JP6657106B2 - 熱溶解フィラメント製法において使用するための支持体材料としてのポリマー - Google Patents
熱溶解フィラメント製法において使用するための支持体材料としてのポリマー Download PDFInfo
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- JP6657106B2 JP6657106B2 JP2016553433A JP2016553433A JP6657106B2 JP 6657106 B2 JP6657106 B2 JP 6657106B2 JP 2016553433 A JP2016553433 A JP 2016553433A JP 2016553433 A JP2016553433 A JP 2016553433A JP 6657106 B2 JP6657106 B2 JP 6657106B2
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- 239000000463 material Substances 0.000 title claims description 164
- 229920000642 polymer Polymers 0.000 title claims description 122
- 238000000034 method Methods 0.000 title claims description 78
- 239000012943 hotmelt Substances 0.000 title claims description 34
- 239000000178 monomer Substances 0.000 claims description 41
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 35
- 125000003118 aryl group Chemical group 0.000 claims description 25
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 24
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 21
- 230000009477 glass transition Effects 0.000 claims description 21
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 claims description 2
- -1 polyethylene Polymers 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- 229920001519 homopolymer Polymers 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000007928 solubilization Effects 0.000 description 9
- 238000005063 solubilization Methods 0.000 description 9
- 239000012815 thermoplastic material Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
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- 125000001424 substituent group Chemical class 0.000 description 7
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- 150000002431 hydrogen Chemical class 0.000 description 6
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- 125000004122 cyclic group Chemical group 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
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- 239000012778 molding material Substances 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 0 CN(*=O)C(*)=C(*)* Chemical compound CN(*=O)C(*)=C(*)* 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011960 computer-aided design Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 2
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000110 selective laser sintering Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- KAIHOCOWYAMXQY-OWOJBTEDSA-N (e)-3-cyanoprop-2-enoic acid Chemical compound OC(=O)\C=C\C#N KAIHOCOWYAMXQY-OWOJBTEDSA-N 0.000 description 1
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- UHKIGXVNMXYBOP-UHFFFAOYSA-M 1-ethenyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].C[N+]=1C=CN(C=C)C=1 UHKIGXVNMXYBOP-UHFFFAOYSA-M 0.000 description 1
- BZVFPIHTRLNAQA-UHFFFAOYSA-M 1-ethenyl-3-methylimidazol-3-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C[N+]=1C=CN(C=C)C=1 BZVFPIHTRLNAQA-UHFFFAOYSA-M 0.000 description 1
- LLLWMXQKXWIRDZ-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one Chemical compound C=CN1CCCC1=O.C=CN1CCCC1=O LLLWMXQKXWIRDZ-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-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
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-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
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- IXMRJEXTYQCAHH-UHFFFAOYSA-N C=CN1CCCCC1=O.C=CN1CCCCC1=O Chemical compound C=CN1CCCCC1=O.C=CN1CCCCC1=O IXMRJEXTYQCAHH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- 239000004609 Impact Modifier Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000289 Polyquaternium Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000007599 discharging 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
