oxide, iron oxide or color paste, but not limited thereto.
為使 貴審查委員得以清楚了解本發明之目的、技術特徵及其實施後之功效，茲以下列各實施例，並搭配圖示進行說明，敬請參閱。 In order to give a clear understanding of the purpose, technical features and effects of the present invention, the following examples will be described with reference to the drawings.
本發明之用於三維列印之生物可分解的光聚合組合物主要由重量百分比為70~90%的一光聚合樹脂、重量百 分比大於0且上限為20%的一無機化合物所組成，除此之外，更可再包括有至少一種添加劑，其中，所述之添加劑為一光引發劑(Phtoinitiator)、一螢光增白劑或一顏色添加劑之其中一種或組合；於其中一個實施例下，本發明之用於三維列印之生物可分解的光聚合組合物，係為以下重量百分百含量的各材料所組成：(1)重量百分比為70~90%的光聚合樹脂；(2)重量百分比大於0且上限為20%的無機化合物；(3)重量百分比大於0且上限為5%的光引發劑；(4)重量百分比大於0且上限為5%的螢光增白劑；(5)重量百分比大於0且上限為10%的顏色添加劑。然而，乃僅為本發明之其中一個實施例，本發明之光聚合組合物亦可為不包含有螢光增白劑或顏色添加劑之添加劑，特先陳明。 The biodegradable photopolymerizable composition for three-dimensional printing of the present invention is mainly composed of a photopolymerized resin having a weight percentage of 70 to 90%, and a weight of one hundred The inorganic compound is composed of an inorganic compound having a ratio of more than 0 and an upper limit of 20%. In addition, at least one additive may be further included, wherein the additive is a photoinitiator (Phtoinitiator), a fluorescent whitening One or a combination of the agents or one color additive; in one embodiment, the biodegradable photopolymerizable composition for three-dimensional printing of the present invention is composed of the following materials having a weight percentage of 100%: (1) a photopolymerizable resin having a weight percentage of 70 to 90%; (2) an inorganic compound having a weight percentage greater than 0 and an upper limit of 20%; (3) a photoinitiator having a weight percentage greater than 0 and an upper limit of 5%; a fluorescent whitening agent having a weight percentage greater than 0 and an upper limit of 5%; (5) a color additive having a weight percentage greater than 0 and an upper limit of 10%. However, it is only one of the embodiments of the present invention, and the photopolymerizable composition of the present invention may also be an additive which does not contain a fluorescent whitening agent or a color additive.
承上，所述之光聚合樹脂為一種具有丙烯酸酯官能基的可光聚合的生物可分解聚合物，其係藉由一丙烯醯氯與聚酯類化合物的一生物可分解聚合物進行反應而得，具體而言，本發明之光聚合樹脂係具有以下結構式(I)：
承上，所述之重量百分比大於0且上限為20%的無機化合物為羥基磷灰石(Hydroxyapatite，HA)、玻璃粉末如二氧化矽(SiO2)或二氧化鋯(ZrO2)、三氧礦化物(Mineral Trioxide Triaggrigate，MTA)，然不以此為限，又，無機化合物可再與一矽烷交聯劑進行矽烷化反應(Silanization)藉以作表面修飾，經矽烷化作表面修飾後的無機化合物，如矽烷化羥基磷灰石，可用以增加粒子於光聚合樹脂中的分散能力、降低材料的黏稠度以及增加粒子與單體的鍵結能力，再者，所述之矽烷交聯劑為矽烷之Si-H鍵的氫原子被烷氧基取代的烷氧基矽烷，如單烷氧基矽烷交聯劑(Monoalkoxysilane)、雙烷氧基矽烷交聯劑(Dialkoxysilane)或三烷氧基矽烷交聯劑(Monoalkoxysilane)，然不以此為限。 The inorganic compound having a weight percentage greater than 0 and an upper limit of 20% is hydroxyapatite (HA), glass powder such as cerium oxide (SiO2) or zirconium dioxide (ZrO2), and trioxide. (Mineral Trioxide Triaggrigate, MTA), but not limited to this, in addition, the inorganic compound can be further subjected to silanization with a decane cross-linking agent for surface modification, and the surface-modified inorganic compound is decanolated. For example, decyl hydroxyapatite can be used to increase the dispersibility of the particles in the photopolymerization resin, reduce the viscosity of the material, and increase the bonding ability of the particles to the monomer. Further, the decane crosslinker is decane. The alkoxy decane in which the hydrogen atom of the Si—H bond is substituted by an alkoxy group, such as a monoalkoxysilane, a dialkoxysilane or a trialkoxy decane crosslink Monoalkoxysilane, but not limited to this.
