JP6974673B2 - 3dプリンティング用の寸法安定アクリルアロイ - Google Patents
3dプリンティング用の寸法安定アクリルアロイ Download PDFInfo
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- JP6974673B2 JP6974673B2 JP2019515771A JP2019515771A JP6974673B2 JP 6974673 B2 JP6974673 B2 JP 6974673B2 JP 2019515771 A JP2019515771 A JP 2019515771A JP 2019515771 A JP2019515771 A JP 2019515771A JP 6974673 B2 JP6974673 B2 JP 6974673B2
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- acrylic
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- acrylate
- acrylic alloy
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 105
- 229910045601 alloy Inorganic materials 0.000 title claims description 73
- 239000000956 alloy Substances 0.000 title claims description 73
- 238000010146 3D printing Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims description 120
- 229920000642 polymer Polymers 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 46
- 229920000058 polyacrylate Polymers 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 41
- 238000001125 extrusion Methods 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 20
- 239000004626 polylactic acid Substances 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 17
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- -1 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
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- 238000007639 printing Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
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- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
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- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
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- 229920000623 Cellulose acetate phthalate Polymers 0.000 claims description 3
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- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
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- 229940081734 cellulose acetate phthalate Drugs 0.000 claims description 3
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- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 239000007850 fluorescent dye Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002121 nanofiber Substances 0.000 claims description 3
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920006260 polyaryletherketone Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000010420 shell particle Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
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- 238000000748 compression moulding Methods 0.000 claims description 2
