JP6897987B2 - 溶融フィラメント印刷 - Google Patents
溶融フィラメント印刷 Download PDFInfo
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- JP6897987B2 JP6897987B2 JP2018546475A JP2018546475A JP6897987B2 JP 6897987 B2 JP6897987 B2 JP 6897987B2 JP 2018546475 A JP2018546475 A JP 2018546475A JP 2018546475 A JP2018546475 A JP 2018546475A JP 6897987 B2 JP6897987 B2 JP 6897987B2
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- 239000000178 monomer Substances 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 26
- 125000004122 cyclic group Chemical group 0.000 claims description 22
- 239000004952 Polyamide Substances 0.000 claims description 15
- 229920002647 polyamide Polymers 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 10
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical group CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 150000001413 amino acids Chemical class 0.000 claims description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 7
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005700 Putrescine Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- XBZSBBLNHFMTEB-WDSKDSINSA-N (1s,3s)-cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)[C@H]1CCC[C@H](C(O)=O)C1 XBZSBBLNHFMTEB-WDSKDSINSA-N 0.000 claims description 3
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 claims description 3
- LKJKDWUEGGOHFB-UHFFFAOYSA-N 4-tert-butylbenzene-1,3-dicarboxylic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1C(O)=O LKJKDWUEGGOHFB-UHFFFAOYSA-N 0.000 claims description 3
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 claims description 3
- 235000010300 dimethyl dicarbonate Nutrition 0.000 claims description 3
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVTZUVMKKRFSCC-UHFFFAOYSA-N cyclohexanamine;methane Chemical compound C.NC1CCCCC1.NC1CCCCC1 QVTZUVMKKRFSCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- BDBZTOMUANOKRT-UHFFFAOYSA-N 4-[2-(4-aminocyclohexyl)propan-2-yl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1C(C)(C)C1CCC(N)CC1 BDBZTOMUANOKRT-UHFFFAOYSA-N 0.000 claims 1
- KEUCYUPOICDBOG-UHFFFAOYSA-N [2-(aminomethyl)-5-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1C2C(CN)CC1C(CN)C2 KEUCYUPOICDBOG-UHFFFAOYSA-N 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 238000002474 experimental method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 229920001519 homopolymer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 229920006017 homo-polyamide Polymers 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012768 molten material Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229960000250 adipic acid Drugs 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 229920006020 amorphous polyamide Polymers 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- JINGUCXQUOKWKH-UHFFFAOYSA-N 2-aminodecanoic acid Chemical compound CCCCCCCCC(N)C(O)=O JINGUCXQUOKWKH-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HJOVHMDZYOCNQW-UHFFFAOYSA-N Isophorone Natural products CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 1