承上，所述之重量百分比大於0且上限為5%的光引發劑在接受或吸收外界能量後會發生化學變化，分解為自由基或陽離子，從而引發本發明之光聚合樹脂進行聚合反應，光引發劑係為苯偶姻化合物、苯乙酮化合物、蒽醌化合物、噻噸酮化合物、縮酮化合物、二苯基酮化合物或醯基膦氧化物，然不以此為限；就苯偶姻化合物而言，可包括如苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚；就苯乙酮化合物而言，可包括如苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮；就蒽醌化合物而言，可包括如2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌；就噻噸酮化合物而言，可包括如2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙基噻噸酮；就縮酮化合物而言，可包括如苯乙酮二甲基縮酮、芐基二甲基縮酮；就二苯基酮化合物而言，可包括如二苯基酮、4-苯甲醯基二苯硫醚、4-苯甲醯基-4'-甲基二苯硫醌、4-苯甲醯基-4'-乙基二苯硫醚、4-苯甲醯基-4'-丙基二苯硫醚；就醯基膦氧化物而言，可包括如2,4,6-三甲基苯甲醯基二苯膦氧化物(簡稱TPO)、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基膦氧化物；又，光引發劑亦可為樟腦酮(Camphorquinone，CQ)、1-苯基-1,2-丙二酮(1-phenyl 1,2-propanedione，PPD)、4-二甲氨基苯甲酸乙酯 (Ethyl-4-4dimethylaminobenzoate，EDAB或EDMAB)、二羥乙基-對甲基苯胺(Dihydroxyethyl-p-toluidine)或甲基丙烯酸二甲氨基乙酯(2-(Dimethylamino)ethyl methacrylate)。在較佳實施例下，本發明之光引發劑係為醯基膦氧化物的2,4,6-三甲基苯甲醯基二苯膦氧化物。 According to the above, the photoinitiator having a weight percentage greater than 0 and an upper limit of 5% undergoes a chemical change after receiving or absorbing external energy, and is decomposed into a radical or a cation, thereby initiating polymerization of the photopolymerization resin of the present invention. The photoinitiator is a benzoin compound, an acetophenone compound, a hydrazine compound, a thioxanthone compound, a ketal compound, a diphenyl ketone compound or a mercaptophosphine oxide, but not limited thereto; In the case of a compound, it may include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; in the case of an acetophenone compound, it may include, for example, acetophenone, 2,2-di Methoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; in the case of a ruthenium compound, may include - methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole; in the case of thioxanthone compounds, may include, for example, 2,4-dimethyl thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; in the case of a ketal compound, may include, for example, acetophenone dimethyl ketal, benzyl Dimethyl ketal In the case of a diphenyl ketone compound, it may include, for example, diphenyl ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfonium, 4-benzylformamide Base-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide; in the case of mercaptophosphine oxides, may include, for example, 2,4,6-trimethyl Benzomidine diphenylphosphine oxide (TPO for short), bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzamide) -2,4,4-trimethylpentylphosphine oxide; in addition, the photoinitiator can also be Camphorquinone (CQ), 1-phenyl-1,2-propanedione (1-phenyl) 1,2-propanedione, PPD), ethyl 4-dimethylaminobenzoate (Ethyl-4-4dimethylaminobenzoate, EDAB or EDMAB), Dihydroxyethyl-p-toluidine or 2-(Dimethylamino)ethyl methacrylate. In a preferred embodiment, the photoinitiator of the present invention is 2,4,6-trimethylbenzimidyldiphenylphosphine oxide which is a mercaptophosphine oxide.