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- 239000012802 nanoclay Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000004609 Impact Modifier Substances 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 27
- 239000000178 monomer Substances 0.000 description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 150000002736 metal compounds Chemical class 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
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- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
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- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YOTGRUGZMVCBLS-UHFFFAOYSA-N pentadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C(C)=C YOTGRUGZMVCBLS-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 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
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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Description
A.ポリマーマトリックスブレンド
を含み、
このポリマーマトリックスブレンドは、
1)1種以上のアクリルポリマー(このアクリルポリマーは、50,000〜300,000g/モル、好ましくは75,000〜150,000g/モルの重量平均分子量を有し、500,000g/モル以上の分子量を有するものが5%未満であるものとする)、
2)5〜60重量%、好ましくは9〜40重量%の、1種以上の低粘度ポリマー(この低粘度ポリマーは、前記アクリルポリマーと適合性、半混和性又は混和性であり、ASTM法D1238によって230℃/10.4kg力において測定した時に10g/10分超、好ましくは25g/10分超のメルトフロー速度を有するものとする)、
c)随意としての、0〜60重量%、好ましくは9〜40重量%の、耐衝撃性改良剤
を含み、
前記アクリル組成物は、ASTM法C965に従って回転粘度計によって測定して、230℃の温度において100,000Pa・秒未満、好ましくは10,000Pa・秒未満、より一層好ましくは50〜1,000Pa・秒の1秒-1の剪断における粘度を有し、且つ、100秒-1の剪断速度において230℃の温度で20〜2,000Pa・sの粘度を有する。
(1)優れた光学明澄性。
本発明の透明アクリルアロイ組成物から形成させた厚さ2mmの圧縮成形プラックは、ASTM法D1003に従って測定した時に、80%超、好ましくは90%超、特に好ましくは92%超のトータル白色光透過度を有し、曇り度は10%未満、好ましくは4%未満である。
(2)引張破断点伸び:本発明の組成物は、ASTM法D638によって測定した時に、10%超、好ましくは20%超の引張伸びを有する。
(3)次の反り試験を用いて測定した時に反りがほとんど又は全くなし:材料のビカット温度に加熱されたガラスベースプレート上にノズルを2回通過させることによって、高さ約1cm、長さ約2cm〜20cmの様々な薄い壁をプリントする。プリントされた材料を側部から見て、ベースプレートから剥離した度合いに基づいて、反りの度合いを質的に観察した(例3の説明を見よ)。反りは、部品が溶融押出プリンターのベースプレートに接着する能力に関連し、これはプリンティングを成功させるために必要である。
(4)降伏応力:ASTM法D638によって測定した時に30MPa超、より一層好ましくは35MPa超の降伏応力。
(5)充填密度:本発明のアクリルアロイ組成物を用いて押出積層造形された物品は、プリントされた部分の密度を材料のバルク密度で割ることによって計算した時に、85%超、好ましくは90%超、特に好ましくは95%超の充填密度を有する。
(6)プリント物品明澄性:前記アクリルアロイ組成物を用いて押出積層造形された物品(プリントされた物品が10層を有し、各層が0.4mmのライン幅を有するもの)は、ASTM法D1003を用いて厚さ2.1mmのサンプルに対して測定した時に、50%超、好ましくは60%超、より一層好ましくは65%超の透過度を有する。
1.材料押出積層造形に用いるためのアクリルアロイ組成物であって、
該アクリル組成物が、
A.ポリマーマトリックスブレンドを含み、
このポリマーマトリックスブレンドが、
1)50,000〜300,000g/モル、好ましくは75,000〜150,000g/モルの重量平均分子量を有する1種以上のアクリルポリマー;
2)5〜60重量%、好ましくは9〜40重量%の、前記アクリルポリマーと適合性、半混和性又は混和性である1種以上の低粘度ポリマー(この低粘度ポリマーは、ASTM法D1238によって230℃/10.4kg力において測定した時に10g/10分超、好ましくは25g/10分超のメルトフロー速度を有する);