- -1 isophorone diamines Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- 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
- B29C64/10—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
- B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/205—Means for applying layers
- B29C64/209—Heads; Nozzles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/004—Semi-crystalline
-
- 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
- B33Y80/00—Products made by additive manufacturing
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- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Wood Science & Technology (AREA)
- Polyamides (AREA)
Description
a)i.アミノ酸A、または
ii.ジアミンBおよび二塩基酸C
に由来する少なくとも70重量%の脂肪族モノマー単位と、
b)環状モノマーに由来する少なくとも0.5重量%のさらなるモノマー単位と
を含み、重量百分率(重量%)は半結晶質コポリアミドの総重量を基準とする、方法によって達成された。
・アミノ酸A、または
・ジアミンBおよび二塩基酸C
に由来するモノマー単位からなるポリアミドであると理解される。
−HN(CH2)5CO− (1)
−HN(CH2)6NHCO(CH2)4CO− (2)
ii.ジアミンBおよび二塩基酸C
に由来する少なくとも70重量%の脂肪族モノマー単位は、広範囲の脂肪族モノマー単位から選択され得る。
−ポリマー組成物のフィラメントを、そのようなフィラメントのコイル、スプールまたはボビンから、押出ノズルを有するプリントヘッドに供給し、
−フィラメントを、制御された速度でプリントヘッド内に押し込み、
−プリントヘッドを加熱して、フィラメントを溶融させ、
−次いで、次第に大きくなる造形部品の始まりを構成する基盤上の最初の層および次第に大きくなる造形部品上のさらなる層について、プリントヘッドの押出ノズルにより、溶融フィラメントを堆積させる。
−堆積後、ポリマー組成物は冷却および固化し、それにより3次元物体を形成する。
−粒質材料を、押出ノズルを有する押出ヘッドを含む溶融押出装置に供給する工程、
−粒質材料を溶融押出装置中で溶融させ、制御された速度で押出ヘッドに供給する工程、
−溶融材料を押出ノズルを通して押出し、それにより溶融フィラメントを形成する工程、
−次いで、次第に大きくなる造形部品の始まりを構成する基盤上の最初の層および次第に大きくなる造形部品上のさらなる層について、プリントヘッドの押出ノズルにより、溶融フィラメントを堆積させる工程
を含み、
−堆積後、ポリマー組成物は冷却および固化し、それにより3次元物体を形成する。
[使用材料]
PA12;Stratasys FDM Nylon 12(商標)(Eden Priairie,US)におけるデータシートからの製品データ
PA−6ホモポリマー;粘度数220。
PA−6コポリマー:1重量%のIPDTが存在するPA−6/IPDT;粘度数220。
PA−6I/6T;I/Tが7/3である非晶質コポリアミド;粘度数40。
PA−6/66コポリマー
PA12については、Stratasys FDM Nylon 12(商標)(Eden Priairie,US)のデータシート中の値を使用した。ここでは、しばしば「オンエッジ」(ZX)方位と称される、Xが試験片の長さ方向、Yが厚さ方向、Zが幅方向とそれぞれ一致するところの、水平面(XY)に印刷することによって試験片を調製した。引張特性は、XZ方向で測定した。すなわち、試験方向は、印刷方向である。データを表1に記載する。
1.75mmの直径を有するPA−6ホモポリマーのフィラメントを、MaukCC(Maastricht,The Netherlands)により製造されたCartesio 3Dプリンタを用いてISO527BA形の引張試験体へと印刷した。そのようなプリンタの概略図を図1に示す。炉の温度は260℃、ノズルの直径は0.4mm、基盤温度は80℃であった。ノズルから出る押出物を1層ずつの様式で基盤上に堆積させた。軌道は、引張方向に対して交互する45°/−45°の角度を有し、図2に示すようなパターンを残す。
比較実験Bと同様であるが、今度は、80/20重量/重量%のPA6ホモポリマーおよびPA−6I/6Tのブレンドを、直径1.75mmのフィラメントへと押出し、同じ条件を用いて引張試験体へと印刷した。結果(3つの試験体の平均値)を表1にまとめる。