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- MEYPYIROLGQIED-UHFFFAOYSA-N n-[12-(dimethylamino)dodecyl]-2-methylprop-2-enamide Chemical compound CN(C)CCCCCCCCCCCCNC(=O)C(C)=C MEYPYIROLGQIED-UHFFFAOYSA-N 0.000 description 1
- VNLHOYZHPQDOMS-UHFFFAOYSA-N n-[3-(diethylamino)propyl]-2-methylprop-2-enamide Chemical compound CCN(CC)CCCNC(=O)C(C)=C VNLHOYZHPQDOMS-UHFFFAOYSA-N 0.000 description 1
- GFOCCLOYMMHTIU-UHFFFAOYSA-N n-[3-(diethylamino)propyl]prop-2-enamide Chemical compound CCN(CC)CCCNC(=O)C=C GFOCCLOYMMHTIU-UHFFFAOYSA-N 0.000 description 1
- BPTMGBPQYPVHCN-UHFFFAOYSA-N n-[3-(dimethylamino)butyl]-2-methylprop-2-enamide Chemical compound CN(C)C(C)CCNC(=O)C(C)=C BPTMGBPQYPVHCN-UHFFFAOYSA-N 0.000 description 1
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- HOZLHJIPBBRFGM-UHFFFAOYSA-N n-dodecyl-2-methylprop-2-enamide Chemical compound CCCCCCCCCCCCNC(=O)C(C)=C HOZLHJIPBBRFGM-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- CNWVYEGPPMQTKA-UHFFFAOYSA-N n-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C=C CNWVYEGPPMQTKA-UHFFFAOYSA-N 0.000 description 1
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000765 poly(2-oxazolines) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
-
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2839/00—Use of polymers with unsaturated aliphatic radicals and with a nitrogen or a heterocyclic ring containing nitrogen in a side chain or derivatives thereof, as mould material
- B29K2839/06—Polymers of N-vinyl-pyrrolidones
-
- 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
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
(A)式(I):
nは、3〜12であり;
mは、0〜3であり;
R1は、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R2、R3およびR4は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第1のモノマー;および
(B)式(II):
R5、R6およびR7は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R8は、C1〜C20−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第2のモノマー
を含むポリマーの、熱溶解フィラメント製法における支持体材料としての使用により解決される。
i)層ベースの付加技術を用いてビルドチャンバに支持体材料を堆積させることにより、支持体構造を形成するステップ、
ii)層ベースの付加技術を用いて前記ビルドチャンバに造形材料を堆積させることにより、3次元物体を形成するステップ、その際、前記3次元物体は、前記支持体構造により支持される少なくとも1つの領域を含むものとする、および
iii)水溶液を用いて、前記3次元物体から前記支持体構造を除去するステップ
を含む、熱溶解フィラメント製法による3次元物体の製造方法において、前記支持体材料が、重合単位(A)および(B):
(A)式(I):
nは、3〜12であり;
mは、0〜3であり;
R1は、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R2、R3およびR4は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第1のモノマー;および
(B)式(II):
R5、R6およびR7は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R8は、C1〜C20−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第2のモノマー
を含むポリマーを含む前記方法である。
造形材料としては、総じて、熱可塑性ポリマーを含む熱可塑性材料が使用される。従って、押出しが可能なあらゆる熱可塑性材料を使用することができる。
本発明によれば、重合単位(A)および(B)を含むポリマーを含む支持体材料が使用される。
(A)式(I):
nは、3〜12であり;
mは、0〜3であり;
R1は、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R2、R3およびR4は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第1のモノマー;および
(B)式(II):
R5、R6およびR7は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R8は、C1〜C20−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第2のモノマー
を含むポリマー、および少なくとも1種のホモポリマーの、熱溶解フィラメント製法における支持体材料としての使用である。
本発明の目的のための「第1のモノマー」という用語と「成分(A)」という用語とは同義であり、本発明全体を通じて互換的に用いられる。
本発明の目的のための「第2のモノマー」という用語と「成分(B)」という用語とは同義であり、本発明全体を通じて互換的に用いられる。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、および
ビニルアセテートからなる重合単位(B)80〜20質量%
を含む。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%、および
N−ビニルカプロラクタムからなる重合単位(C)1〜10質量%
を含む。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%、および
式(III)
R9は、C3〜C20−アルキルであり、好ましくはC4〜C15−アルキルであり、特にC8〜C12−アルキルである]
の少なくとも1種のモノビニルエステルからなる重合単位(C)1〜10質量%
を含む。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%、および
式(III)
R9は、C3〜C20−アルキルである]
の少なくとも1種のモノビニルエステルからなる重合単位(C)1〜10質量%
を含む。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%、および
式(III)
R9は、C3〜C20−アルキルであり、好ましくはC4〜C15−アルキルであり、特にC8〜C12−アルキルである]
の1種のモノビニルエステルからなる重合単位(C)1〜10質量%
を含む。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%