c)随意としての、0〜60重量%、好ましくは9〜40重量%の、耐衝撃性改良剤:
を含み、
ここで、該アクリル組成物が、ASTM法C965に従って回転粘度計によって測定して、230℃の温度において100,000Pa・秒未満、好ましくは10,000Pa・秒未満、より一層好ましくは50〜1,000Pa・秒の1秒-1の剪断における粘度を有し、且つ、100秒-1の剪断速度において230℃の温度で20〜2,000Pa・s、好ましくは25〜1,000Pa・s、より一層好ましくは30〜500Pa・sの粘度を有する、前記組成物。
2.前記アクリルポリマーが500,000g/モル超の重量平均分子量を有するポリマーを5重量%未満、好ましくは2重量%未満含有する、局面1のアクリル組成物。
3.2種以上の異なるアクリルポリマーを含む、局面1又は2のアクリル組成物。
4.前記ポリマーマトリックスブレンドがA1)の50,000〜300,000g/モルの重量平均分子量を有するアクリルポリマーを1種含み、第2のアクリルポリマーが低粘度ポリマーA2)である、局面1〜3のいずれかのアクリル組成物。
5.前記アクリルポリマーがメタクリル酸メチルモノマー単位を少なくとも60重量%、好ましくは70〜99.5重量%含む、局面1〜4のいずれかのアクリル組成物。
6.前記低粘度ポリマーが50,000未満の重量平均分子量を有する低分子量アクリルポリマーである、局面1〜5のいずれかのアクリル組成物。
7.前記低粘度ポリマーがアクリルポリマーではなく、ポリエステル、セルロースエステル、ポリエチレンオキシド、ポリプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、スチレン−アクリロニトリルコポリマー、ポリ塩化ビニル、ポリ酢酸ビニル、ポリビニルアルコール、エチレン−酢酸ビニルコポリマー、オレフィン−アクリレートコポリマー、オレフィン−アクリレート−無水マレイン酸コポリマー、ポリフッ化ビニリデン及び無水マレイン酸−スチレン−酢酸ビニルコポリマーより成る群から選択される、局面1〜6のいずれかのアクリル組成物。
8.前記ポリエステルがポリ(ブチレンテレフタレート)、ポリ(エチレンテレフタレート)ポリエチレンテレフタレートグリコール及びポリ乳酸より成る群から選択される、 局面7のアクリル組成物。
9.前記低粘度ポリマーがポリ乳酸である、局面1〜8のいずれかのアクリル組成物。
10.前記セルロースエステルがセルロースアセテート、セルローストリアセテート、セルロースプロピオネート、セルロースアセテートプロピオネート、セルロースアセテートブチレート及びセルロースアセテートフタレートより成る群から選択される、局面7のアクリル組成物。
11.前記耐衝撃性改良剤がハードコア型コア−シェル耐衝撃性改良剤である、局面1〜10のいずれかのアクリル組成物。
12.該組成物が透明であり、該組成物から圧縮成形によって成形した厚さ2mmのプラックが、ASTM法D1003に従って測定した時に、80%超、好ましくは90%超、特に好ましくは92%超のトータル白色光透過度を、10%未満、好ましくは4%未満の曇り度と共に有する、局面1〜11のいずれかのアクリル組成物。
13.前記耐衝撃性改良剤がアクリルマトリックスポリマーと屈折率整合し、前記コア−シェル粒子の屈折率がマトリックスポリマーアロイの0.03単位以内、好ましくは0.02単位以内である、局面1〜12のいずれかのアクリル組成物。
14.該組成物が粉体、ペレット又はフィラメントの形にある、局面1〜13のいずれかのアクリル組成物。
15.フィラー、炭素繊維、ミルド炭素繊維、カーボンパウダー、カーボンナノチューブ、ガラスビーズ、ガラス繊維、ナノシリカ、クレー、ナノクレー、アラミド繊維、ポリアリールエーテルケトン繊維、BaSO4、タルク、CaCO3、グラフェン、ミルド炭素繊維、ナノファイバー、中空球体、染料、着色剤、金属粒子、金属フレーク、乳白光染料、蛍光染料及びそれらの混合物より成る群から選択される1種以上の添加剤をさらに含む、局面1〜14のいずれかのアクリル組成物。
16.局面1〜15のいずれかのアクリルアロイ組成物を用いて材料押出積層造形法によって製造されたアクリル物品。
17.次の特性:
a)ASTM法D638によって測定して10%超、好ましくは20%超の引張伸び、
b)85%超、好ましくは90%超、特に好ましくは95%超の充填密度、
c)ASTM法D638によって測定した時に35MPa超の降伏時応力、
d)ASTM法D1003を用いて厚さ2.1mmのサンプルに対して測定した時に、50%超、好ましくは60%超、より一層好ましくは65%超の光透過度
の内の1つ以上を有する、局面16の物品。
18.局面1〜15のいずれかの組成物を含む3Dプリンティング用フィラメントであって、10フィートの長さの間での直径の変化が±5%未満である、前記フィラメント。
19.前記フィラメントが同時押出された多相フィラメントである、局面18のフィラメント。
20.前記多相フィラメントが視覚的特殊効果を提供する1種以上の添加剤を含む、局面18又は19のフィラメント。
21.押出積層(3D)アクリル製品を形成させる方法であって、
・3Dプリンターのソフトウェアを、前記物品のプリンティングのための設定体積流量およびライン間隔にプリセットする工程;
・局面1〜15のいずれかのアクリルアロイ組成物をフィラメント、ペレット又は粉体の形で前記3Dプリンターに供給する工程;
・前記プリンターによる前記アクリル組成物の溶融物を加熱ノズルに供給する工程;
・前記アクリル組成物溶融物を、前記ソフトウェアにより設定されたライン間隔および流量で設定位置に堆積させて、物品を形成させる工程:
を含む、前記方法。
22.前記流量及び/又はライン間隔が10〜20体積%の余剰を示す、局面21の方法。
23.前記ノズルを190℃〜250℃の範囲、好ましくは210℃〜240℃の範囲に加熱する、局面21又は22の方法。
Claims (21)