比較実験Bと同様であるが、今度は、1重量%のIPDTが存在するPA−6/IPDTコポリマーを使用した。結果(3つの試験体の平均値)を表1にまとめる。
[実施例II]
コポリマーPA−6/IPDTを10〜50mm/秒の範囲の様々な印刷速度で印刷することにより、伸長された五角形を有する単一外周物体を調製した。1.75mmの直径を有するコポリマーのフィラメントを、MaukCC(Maastricht,The Netherlands)により製造されたCartesio 3Dプリンタを用いて印刷した。炉の温度は260℃、ノズルの直径は0.4mm、基盤温度は80℃であった。ノズルから出る押出物を1層ずつの様式で基盤上に堆積させ、物体を垂直方向(z軸)に成長させた。印刷された物体から、小形引張試験片(ISO 527 1BA)を長さ方向(z軸)で打ち抜いた。よって、引張試験は、印刷方向に垂直なz方向で行った。結果を表2に示す。
PA−6/IPDTの代わりにPA−6ホモポリマーを使用した以外は実施例IIを繰り返した。溶融温度を260℃に設定した。結果を表2に示す。
PA−6/IPDTの代わりにPA−6/66コポリマーを使用した以外は実施例IIを繰り返した。溶融温度を240℃に設定した。より低速での印刷は順調に運び、より高速では問題を孕んでいた。40mm/秒以上の速度では、溶融層が常に互いの上に堆積されるわけではなかった。温度を上げることはいくらかの改善をもたらしたが、印刷された層が、次の層が堆積される前に流れ始めた。それゆえ、これらの速度での引張データは決定され得なかった。質的良好製品(30mm/秒まで)を試験した。結果を表2に示す。
Claims (11)
- 半結晶質コポリアミドを含有するポリマー組成物を3次元物体の一部の形状に従って選択的に計量配分する工程を含む溶融フィラメント製造により3次元物体を形成する方法であって、前記半結晶質コポリアミドは、
a)i.アミノ酸A、または
ii.ジアミンBおよび二塩基酸C
に由来する少なくとも70重量%の脂肪族モノマー単位と
b)環状モノマーに由来する少なくとも0.5重量%のさらなるモノマー単位と
を含むことを特徴とし、前記重量百分率(重量%)は前記半結晶質コポリアミドの総重量を基準とする、方法。 - 前記ポリマー組成物が少なくとも30重量%の半結晶質コポリアミドを含み、重量%は前記ポリマー組成物の総重量を基準とする、請求項1に記載の方法。
- 前記脂肪族モノマー単位が、ε−カプロラクタム、1,4−ジアミノブタンおよび1,10−デカン二酸、1,6−ジアミノヘキサンおよび1,6−ヘキサン二酸からなる群から選択されるモノマーに由来する、請求項1または2に記載の方法。
- 前記環状モノマーが、芳香族モノマー、または脂環式モノマー、またはそれらの組み合わせである、請求項1〜3のいずれか一項に記載の方法。
- 前記環状モノマーが、イソホロンジアミン(IPD)、シス−1,4−ジアミノシクロヘキサン、トランス−1,4−ジアミノシクロヘキサン、ビス−(p−アミノシクロヘキサン)メタン(PACM)、2,2−ジ−(4−アミノシクロへキシル)−プロパン、3,3’−ジメチル−4−4’−ジアミノジシクロへキシルメタン(DMDC)、p−キシリレンジアミン、m−キシリレンジアミン、3,6−ビス(アミノメチル)ノルボルナン、イソフタル酸(I)、テレフタル酸(T)、4−メチルイソフタル酸、4−tert−ブチルイソフタル酸、1,4−ナフタレンジカルボン酸および2,6−ナフタレンジカルボン酸、シス−1,4−シクロヘキサンジカルボン酸、トランス−1,4−シクロヘキサンジカルボン酸、シス−1,3−シクロヘキサンジカルボン酸およびトランス−1,3−シクロヘキサンジカルボン酸からなる群から選択される、請求項1〜4のいずれか一項に記載の方法。
- A、またはBおよびCに由来する前記脂肪族モノマー単位が、εカプロラクタム、1,4−ジアミノブタンおよび1,10−デカン二酸、1,6−ジアミノヘキサンおよび1,6−ヘキサン二酸からなるモノマーの群から選択され、環状モノマーに由来する前記さらなるモノマー単位が、イソホロンジアミン(IPD)、シス−1,4−ジアミノシクロヘキサン、トランス−1,4−ジアミノシクロヘキサン、ビス−(p−アミノシクロヘキサン)メタン(PACM)、2,2−ジ−(4−アミノシクロへキシル)−プロパン、3,3’−ジメチル−4−4’−ジアミノジシクロへキシルメタン(DMDC)、p−キシリレンジアミン、m−キシリレンジアミン、3,6−ビス(アミノメチル)ノルボルナン、イソフタル酸(I)、テレフタル酸(T)、4−メチルイソフタル酸、4−tert−ブチルイソフタル酸、1,4−ナフタレンジカルボン酸、2,6−ナフタレンジカルボン酸、シス−1,4−シクロヘキサンジカルボン酸、トランス−1,4−シクロヘキサンジカルボン酸、シス−1,3−シクロヘキサンジカルボン酸およびトランス−1,3−シクロヘキサンジカルボン酸からなるモノマーの群から選択される、請求項1〜5のいずれか一項に記載の方法。
- 印刷速度が少なくとも10mm/秒である、請求項1〜6のいずれか一項に記載の方法。
- 環状モノマーに由来する前記さらなるモノマー単位が、イソホロンジアミンおよびテレフタル酸を含む、請求項1〜7のいずれか一項に記載の方法。
- 前記フィラメントが、コイルから供給される、請求項1〜8のいずれか一項に記載の方法。
- 前記フィラメントが、前記ポリマー組成物を含む粒質材料の溶融押出により生成される、請求項1〜8のいずれか一項に記載の方法。
- 半結晶質コポリアミドを含有するポリマー組成物を含み、前記半結晶質コポリアミドは、
a)i.アミノ酸A、または
ii.ジアミンBおよび二塩基酸C
に由来する少なくとも70重量%の脂肪族モノマー単位と
b)環状モノマーに由来する少なくとも0.5重量%のさらなるモノマー単位と
を含むことを特徴とし、前記重量百分率(重量%)は前記半結晶質コポリアミドの総重量を基準とし、1〜3.5mmの間の直径を有するフィラメント。
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