からなる。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%、および
N−ビニルカプロラクタムからなる重合単位(C)1〜10質量%
からなる。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%、および
式(III)
R9は、C3〜C20−アルキルであり、好ましくはC4〜C15−アルキルであり、特にC8〜C12−アルキルである]
の少なくとも1種のモノビニルエステルからなる重合単位(C)1〜10質量%
からなる。
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%、および
式(III)
R9は、C3〜C20−アルキルであり、好ましくはC4〜C15−アルキルであり、特にC8〜C12−アルキルである]
の1種のモノビニルエステルからなる重合単位(C)1〜10質量%
からなる。
造形材料、支持体材料、並びに重合単位(A)、(B)および任意に(C)を含むポリマーに関して上述した実施形態および優先物は、3次元物体の製造方法にも同様に該当する。
比較例1(C1):アクリル系コポリマー;Stratasysより入手した商品名P400 SR
比較例(C2):N−ビニルピロリドンK30ホモポリマー
比較例(C3):N−ビニルピロリドンK90ホモポリマー
本発明の実施例(E4):N−ビニルピロリドンおよびビニルアセテートの重合単位を含むコポリマー
本発明の実施例(E5):N−ビニルピロリドン、ビニルアセテートおよびC4〜C20−モノカルボン酸のモノビニルエステルの重合単位を含むコポリマー
重量平均分子量(Mw)を、ポリメチルメタクリレート標準物質(PSS Polymer standards services GmbH)を用いたゲル浸透クロマトグラフィーにより測定した。この測定を、ヘキサフルオロイソプロパノール(0.05質量%のトリフルオロ酢酸のナトリウム塩を含有するHFIP)を用いて40℃の炉温度で行った。HFIP−LGガードカラムを、2つのHFIPゲルカラム(内径7.5mm、長さ30cm)(Polymer Laboratories Ltd.)と組み合わせてRI検出器と共に使用した。
バッファ処理したポリマーをDSMミニエクストルーダーで加工した後に、寸法(10×4×8mm)のノッチなしシャルピーバーを導入した。このポリマーを、2回、それぞれ80rpmのスクリュー速度を用いて2分間押出した。これらは、ISO 178:2010試験を用いた曲げ弾性率並びに曲げ引張破断時の応力および伸びを測定するための試験片として用いたバーであった。曲げ速度を2mm/分に設定した。この試験を室温(23℃)で行った。
Claims (13)
- 重合単位(A)および(B):
(A)式(I):
nは、3〜12であり;
mは、0〜3であり;
R1は、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R2、R3およびR4は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第1のモノマー;および
(B)式(II):
R5、R6およびR7は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R8は、C1〜C20−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第2のモノマー
を含むポリマーの、熱溶解フィラメント製法における支持体材料としての使用であって、
前記ポリマーが、該ポリマーの総質量を基準として、重合単位(A)20〜80質量%および重合単位(B)80〜20質量%を含む、前記使用。 - 重合単位(A)が、N−ビニルピロリドン、N−ビニルピペリドンおよびN−ビニルカプロラクタムからなる群から選択される少なくとも1種のモノマーを含む、請求項1に記載の使用。
- 重合単位(A)が、成分(A)の総質量を基準として、N−ビニルピロリドンを少なくとも80質量%含み、かつ、N−ビニルピロリドン以外の式(I)の少なくとも1種のモノマーを0〜20質量%含む、請求項1または2に記載の使用。
- 重合単位(A)が、成分(A)の総質量を基準として、N−ビニルピロリドンを少なくとも80質量%含み、かつN−ビニルカプロラクタムを0〜20質量%含む、請求項1〜3のいずれかに記載の使用。
- 重合単位(B)が、成分(B)の総質量を基準として、ビニルアセテートを少なくとも80質量%含み、かつ、N−ビニルアセテート以外の式(II)の少なくとも1種のモノマーを0〜20質量%含む、請求項1〜4のいずれかに記載の使用。
- 重合単位(B)が、成分(B)の総質量を基準として、ビニルアセテートを少なくとも80質量%含み、かつ、C4〜C20−モノカルボン酸の少なくとも1種のモノビニルエステルを0〜20質量%含む、請求項1〜5のいずれかに記載の使用。
- ポリマーが、30〜1000kg/モルの範囲内の重量平均分子量(Mw)を有する、請求項1〜6のいずれかに記載の使用。
- ポリマーが、40〜200℃の範囲内のガラス転移温度を有する、請求項1〜7のいずれかに記載の使用。
- ポリマーの粘度が、10rad/sのせん断速度で240℃で測定して、1〜10000Pa・sの範囲内である、請求項1〜8のいずれかに記載の使用。
- ポリマーが、該ポリマーの総質量を基準として、
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、および
ビニルアセテートからなる重合単位(B)80〜20質量%
を含む、請求項1〜9のいずれかに記載の使用。 - ポリマーが、該ポリマーの総質量を基準として、
N−ビニルピロリドンからなる重合単位(A)20〜80質量%、
ビニルアセテートからなる重合単位(B)80〜20質量%、および
N−ビニルカプロラクタムからなる重合単位(C)1〜10質量%
を含む、請求項1〜10のいずれかに記載の使用。 - 以下:
i)層ベースの付加技術を用いてビルドチャンバに支持体材料を堆積させることにより、支持体構造を形成するステップ、
ii)層ベースの付加技術を用いて前記ビルドチャンバに造形材料を堆積させることにより、3次元物体を形成するステップ、その際、前記3次元物体は、前記支持体構造により支持される少なくとも1つの領域を含むものとする、および
iii)水溶液を用いて、前記3次元物体から前記支持体構造を除去するステップ
を含む、熱溶解フィラメント製法による3次元物体の製造方法において、前記支持体材料が、重合単位(A)および(B):
(A)式(I):
nは、3〜12であり;
mは、0〜3であり;
R1は、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R2、R3およびR4は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第1のモノマー;および
(B)式(II):
R5、R6およびR7は、互いに独立してそれぞれ、水素、C1〜C10−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルであり;
R8は、C1〜C20−アルキル、C2〜C10−アルケニル、アリールまたはアラルキルである]
の少なくとも1種の第2のモノマー
を含むポリマーを含み、前記ポリマーが、該ポリマーの総質量を基準として、重合単位(A)20〜80質量%および重合単位(B)80〜20質量%を含む、前記方法。
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CN113529207B (zh) | 2015-07-14 | 2024-04-12 | 巴斯夫欧洲公司 | 基于涂覆芯材料的纤丝 |
US11045997B2 (en) * | 2015-12-24 | 2021-06-29 | Stratasys, Inc. | Water soluble support materials for high temperature additive manufacturing applications |
WO2017112689A1 (en) | 2015-12-24 | 2017-06-29 | Stratasys, Inc. | Water soluble support materials for high temperature additive manufacturing applications |
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