- 材料押出積層造形に用いるためのアクリルアロイ組成物であって、
該アクリルアロイ組成物が、
A.1)50,000〜300,000g/モルの重量平均分子量を有する1種以上のアクリルポリマー(ここで、重量平均分子量はGPCによって測定され、前記アクリルポリマーはメタクリル酸メチルモノマー単位を少なくとも60重量%含む);及び
2)9〜40重量%の、前記アクリルポリマーと適合性、半混和性又は混和性である1種以上の低粘度ポリマー(この低粘度ポリマーは、ASTM法D1238によって230℃/10.4kg力において測定した時に10g/10分を超えるメルトフロー速度を有する):
を含むポリマーマトリックスブレンド、並びに
B.随意としての、0〜60重量%の、耐衝撃性改良剤:
を含み、
ここで、該アクリルアロイ組成物が、ASTM法C965に従って回転粘度計によって測定して、230℃の温度において100,000Pa・秒未満の1秒-1の剪断における粘度を有し、且つ、100秒-1の剪断速度において230℃の温度で20〜2,000Pa・秒の粘度を有する、前記組成物。 - 前記アクリルポリマーが500,000g/モル超の重量平均分子量を有するポリマーを5重量%未満含有する、請求項1に記載のアクリルアロイ組成物。
- 2種以上の異なるアクリルポリマーを含む、請求項1に記載のアクリルアロイ組成物。
- 前記ポリマーマトリックスブレンドがA1)の50,000〜300,000g/モルの重量平均分子量を有するアクリルポリマーを1種含み、第2のアクリルポリマーが低粘度ポリマーA2)である、請求項3に記載のアクリルアロイ組成物。
- 前記低粘度ポリマーが50,000未満の重量平均分子量を有する低分子量アクリルポリマーである、請求項1に記載のアクリルアロイ組成物。
- 前記低粘度ポリマーがアクリルポリマーではなく、ポリエステル、セルロースエステル、ポリエチレンオキシド、ポリプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、スチレン−アクリロニトリルコポリマー、ポリ塩化ビニル、ポリ酢酸ビニル、ポリビニルアルコール、エチレン−酢酸ビニルコポリマー、オレフィン−アクリレートコポリマー、オレフィン−アクリレート−無水マレイン酸コポリマー、ポリフッ化ビニリデン及び無水マレイン酸−スチレン−酢酸ビニルコポリマーより成る群から選択される、請求項1に記載のアクリルアロイ組成物。
- 前記ポリエステルがポリ(ブチレンテレフタレート)、ポリ(エチレンテレフタレート)、ポリエチレンテレフタレートグリコール及びポリ乳酸より成る群から選択される、請求項6に記載のアクリルアロイ組成物。
- 前記低粘度ポリマーがポリ乳酸である、請求項7に記載のアクリルアロイ組成物。
- 前記セルロースエステルがセルロースアセテート、セルローストリアセテート、セルロースプロピオネート、セルロースアセテートプロピオネート、セルロースアセテートブチレート及びセルロースアセテートフタレートより成る群から選択される、請求項6に記載のアクリルアロイ組成物。
- 前記耐衝撃性改良剤がハードコア型コア−シェル耐衝撃性改良剤である、請求項1に記載のアクリルアロイ組成物。
- 該組成物が透明であり、該組成物から圧縮成形によって成形した厚さ2mmのプラックが、ASTM法D1003に従って測定した時に、80%超のトータル白色光透過度を、10%未満の曇り度と共に有する、請求項1に記載のアクリルアロイ組成物。
- 前記耐衝撃性改良剤がアクリルマトリックスポリマーと屈折率整合し、前記コア−シェル粒子の屈折率がマトリックスポリマーアロイの0.03単位以内である、請求項1に記載のアクリルアロイ組成物。
- 粉体、ペレット又はフィラメントの形にある、請求項1に記載のアクリルアロイ組成物。
- フィラー、炭素繊維、ミルド炭素繊維、カーボンパウダー、カーボンナノチューブ、ガラスビーズ、ガラス繊維、ナノシリカ、クレー、ナノクレー、アラミド繊維、ポリアリールエーテルケトン繊維、BaSO4、タルク、CaCO3、グラフェン、ナノファイバー、中空球体、染料、着色剤、顔料、金属粒子、金属フレーク、乳白光染料、蛍光染料及びそれらの混合物より成る群から選択される1種以上の添加剤をさらに含む、請求項1に記載のアクリルアロイ組成物。
- 請求項1〜14のいずれかに記載のアクリルアロイ組成物を用いて材料押出積層造形法によって製造されたアクリル物品。
- 次の特性:
a)ASTM法D638によって測定して10%超の引張伸び、
b)85%超の充填密度、
c)ASTM法D638によって測定した時に35MPa超の降伏応力、
d)ASTM法D1003を用いて厚さ2.1mmのサンプルに対して測定した時に、50%超の透過度
の内の1つ以上を有する、請求項15に記載の物品。 - 請求項1〜14のいずれかに記載の組成物を含む3Dプリンティング用フィラメントであって、10フィートの長さの間での直径の変化が±5%未満である、前記フィラメント。
- 同時押出された多相フィラメントである、請求項17に記載のフィラメント。
- 押出積層(3D)アクリル製品を形成させる方法であって、
・3Dプリンターのソフトウェアを、前記物品のプリンティングのための設定体積流量およびライン間隔にプリセットする工程;
・請求項1〜14のいずれかに記載のアクリルアロイ組成物をフィラメント、ペレット又は粉体の形で前記3Dプリンターに供給する工程;
・前記プリンターによる前記アクリルアロイ組成物の溶融物を加熱ノズルに供給する工程;
・前記アクリルアロイ組成物溶融物を、前記ソフトウェアにより設定されたライン間隔および流量で設定位置に堆積させて、物品を形成させる工程:
を含む、前記方法。 - 前記流量及び/又はライン間隔が1〜10%の余剰を示す、請求項19に記載の方法。
- 前記ノズルを190℃〜250℃の範囲に加熱する、請求項19に記載の方法。
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