承上，所述之重量百分比大於0且上限為5%的螢光增白劑主要用以吸收紫外光，並將其轉換為其他波長的光，其可為產品名稱為DOUBLE 127、DOUBLE CBS-1、DOUBLE KCB、DOUBLE KSN、DOUBLE OB、DOUBLE OB-1、DOUBLE OB-80、DOUBLE OB-90或螢光增白劑28(Fluorescent brightener 28)之其中一種，然不以此為限。於較佳實施例下，本發明之螢光增白劑係為產品名稱DOUBLETEX OB。 The fluorescent whitening agent having a weight percentage greater than 0 and an upper limit of 5% is mainly used for absorbing ultraviolet light and converting it into light of other wavelengths, which may be the product name DOUBLE 127, DOUBLE CBS- 1. One of DOUBLE KCB, DOUBLE KSN, DOUBLE OB, DOUBLE OB-1, DOUBLE OB-80, DOUBLE OB-90 or Fluorescent brightener 28, but not limited thereto. In the preferred embodiment, the fluorescent whitening agent of the present invention is the product name DOUBLETEX OB.
承上，所述之重量百分比大於0且上限為10%的顏色添加劑主要用以改變材料的顏色，如可為氧化鈦、氧化鐵或色膏，然不以此為限。 The color additive having a weight percentage greater than 0 and an upper limit of 10% is mainly used to change the color of the material, such as titanium oxide, iron oxide or color paste, but not limited thereto.
綜上所述可知，本發明之用於三維列印之生物可分解的光聚合組合物主要由重量百分比為70~90%的一光聚合樹脂，以及重量百分比大於0且上限為20%的一無機化合物所組成，又，可再添加如重量百分比大於0且上限為5%的一光引發劑、重量百分比大於0且上限為5%的一螢光增白劑或
重量百分比大於0且上限為10%的一顏色添加劑之其中一種或其組合，其中，無機化合物可未經矽烷化或經矽烷化反應，又，光聚合樹脂係具有以下結構式(I)：
是以，本發明據以實施後，確實可達到本發明之目的，即提供一種以具有丙烯酸酯官能基之可光聚合的生物可分解聚合物，及未矽烷化或矽烷化的無機化合物作為主體材料，以利進行光聚合反應的用於三維列印之生物可分解的光聚合組合物。 Therefore, after the present invention is implemented, it is indeed achieved that the object of the present invention is to provide a photopolymerizable biodegradable polymer having an acrylate functional group, and an unalkylated or decylated inorganic compound as a main component. A biodegradable photopolymerizable composition for three-dimensional printing for the photopolymerization.
唯，以上所述者，僅為本發明之較佳之實施例而已，並非用以限定本發明實施之範圍；任何熟習此技藝者，在不脫離本發明之精神與範圍下所作之均等變化與修飾，皆應涵蓋於本發明之專利範圍內。 The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; any changes and modifications made by those skilled in the art without departing from the spirit and scope of the invention All should be covered by the patent of the present invention.
綜上所述，本發明之功效，係具有發明之「產業可利用性」、「新穎性」與「進步性」等專利要件；申請人爰 依專利法之規定，向 鈞局提起發明專利之申請。 In summary, the effects of the present invention are patents such as "industry availability," "novelty," and "progressiveness" of the invention; According to the provisions of the Patent Law, an application for an invention patent is filed with the bureau.
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| CN101213070A (en) | 2005-06-30 | 2008-07-02 | 维也纳科技大学 | Rapid replication process and radiation curable composition for use therein |
| CN103975014A (en) | 2011-10-03 | 2014-08-06 | 新特斯有限责任公司 | Thiol-ene Polymerization Using Vinyl Esters and Vinyl Carbonates |
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| CN101213070A (en) | 2005-06-30 | 2008-07-02 | 维也纳科技大学 | Rapid replication process and radiation curable composition for use therein |
| CN103975014A (en) | 2011-10-03 | 2014-08-06 | 新特斯有限责任公司 | Thiol-ene Polymerization Using Vinyl Esters and Vinyl Carbonates |
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